Laminate, resin composition, display device, and information terminal

Abstract

An object of the present invention is to provide a laminate having a cured film which has high liquid repellency, facilitates selective coating of a wavelength-converting layer after being formed as a partition wall pattern, and has high adhesiveness to a side SiO2 of an upper layer or an inorganic film such as SiN.SOLUTION: The present invention is a laminate including a substrate and a cured film formed by curing a resin composition, wherein the cured film does not show a peak derived from a fluorine atom F1s in X-ray photoelectron spectroscopy (XPS) analysis of the upper surface of the cured film, and the upper surface of the cured film has a surface free energy of 10 mN / m or more and 29 mN / m or less.SELECTED DRAWING: Figure 9

Description

[Technical Field]

[0001] The present invention relates to a laminate having a substrate and a cured film, a resin composition, a display device, and an information terminal. [Background technology]

[0002] In recent years, to achieve a wider color gamut and higher contrast in displays, display devices have been proposed that use a blue light source for the backlight and convert colors using a color filter (wavelength conversion unit) filled with wavelength-converting phosphors and / or light-diffusing particles in each pixel separated by partitions (see, for example, Patent Document 1). A method has been proposed for forming the wavelength conversion unit by photolithography using a resin composition to form partitions, and then inkjet-applying wavelength-converting phosphor ink to the green and red pixels and light-diffusing particle ink to the blue pixels (see, for example, Patent Documents 2 and 3). To accurately apply each ink, it is necessary to prevent the ink from running onto the tops of the partitions during application, and therefore the tops of the partitions must be liquid-repellent to repel ink. Conversely, the interior of the pixels must be lyophilic so that the ink can be spread.

[0003] As a method for imparting liquid repellency to the top of the partition wall, a method of forming the partition wall using a resin composition containing a liquid repellent compound has been proposed. For example, in Patent Document 3, a resin composition containing a liquid repellent compound having a photopolymerizable group and a fluoroalkyl group is applied to a substrate, dried, and then photocured, thereby photocuring the liquid repellent compound on the film surface and imparting liquid repellency to the top of the partition wall.

[0004] In recent years, quantum dots, which are nano-sized inorganic particles, have been widely used as wavelength conversion phosphors due to the narrow half-width of their emission spectra (see, for example, Patent Documents 1 to 3). However, quantum dots have the drawback that their emission lifetime is easily deteriorated by the presence of moisture and oxygen. Therefore, after filling the pixel with ink containing quantum dots and curing it, it is necessary to form an inorganic film such as SiO2 or SiN as a protective film by a method such as sputtering. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2021-111681 [Patent Document 2] Japanese Patent Application Publication No. 2023-98817 [Patent Document 3] Japanese Patent Publication No. 2022-33154 Summary of the Invention [Problem to be solved by the invention]

[0006] The inventors, with reference to Patent Document 3, formed partition walls using a resin composition containing a liquid-repellent compound having a photopolymerizable group and a fluoroalkyl group, then formed a wavelength conversion layer by inkjet coating and photo-curing a wavelength-converting phosphor ink and a light-diffusing particle ink, and finally formed an SiO2 film as an inorganic protective film by sputtering, and evaluated the results. However, after forming the SiO2 film, they conducted a moist heat resistance test (temperature 85°C, humidity 85%) for 100 hours and a cross-cut tape peel test (<Adhesion to inorganic protective layer> test described below), and found that peeling occurred at the interface between the partition walls and the SiO2 film, indicating an issue with adhesion.

[0007] Therefore, an object of the present invention is to provide a laminate having a cured film that has high liquid repellency, that allows easy application of wavelength conversion layers after formation of a partition wall pattern, and that has high adhesion to an overlying inorganic film such as SiO or SiN. [Means for solving the problem]

[0008] As a result of extensive research, the inventors of the present invention have found that when the liquid-repellent compound cured in the film contains a fluorine atom-containing functional group such as a fluoroalkyl group, the adhesion to the overlying SiO2 or SiN film decreases. In other words, they have found that the desired cured film can be obtained by not containing fluorine atoms in the cured film and having low surface free energy.

[0009] That is, the object of the present invention is achieved by the following configuration. A laminate having a substrate and a cured film obtained by curing a resin composition, wherein the cured film exhibits no peak attributable to fluorine atoms F1s in X-ray photoelectron spectroscopy (XPS analysis) of the upper surface of the cured film, and the surface free energy of the upper surface of the cured film is 10 mN / m or more and 29 mN / m or less. A resin composition comprising (A) a polysiloxane and (D) a liquid-repellent compound. [Effects of the Invention]

[0010] The laminate of the present invention can provide a laminate having a cured film that has high liquid repellency, that can be easily coated with wavelength conversion layers after being formed as a partition wall pattern, and that has high adhesion to an overlying inorganic film such as SiO or SiN. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is a cross-sectional view showing one embodiment of a laminate of the present invention having a cured film. [Figure 2] FIG. 1 is a cross-sectional view showing one embodiment of a laminate of the present invention having partition walls patterned as a cured film. [Figure 3] A top-view microscope photograph of the state in which 1,6-hexanediol diacrylate was applied to the center of the cell using an inkjet printer, and the coating spread well throughout the cell. [Figure 4-1] A top-view microscope photograph showing that when a small amount of 1,6-hexanediol diacrylate is applied to the center of a cell by inkjet, it does not spread well throughout the cell. [Figure 4-2] A top-view microscope photograph showing that when a small amount of 1,6-hexanediol diacrylate is applied to the center of a cell by inkjet, it does not spread well throughout the cell. [Figure 4-3]A top-view microscope photograph showing that when a small amount of 1,6-hexanediol diacrylate is applied to the center of a cell by inkjet, it does not spread well throughout the cell. [Figure 5] A top-view microscope image of the state where "top liquid repellency is good" when 1,6-hexanediol diacrylate is excessively applied to the center of the cell by inkjet printing. [Figure 6] A top-view microscope image showing poor liquid repellency at the top when excessive 1,6-hexanediol diacrylate was applied to the center of the cell by inkjet printing. [Figure 7] FIG. 1 is a cross-sectional view showing one embodiment of a laminate of the present invention having partition walls and a wavelength conversion layer patterned as a cured film. [Figure 8] FIG. 1 is a cross-sectional view showing one embodiment of a laminate of the present invention having partition walls patterned as a cured film, a wavelength conversion layer, and an inorganic protective layer. [Figure 9] FIG. 1 is a cross-sectional view showing one embodiment of a laminate of the present invention having partition walls patterned as cured films, a wavelength conversion layer, an inorganic protective layer, and a color filter layer. [Figure 10] FIG. 1 is a cross-sectional view showing one embodiment of a laminate of the present invention having a partition wall patterned as a cured film, a wavelength conversion layer, and a light-emitting source selected from an organic EL cell, a mini LED cell, and a micro LED cell. [Figure 11] FIG. 1 is a cross-sectional view showing the configuration of a display device used for evaluating color mixing in Examples. [Figure 12] This is an example of an XPS analysis result in which no peaks due to the atom F1S were observed. [Figure 13] This is an example of an XPS analysis result in which a peak due to the atom F1S is observed. DETAILED DESCRIPTION OF THE INVENTION

[0012] The present invention will be described in more detail below. Preferred embodiments of the laminate, resin composition, display device, and information terminal of the present invention will be specifically described below, but the present invention is not limited to the following embodiments and can be practiced with various modifications depending on the purpose and application.

[0013] The laminate of the present invention is a laminate having a substrate and a cured film obtained by curing a resin composition, characterized in that in X-ray photoelectron spectroscopy (XPS analysis) of the upper surface of the cured film, no peak derived from fluorine atoms FlS is observed, and the surface free energy of the upper surface of the cured film is 10 mN / m or more and 29 mN / m or less.

[0014] The substrate in the laminate of the present invention refers to the underlying base material in the laminate of the present invention. Examples of the substrate include a glass substrate, a resin plate, a resin film, and a driving substrate such as a TFT or PCB. The material for the glass substrate is preferably alkali-free glass. The material for the resin plate and resin film is preferably polyester, (meth)acrylic polymer, transparent polyimide, polyether sulfone, etc. The thickness of the glass plate and resin plate is preferably 1 mm or less, and more preferably 0.8 mm or less. The material for the resin film is preferably polyethylene terephthalate, TAC (triacetyl cellulose), polyimide, cycloolefin polymer, polycarbonate, etc. The thickness of the resin film is preferably 100 μm or less.

[0015] When a driving substrate such as a TFT or PCB is used as the substrate, it is preferable to further have a light emitting source selected from an organic EL cell, a mini LED cell, and a micro LED cell, which will be described later, on the substrate.

[0016] The cured film in the laminate of the present invention is a cured film obtained by curing a resin composition, and refers to a film obtained by using a resin composition and curing it, for example, by heat and / or light.

[0017] 1 shows a cross-sectional view of one embodiment of the laminate of the present invention having a substrate and a cured film. A cured film 2 is provided on a base substrate 1.

[0018] Examples of the resin composition include a thermosetting resin composition that is cured by heat, a photocurable resin composition that is cured by light irradiation, a negative photosensitive resin composition that is cured by heat and light irradiation and can form a pattern by removing the exposed or unexposed areas in a development step described later, and a positive photosensitive resin composition that is cured mainly by heat and can form a pattern by removing the exposed areas in a development step described later. The resin composition preferably has the composition described below.

[0019] The method for forming the cured film in the laminate of the present invention can be selected from, for example, (i) a coating step in which a resin composition is applied to a substrate and dried to obtain a dry film, (ii) an exposure step in which the obtained dry film is irradiated with light, (iii) a development step in which a portion of the exposed dry film that is soluble in a developer is dissolved and removed, and (iv) a heating step in which the developed film is cured.

[0020] When the resin composition is a thermosetting resin composition, it is preferable to have at least (i) a coating step and (iv) a heating step. When the resin composition is a photocurable resin composition, it is preferable to have at least (i) a coating step and (ii) an exposure step. When the resin composition is a negative-type photosensitive resin composition, it is preferable to have at least (i) a coating step, (ii) an exposure step, (iii) a development step, and (iv) a heating step. When the resin composition is a positive-type photosensitive resin composition and no pattern is to be formed, it is preferable to have at least (i) a coating step, (iii) a development step, (ii) an exposure step, and (iv) a heating step in this order. When a pattern is to be formed, it is preferable to have at least (i) a coating step, (ii) an exposure step, (iii) a development step, and (iv) a heating step in this order.

[0021] (i) Examples of the coating method in the coating step include slit coating and spin coating. (i) Examples of the drying method in the coating step include using a drying device such as an oven or a hot plate. The atmosphere of the drying device is not particularly limited, and examples include nitrogen and air. The drying temperature is preferably 80 to 120°C, and the drying time is preferably 1 to 60 minutes.

[0022] (ii) Examples of exposure equipment used in the exposure step include proximity exposure equipment and reduced projection exposure equipment. (ii) Examples of actinic rays irradiated in the exposure step include near-infrared rays, visible light, and ultraviolet rays, with ultraviolet rays being preferred. Among ultraviolet rays, it is more preferable to use a wavelength selected from i-rays with a wavelength of 365 nm, h-rays with a wavelength of 405 nm, and g-rays with a wavelength of 436 nm, and it is even more preferable to use a mixed wavelength of i-rays, h-rays, and g-rays. Furthermore, examples of light sources include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, halogen lamps, and germicidal lamps, with high-pressure mercury lamps and ultra-high-pressure mercury lamps being preferred. Exposure conditions can be appropriately selected depending on the thickness of the dried film to be exposed. Generally, 1 to 100 mW / cm 2 Using an ultra-high pressure mercury lamp with an output of 1 to 10,000 mJ / cm 2 In the (ii) exposure step, in order to form a pattern such as a partition wall, which will be described later, exposure may be performed through a photomask having predetermined openings, or any desired pattern may be directly written using laser light or the like without using a photomask.

[0023] (iii) Examples of the developing method in the developing step include immersion, spraying, and brushing. The developer used can be selected from solvents capable of dissolving unnecessary portions of the exposed film, and an aqueous solution containing water as the main component is preferred. Examples of the developer include inorganic alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, and calcium hydroxide; and organic alkaline aqueous solutions such as tetramethylammonium hydroxide and trimethylbenzylammonium hydroxide. Among these, an aqueous potassium hydroxide solution or an aqueous tetramethylammonium hydroxide solution is preferred from the viewpoint of improving resolution. The concentration of the aqueous alkaline solution is preferably 0.01% by weight or more, more preferably 0.03% by weight or more, from the viewpoint of improving developability. On the other hand, the concentration of the aqueous alkaline solution is preferably 5% by weight or less, more preferably 1% by weight or less, from the viewpoint of suppressing peeling or corrosion of the pattern before heating. Furthermore, a surfactant may be contained in the developer from the viewpoint of improving resolution. The development temperature is preferably 20 to 50°C to facilitate process control.

[0024] (iv) Examples of the heating device used in the heating step include an oven, a hot plate, etc. The atmosphere of the heating device is not particularly limited, and examples include nitrogen, air, etc. The heating temperature is preferably 80 to 250°C, and the drying time is preferably 1 to 60 minutes.

[0025] The cured film in the laminate of the present invention is characterized in that, in X-ray photoelectron spectroscopy (XPS analysis) of the upper surface of the cured film, no peak derived from fluorine atoms F1S is observed, and the surface free energy of the upper surface of the cured film is 10 mN / m or more and 29 mN / m or less.

[0026] XPS analysis can be performed as described in the Examples below. In XPS analysis of the upper surface of the cured film, "no peak due to fluorine atom F1S is observed" means that no peak is observed at 691 eV, below the detection limit of the measuring device. The absence of a peak due to fluorine atom F1S can ensure high adhesion to an overlying inorganic film such as SiO2 or SiN.

[0027] The surface free energy of the upper surface of the cured film in the laminate of the present invention is 10 mN / m or more, preferably 11 mN / m or more, and more preferably 12 mN / m or more. The surface free energy of the upper surface of the cured film is 29 mN / m or more, preferably 28 mN / m or less, more preferably 25 mN / m or less, and even more preferably 23 mN / m or less. By setting the surface free energy within this range, when the wavelength-converting phosphor ink and the light-diffusing particle ink are inkjet-coated after forming the partition wall pattern described below, the inks can be applied smoothly and separately without running onto the tops of the partition walls.

[0028] As described in the Examples below, the surface free energy can be calculated by measuring the contact angles of water and diiodomethane on the cured film and using the theoretical formula of Owents and Wendt based on the measured values.

[0029] In addition, as a means for ensuring that no peak derived from fluorine atoms F1S is observed in XPS analysis and for keeping the surface free energy value within the above range, for example, a cured film may be formed using a preferred composition of the resin composition described below.

[0030] In FT-IR analysis (ATR method), the cured film of the laminate of the present invention has a wavelength of 950 to 1250 cm derived from siloxane bonds (Si—O). -1 The absorption intensity of the peak top (E SiO ) and 1650-1750 cm originating from carbonyl groups (C=O groups) -1 The absorption intensity of the peak top (E CO ) ratio (E SiO / E CO) preferably satisfies the following relational formula (I): 1.2≦ E SiO / E CO ≦20 (I) FT-IR analysis can be performed as described in the Examples below.

[0031] The peak top refers to the peak position where the peak height is maximum in each wavenumber range. 950-1250cm -1 The absorption intensity of the peak top (E SiO ) is the wavenumber in the spectrum of 950 cm -1 point and 1250cm -1 Connect the points with a straight line and measure 950~1250cm -1 When a perpendicular line is drawn from the peak top to this line, it represents the distance from the peak top to the intersection point of the line and the perpendicular line. 1650~1750cm -1 The absorption intensity of the peak top (E CO ) is a wave number of 1650-1750 cm -1 It represents the distance measured in the same way within the range.

[0032] E SiO / E CO When the E is 1.2 or more, the siloxane bond components in the cured film can enhance the liquid repellency and weather resistance. SiO / E CO is preferably 1.5 or more, and more preferably 2.0 or more. SiO / E CO When the E is 20 or less, the organic components in the cured film can enhance the crack resistance of the cured film. SiO / E CO is preferably 15 or less, and more preferably 10 or less.

[0033] In addition, E in the relational formula (I) SiO / E CO As a means for adjusting the thickness to the above range, for example, a cured film may be formed using a preferred composition of the resin composition described below.

[0034] The cured film in the laminate of the present invention is preferably a patterned partition wall. The partition wall refers to, for example, a layer that separates wavelength conversion layers or light-emitting layers, which will be described later. Examples of the repeated pattern of the formed partition wall include a lattice pattern, a stripe pattern, and a hole pattern.

[0035] 2 shows a cross-sectional view of one embodiment of the laminate of the present invention having a substrate and partition walls patterned as a cured film. The laminate has a base substrate 1 on which partition walls 3 are patterned.

[0036] The height of the partition wall is not particularly limited, but when used as a partition wall separating wavelength conversion layers or light emitters described below, it is preferably 5 μm or more and 50 μm or less. By setting the height of the partition wall within this range, good light extraction efficiency can be achieved. The height of the partition wall is preferably 8 μm or more, more preferably 10 μm or more. In addition, it is preferably 30 μm or less, more preferably 20 μm or less.

[0037] The partition walls preferably have a reflectance of 20% to 85% at a wavelength of 550 nm per 10 μm of thickness. The thickness of the partition walls refers to the height and / or width of the partition walls described above. The height of the partition walls refers to the length of the partition walls in a direction perpendicular to the underlying surface (height direction). In the case of the laminate shown in FIG. 2, the height of the partition walls 3 is represented by the symbol H. The width of the partition walls refers to the length of the partition walls in a direction parallel to the underlying surface. In the case of the laminate shown in FIG. 2, the width of the partition walls 3 is represented by the symbol L. In this specification, "height" may also be referred to as "thickness." In the present invention, it is believed that the reflectance on the side surface of the partition walls contributes to improving the light extraction efficiency, and the OD value (light blocking property) contributes to suppressing color mixing between adjacent pixels. However, since the reflectance and OD value per thickness are believed to be the same regardless of the height or width direction, the present invention focuses on the reflectance and OD value per thickness of the partition walls. As mentioned above, the height of the partition wall is preferably 5 μm or more and 50 μm or less, and the width is preferably 1 μm or more and 100 μm or less. Therefore, in the present invention, 10 μm was selected as a representative value for the thickness of the partition wall, and attention was paid to the reflectance and OD value per 10 μm of thickness.

[0038] If the reflectance at a wavelength of 550 nm per 10 μm of thickness is less than 20%, the reflection at the side surface of the partition wall will be small, the light extraction efficiency will be poor, and the brightness of the display device will be insufficient. The reflectance at a wavelength of 550 nm per 10 μm of thickness is more preferably 25% or more, and even more preferably 30% or more. The higher the reflectance, the greater the reflection at the side surface of the partition wall, and the more improved the light extraction efficiency will be. However, if the reflectance at a wavelength of 550 nm per 10 μm of thickness exceeds 85%, light mixing will occur between adjacent pixels.

[0039] The reflectance at a wavelength of 550 nm per 10 μm of partition wall thickness can be measured as described in the Examples below.

[0040] The partition wall preferably has an OD value of 1.5 or more and 3.0 or less at a wavelength of 450 nm per 10 μm of thickness. If the OD value at a wavelength of 450 nm per 10 μm of thickness is less than 1.5, the partition wall will not be able to block blue light sufficiently. For example, when used as a partition wall separating wavelength conversion layers (described later), blue light (excitation light) will leak into adjacent pixels, causing emission from the adjacent pixels and resulting in color mixing. The OD value at a wavelength of 450 nm per 10 μm of thickness is more preferably 1.7 or more, and even more preferably 2.0 or more. The higher the OD value, the greater the partition wall's ability to block blue light, preventing color mixing between adjacent pixels and improving the contrast of the display device. However, if the OD value at a wavelength of 450 nm per 10 μm of thickness exceeds 3.0, the brightness of the display device will be insufficient.

[0041] The OD value at a wavelength of 450 nm per 10 μm of partition wall thickness can be calculated by measuring the transmittance of a 10 μm-thick partition wall from the top surface using an optical densitometer / spectrophotometer (e.g., U-4100 manufactured by Hitachi High-Tech Science) and using the following calculation formula (1). However, if an area sufficient for measurement cannot be secured or a 10 μm-thick measurement sample cannot be obtained, and the composition of the partition wall is known, the OD value per 10 μm of thickness can be obtained by preparing a 10 μm-thick solid film with the same composition as the partition wall, as in the case of measuring the reflectance, and measuring the transmittance of the solid film instead of the partition wall. OD value = -log10(T / 100) (1) T: Transmittance.

[0042] The taper angle of the partition wall is preferably 45° to 110°. The taper angle of the partition wall refers to the angle between the side edge and the bottom edge of the partition wall cross section. In the case of the laminate shown in Figure 2, the taper angle of the partition wall 3 is represented by the symbol θ. By setting the taper angle to 45° or more, the difference in width between the top and bottom of the partition wall is reduced, making it easy to form the partition wall width within the preferred range described above. The taper angle is more preferably 80° or more. On the other hand, by setting the taper angle to 110° or less, ink breakage can be suppressed when forming the color-conversion phosphor described below by inkjet coating, thereby improving inkjet coating properties. Here, ink breakage refers to the phenomenon in which ink overcomes the partition wall and mixes into adjacent pixel areas. The taper angle is more preferably 95° or less. The taper angle of the partition wall can be determined by observing an arbitrary cross section of the partition wall using a scanning electron microscope (FE-SEM (e.g., S-4800 manufactured by Hitachi, Ltd.)) at an acceleration voltage of 3.0 kV and a magnification of 2,500 times, and measuring the angle between the side edge and the bottom edge of the cross section of the partition wall.

[0043] In addition, as a means for setting the reflectance, OD value and taper angle of the partition walls within the above ranges, for example, the partition walls may be formed using a preferred composition of the resin composition described below.

[0044] The partition walls are formed on a glass substrate to a height of 10 μm to separate cells with a width of 10 μm and an opening of (X × 10) μm × (Y × 10) μm. When 0.2 × Y pL of 1,6-hexanediol diacrylate is applied by inkjet to the center of the cell, the 1,6-hexanediol diacrylate spreads well throughout the cell, and when 1.5 × Y pL of 1,6-hexanediol diacrylate is applied by inkjet to the center of the cell, the 1,6-hexanediol diacrylate does not climb onto the top of the partition walls, resulting in good liquid repellency.

[0045] When 10-μm-high partition walls are formed on a glass substrate to separate cells with a width of 10 μm and an opening of (X × 10) μm × (Y × 10) μm, the volume of the space separated by the partition walls is XY pL. When 0.2 XY pL of 1,6-hexanediol diacrylate is applied to the center of the cell by inkjet printing, if the 1,6-hexanediol diacrylate spreads well throughout the cell, the wavelength-converting layer (described below) can be filled into the partition walls without gaps. "Good spreadability throughout the cell" refers to the state in which, when the laminate after coating with 1,6-hexanediol diacrylate is observed from above with an optical microscope, the coated 1,6-hexanediol diacrylate is not concentrated in the center of the cell or around sides 1 to 3 of the partition walls, but is present and spread around all four sides of the partition walls. For example, Figure 3 shows a state in which "the coating spreads well throughout the entire cell," while Figures 4-1, 4-2, and 4-3 show states in which "the coating spreads poorly throughout the cell."

[0046] Furthermore, when 1.5 pL of 1,6-hexanediol diacrylate is dropped onto the center of a cell by inkjet printing and excessively coated, if the 1,6-hexanediol diacrylate does not climb onto the top of the partition walls and the top liquid repellency is good, the wavelength conversion layer (described below) can be accurately coated within the partition walls. "Good top liquid repellency" refers to the state in which, when the laminate after coating with 1,6-hexanediol diacrylate is observed from above with an optical microscope, the coated 1,6-hexanediol diacrylate does not climb onto the partition walls and remains within the cell. For example, Figure 5 shows a state in which "good top liquid repellency" and Figure 6 show a state in which "good top liquid repellency" are good.

[0047] Inkjet coating of 1,6-hexanediol diacrylate can be carried out as described in the Examples below. For example, after forming a 10-μm-high partition wall on a glass substrate to separate cells with a width of 10 μm and an opening of 140 μm × 40 μm, and then inkjetting 11 pL of 1,6-hexanediol diacrylate into the center of the cell, the 1,6-hexanediol diacrylate spreads well throughout the cell. Furthermore, when inkjetting 84 pL of 1,6-hexanediol diacrylate into the center of the cell, the 1,6-hexanediol diacrylate does not climb onto the top of the partition wall, resulting in good liquid repellency.

[0048] In order to improve the wetting spreadability over the entire cell and the liquid repellency at the top, for example, the partition walls may be formed using a preferred composition of the resin composition described below.

[0049] The cured film in the laminate of the present invention is preferably a patterned partition wall, and preferably has a wavelength converting layer in a cell partitioned by the partition wall.

[0050] 7 shows a cross-sectional view of one embodiment of the laminate of the present invention having a wavelength-converting layer. The laminate has partition walls 3 patterned as a cured film on a base substrate 1, and wavelength-converting layers 4 in the pixels separated by the partition walls.

[0051] The wavelength conversion layer refers to a cured layer containing a phosphor that is excited by the wavelength of a backlight and emits light of a different wavelength and / or light-diffusing particles that diffuse light of the wavelength of the backlight. Each pixel may contain a different phosphor and / or light-diffusing particles. For example, when used in combination with a backlight that emits blue light, the region corresponding to the red pixel preferably contains a red phosphor that is excited by blue excitation light and emits red fluorescence. Similarly, the region corresponding to the green pixel preferably contains a green phosphor that is excited by blue excitation light and emits green fluorescence. The region corresponding to the blue pixel preferably does not contain a phosphor but contains light-diffusing particles that diffuse blue light. The wavelength conversion layer preferably contains a phosphor selected from inorganic phosphors and organic phosphors.

[0052] The inorganic phosphor is preferably one that emits colors such as green and red when excited by blue excitation light, i.e., one that is excited by excitation light with a wavelength of 400 to 500 nm and has an emission spectrum with a peak in the range of 500 to 700 nm. Examples of such inorganic phosphors include YAG phosphors, TAG phosphors, sialon phosphors, Mn 4+ Examples of such phosphors include activated fluoride complex phosphors and inorganic semiconductors known as quantum dots. Two or more of these may be used. Among these, quantum dots are preferred. Quantum dots have a smaller average particle size than other phosphors, and therefore can smooth the surface of the (B) pixel and suppress light scattering on the surface, thereby further improving light extraction efficiency and brightness.

[0053] Examples of quantum dot materials include semiconductors of Group II-IV, Group III-V, Group IV-VI, and Group IV. Examples of 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, Si3N4, Ge3N4, and Al2O3. Two or more of these may be used.

[0054] The organic fluorescent material is preferably one that emits various colors such as green and red when excited by blue light. Examples of the organic fluorescent material include pyrromethene derivatives, perylene derivatives, porphyrin derivatives, oxazine derivatives, and pyrazine derivatives. Two or more of these may be contained. Among these, pyrromethene derivatives are preferred because of their high quantum yield. Pyrromethene derivatives can be obtained, for example, by the method described in JP-A-2011-241160.

[0055] The thickness of the wavelength conversion layer is preferably 0.5 μm or more, more preferably 1 μm or more, from the viewpoint of improving color characteristics, while the thickness of the wavelength conversion layer is preferably 30 μm or less, more preferably 20 μm or less, from the viewpoint of thinning the display device and curved surface processability.

[0056] The wavelength conversion layers are preferably arranged so as to be separated by partition walls, which can further suppress the diffusion and color mixing of emitted light.

[0057] The wavelength conversion layer can be formed, for example, by filling a coating liquid containing a phosphor and / or light-diffusing particles (hereinafter referred to as wavelength conversion material coating liquid) into the spaces separated by the partition walls. The wavelength conversion material coating liquid may further contain a resin and a solvent.

[0058] Examples of methods for filling the wavelength converting material coating liquid include photolithography and inkjet coating. From the viewpoint of easily applying different types of color converting luminescent materials to each pixel, inkjet coating is preferred.

[0059] The laminate of the present invention may further include an inorganic protective layer on the wavelength converting layer, which serves to protect the wavelength converting layer from oxygen and water.

[0060] 8 shows a cross-sectional view of one embodiment of the laminate of the present invention having an inorganic protective layer. The laminate has partition walls 3 patterned as a cured film on a base substrate 1, wavelength conversion layers 4 in the pixels separated by the partition walls, and an inorganic protective layer 5 thereon.

[0061] Examples of materials constituting the inorganic protective layer include metal oxides such as silicon oxide (SiO), indium tin oxide, and gallium zinc oxide; and metal nitrides such as silicon nitride (SiN). Two or more of these may be contained. Among these, silicon oxide (SiO) or silicon nitride (SiN) are more preferred because of their low water vapor permeability and high permeability.

[0062] Examples of methods for forming the inorganic protective layer include sputtering. The thickness of the inorganic protective layer is preferably 50 nm or more from the viewpoint of sufficiently suppressing the permeation of substances such as water vapor. On the other hand, the thickness of the inorganic protective layer is preferably 800 nm or less from the viewpoint of suppressing a decrease in transmittance. The thickness of the inorganic protective layer can be measured by exposing a cross section perpendicular to the base substrate using a polishing device such as a cross-section polisher and then observing the cross section under magnification using a scanning electron microscope or a transmission electron microscope.

[0063] The laminate of the present invention may further include a color filter layer (hereinafter, sometimes referred to as "color filter"). The color filter has the function of transmitting visible light in a specific wavelength range and giving the transmitted light a desired hue. By including a color filter, the color purity of the display device can be improved.

[0064] 9 shows a cross-sectional view of one embodiment of the laminate of the present invention having a color filter layer. A color filter layer 6 is formed on a base substrate 1, and partition walls 3 formed as a patterned cured film are formed thereon. Each pixel separated by the partition walls has a wavelength conversion layer 4, and an inorganic protective layer 5 is formed thereon.

[0065] Examples of color filters include color filters using pigment-dispersed materials in which pigments are dispersed in photoresist, which are used in flat panel displays such as liquid crystal displays. More specifically, examples include a blue color filter section that selectively transmits wavelengths of 400 nm to 550 nm, a green color filter section that selectively transmits wavelengths of 500 nm to 600 nm, a yellow color filter section that selectively transmits wavelengths of 500 nm or longer, and a red color filter section that selectively transmits wavelengths of 600 nm or longer. A black material may be included as a black matrix separating each color filter section. Alternatively, an overcoat section may be formed by applying a transparent overcoat material after forming each color filter section and the black matrix. When a black matrix and color filter sections of each color are provided, a preferred configuration is one in which a black matrix 7 is formed under the partition wall and color filter sections 8 of each color are formed under the wavelength conversion layer, as shown in FIG. 9.

[0066] The cured film in the laminate of the present invention may be a solid film without a pattern formed thereon, instead of the patterned partition wall. When the cured film is a solid film, it can be suitably used, for example, as an antireflection layer of a low-reflection film that requires water repellency and antifouling properties.

[0067] Next, the resin composition that forms the cured film in the laminate of the present invention will be described.

[0068] The cured film in the laminate of the present invention is a cured film obtained by curing a resin composition containing (A) polysiloxane, (B) a photopolymerization initiator, (C) a photopolymerizable compound, and (D) a liquid-repellent compound, and it is preferable that the liquid-repellent compound (D) is a surfactant that does not contain a fluorine atom in the molecule and contains a photopolymerizable group.

[0069] (A) Polysiloxane Polysiloxane is a hydrolysis / dehydration condensation product of organosilane compounds, and refers to a resin with a siloxane bond (Si-O bond) as the main skeleton and 0 to 3 organic groups on the Si atom. It may also contain a silicone group (a dimethylsiloxane skeleton with two methyl groups on the Si atom), which will be described later, but a resin that has one or more skeletons other than silicone groups at locations other than the terminals is defined as (A) polysiloxane.

[0070] The organosilane compound preferably contains a repeating unit derived from a bifunctional organosilane compound represented by general formula (1) and / or a repeating unit derived from a trifunctional organosilane compound represented by general formula (2), and more preferably contains both a repeating unit derived from a bifunctional organosilane compound and a repeating unit derived from a trifunctional organosilane compound.

[0071] [ka]

[0072] [ka]

[0073] In the above general formula (1), R 1 and R 2 may be the same or different and each represent a monovalent organic group having 1 to 20 carbon atoms. 1 and R 2The repeating unit may contain two or more types of repeating units represented by general formula (1) having R 1 and R 2 is preferably a group selected from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 12 carbon atoms, from the viewpoint of facilitating molecular weight control of the polysiloxane during polymerization. However, at least a portion of the hydrogen atoms of the alkyl and aryl groups may be substituted with radically polymerizable groups, and in the cured product, the radically polymerizable groups may be radically polymerized. In the above general formula (2), R 3 represents a monovalent organic group having 1 to 20 carbon atoms. 3 The repeating unit may contain two or more types of repeating units represented by general formula (2) having R 3 From the viewpoint of facilitating molecular weight control of the polysiloxane during polymerization, it is preferable that the alkyl group contains a group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 12 carbon atoms. However, at least a portion of the hydrogen atoms of the alkyl group and aryl group may be substituted with a radically polymerizable group, and in the cured product, the radically polymerizable group may be radically polymerized.

[0074] The inclusion of repeating units derived from a bifunctional organosilane compound can suppress excessive thermal polymerization (condensation) of the polysiloxane due to heating, thereby improving the crack resistance of the cured film. It is preferable that the polysiloxane contains 10 to 70 mol% of repeating units derived from a bifunctional organosilane compound among all repeating units. From the viewpoint of achieving both crack resistance and liquid repellency in the cured film, it is more preferable that the polysiloxane contains 15 to 35 mol% of repeating units derived from a bifunctional organosilane compound among all repeating units. On the other hand, the inclusion of repeating units derived from a trifunctional organosilane compound increases the crosslink density of the polysiloxane in the cured film, thereby improving the film's hardness and chemical resistance. It is preferable that the polysiloxane contains 30 to 90 mol% of repeating units derived from a trifunctional organosilane compound among all repeating units.

[0075] The repeating units represented by the general formulas (1) and (2) are derived from organosilane compounds represented by the following general formulas (3) and (4), respectively. That is, polysiloxanes containing repeating units represented by the general formulas (1) and (2) can be obtained by hydrolyzing and polycondensing organosilane compounds represented by the following general formulas (3) and (4), respectively. Other organosilane compounds may also be used. In addition, in the general formulas (3) and (4), "-(OR 4 )2" and "-(OR 4 )3" is written as "-(OR 4 )" means that two and three are bonded together, respectively.

[0076] [ka]

[0077] In the above general formula (3), R 1 ~R 2 represents R in the above general formula (1). 1 ~R 2 In the above general formula (4), R 3 represents R in the above general formula (2). 3 In the above general formulas (3) and (4), R 4 may be the same or different and represent a monovalent organic group having 1 to 20 carbon atoms or hydrogen, and preferably an alkyl group having 1 to 6 carbon atoms.

[0078] Examples of the organosilane compound represented by the general formula (3) include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenylsilanediol, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- Examples include glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, 3-dimethylmethoxysilylpropylsuccinic anhydride, 3-dimethylethoxysilylpropylsuccinic anhydride, 3-dimethylmethoxysilylpropionic acid, 3-dimethylethoxysilylpropionic acid, 3-dimethylmethoxysilylpropylcyclohexyldicarboxylic anhydride, etc. Two or more of these may be used.

[0079] Examples of the organosilane compound represented by general formula (4) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-Glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-ethyl-3-{[3-(trimethoxysilyl)propoxy]methyl}oxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, phenyltrimethoxysilane, phenyltriethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane Silane, 2-naphthyltrimethoxysilane, tolyltrimethoxysilane, tolyltriethoxysilane, styryltrimethoxysilane, styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, γ-acryloylpropyltrimethoxysilane, γ-acryloylpropyltriethoxysilane, γ-methacryloylpropyltrimethoxysilane, γ-methacryloylpropyltriethoxysilane, 3-trimethoxysilylpropionate, 3-trimethylsilane ... Examples thereof include ethoxysilylpropionic 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, and 3-triethoxysilylpropylphthalic anhydride. Two or more of these may be used.

[0080] Other organosilane compounds may be contained. Examples of other organosilane compounds include tetrafunctional organosilane compounds such as tetramethoxysilane, tetraethoxysilane, and silicate 51 (tetramethoxysilane oligomer). Two or more of these may be used.

[0081] The (A) polysiloxane preferably contains at least one radically polymerizable group. That is, the organosilane compound represented by general formula (3) and / or (4) preferably contains at least one radically polymerizable group-containing organosilane compound. When the (A) polysiloxane contains a radically polymerizable group-containing organosilane compound, a crosslinking reaction proceeds with radicals generated from the (B) photopolymerization initiator (described below) upon light irradiation, thereby increasing the degree of curing in the exposed area. Furthermore, the reaction with the (D) liquid-repellent compound (described below) can proceed efficiently, thereby increasing the liquid repellency of the cured film and reducing the surface free energy. Examples of radically polymerizable groups include vinyl groups, methacrylic groups, acrylic groups, allyl groups, and styryl groups. Two or more of these groups may be contained. Among these, from the viewpoint of photoreactivity, the (A) polysiloxane preferably contains a methacrylic group, an acrylic group, or a styryl group, and more preferably contains at least a styryl group. The inclusion of a styryl group lowers the surface free energy of the cured film due to its high reactivity with the (D) liquid-repellent compound and the structure after the reaction. Furthermore, the inclusion of a styryl group improves the curability (low-temperature curability) when cured at low temperatures of 80 to 100°C in the (iv) heating step, thereby improving the chemical resistance of the cured film.

[0082] The polysiloxane (A) preferably contains 10 to 60 mol % of repeating units having a styryl group out of all repeating units. If the repeating units having a styryl group out of all repeating units are less than 10 mol %, the photoreactivity will be insufficient, the surface free energy of the cured film will be high, and the low-temperature curing property will be deteriorated. If the repeating units having a styryl group out of all repeating units are more than 60 mol %, the film stress due to photocuring will be high, and the crack resistance of the cured film will be deteriorated. More preferably, the repeating units having a styryl group out of all repeating units are 15 mol % to 40 mol %.

[0083] The polysiloxane (A) preferably contains at least one carboxyl group. That is, the organosilane compound represented by general formula (3) and / or (4) preferably contains at least one carboxyl group- and / or carboxylic anhydride group-containing organosilane compound. By including the carboxyl group- and / or carboxylic anhydride group-containing organosilane compound, developability can be improved during barrier rib pattern formation.

[0084] From the viewpoint of coatability, the weight-average molecular weight (Mw) of the (A) polysiloxane is preferably 1,000 or more, more preferably 2,000 or more. In particular, when the (A) polysiloxane does not contain a styryl group, Mw is more preferably 4,000 or more. When Mw is 4,000 or more, after reaction with the (D) liquid-repellent compound in the exposure step, the surface is less likely to be dissolved by development during the development step, and the surface free energy of the cured film can be reduced. On the other hand, from the viewpoint of developability and pattern processability, Mw of the polysiloxane is preferably 500,000 or less, more preferably 300,000 or less. Here, the Mw of the polysiloxane in the present invention refers to the polystyrene equivalent value measured by gel permeation chromatography (GPC). The measurement method is as described in the Examples below.

[0085] (A) Polysiloxane 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. A catalyst such as an acid or a base may be used in the hydrolysis-dehydration condensation reaction.

[0086] The content of (A) polysiloxane is preferably 10% by weight or more of the solid content from the viewpoint of improving the liquid repellency and pattern processability of the cured film.

[0087] (B) Photopolymerization initiator The (B) photopolymerization initiator may be any one that decomposes and / or reacts with the actinic rays irradiated in the (ii) exposure step to generate radicals, and is preferably one that decomposes and / or reacts with at least one of i-rays, h-rays, and g-rays to generate radicals. Examples of the (B) photopolymerization initiator include α-aminoalkylphenone compounds such as 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; 2,4,6-trimethylbenzoylphenylphosphine; acylphosphine oxide compounds such as 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], ... Oxime ester compounds such as 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, and ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime); α-hydroxyketone compounds such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexyl-phenyl ketone; and acetophenone compounds such as 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-t-butyldichloroacetophenone, benzalacetophenone, and 4-azidobenzalacetophenone. Two or more of these may be contained.Among these, it is preferable that the (B) photopolymerization initiator contains at least an oxime ester compound, from the viewpoints of generating radicals that are resistant to oxygen damage, enhancing the reactivity of the (D) liquid-repellent compound (described below) on the surface of the cured film, and reducing the surface free energy of the cured film.Furthermore, it is preferable that the (B) photopolymerization initiator further contains an acylphosphine oxide compound, from the viewpoints of absorbing long-wavelength light and achieving excellent thick-film curing properties.

[0088] The content of the (B) photopolymerization initiator is preferably 0.5% by weight or more, more preferably 1% by weight or more, of the solid content from the viewpoint of effectively promoting radical curing, while the content of the (B) photopolymerization initiator is preferably 20% by weight or less, more preferably 10% by weight or less, of the solid content from the viewpoint of suppressing elution of the remaining (B) photopolymerization initiator.

[0089] (C) Photopolymerizable compound The (C) photopolymerizable compound refers to a compound having two or more ethylenically unsaturated double bonds in the molecule, but not having a siloxane bond (Si-O bond) or a liquid-repellent functional group (described later). Considering the ease of radical polymerization, the (C) photopolymerizable compound preferably contains a vinyl group, an allyl group, a methacryl group, an acrylic group, or a styryl group, with methacryl group, acrylic group, and styryl group being more preferred.

[0090] Examples of the (C) photopolymerizable compound include 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, tripentaerythritol heptamethacrylate, tripentaerythritol octamethacrylate, tetrapentaerythritol nonamethacrylate, and tetrapentaerythritol decamethacrylate. Two or more of these may be contained.

[0091] The content of the (C) photopolymerizable compound is preferably 1% by weight or more of the solid content from the viewpoint of effectively promoting radical curing, while the content of the (C) photopolymerizable compound is preferably 50% by weight or less of the solid content from the viewpoint of suppressing excessive radical reaction and improving resolution.

[0092] (D) Liquid repellent compound The liquid-repellent compound (D) in the present invention refers to a surfactant that does not contain a fluorine atom in the molecule and contains a photopolymerizable group. A surfactant refers to a compound that has the effect of reducing the surface tension or interfacial tension at the interface between substances (such as the boundary between liquids, liquids and solids, or liquids and gases), and in this case refers to a compound that has a liquid-repellent functional group. Examples of the liquid-repellent functional group include a hydrocarbon group and a silicone group.

[0093] The absence of fluorine atoms in the molecule improves the adhesion of the resulting cured film to the overlying inorganic layer, such as SiO2 or SiN. XPS analysis only analyzes the atoms present on the film surface, and in recent years, concerns have arisen about the harmful effects of organic fluorine compounds on the human body due to their persistence in the environment and bioaccumulation, with regulations currently being considered, primarily in Europe. This allows for the production of environmentally friendly cured films.

[0094] Furthermore, by using a surfactant containing a photopolymerizable group, (i) after the coating step, (D) the liquid-repellent compound is localized on the film surface, and (ii) in the exposure step, the photopolymerizable group in (D) the liquid-repellent compound reacts with the radicals generated from the (B) photopolymerization initiator, thereby efficiently improving the liquid repellency of the cured film surface. The photopolymerizable group preferably contains, for example, a vinyl group, an allyl group, a methacryl group, an acrylic group, or a styryl group, with methacryl group, acrylic group, and styryl group being more preferred, and acrylic group and styryl group being even more preferred.

[0095] The liquid-repellent compound (D) is preferably a silicone-based surfactant. The silicone-based surfactant can impart high water repellency derived from the silicone group to the surface of the cured film. A silicone-based surfactant refers to a surfactant that has a resin structure such as an acrylic resin or a polyimide resin as its main skeleton and further contains a silicone group as a liquid-repellent functional group. The silicone group refers to a dimethylsiloxane skeleton that has a siloxane bond (Si-O bond) as its main skeleton and has two methyl groups on the Si atom.

[0096] The liquid-repellent compound (D) may be a synthesized compound or a commercially available product. Examples of commercially available liquid-repellent compounds (D) include "BYK" (registered trademark)-UV3500, UV3510, UV3530, UV3519, UV3575, and UV3576 (all trade names, manufactured by BYK Japan KK) and "RS" (registered trademark)-57 (trade name, manufactured by DIC Corporation), and other silicone surfactants with photopolymerizable groups. Among these, RS-57 is preferred from the viewpoint of reducing surface free energy.

[0097] The content of the (D) liquid-repellent compound is preferably 0.05 wt % to 2.00 wt % of the total solid content of the resin composition. If the content of the (D) liquid-repellent compound is less than 0.05 wt % of the total solid content, the amount of (D) liquid-repellent compound cured on the film surface will be insufficient, and the surface free energy will not be sufficiently reduced. If the content of the (D) liquid-repellent compound is more than 2.00 wt % of the total solid content, the (D) liquid-repellent compound that has not completely cured on the film surface will peel off into the pixels of the partition wall during the (iii) development process, resulting in the aforementioned "poor spreadability throughout the entire cell" when the wavelength conversion layer is formed by inkjet coating. The content of the (D) liquid-repellent compound is more preferably 0.10 wt % to 1.00 wt % of the total solid content, and even more preferably 0.15 wt % to 0.50 wt % of the total solid content.

[0098] The cured film in the laminate of the present invention is preferably a cured film obtained by curing a resin composition further containing (E) a metal chelating agent. (E) The metal chelating agent refers to a complex compound having a structure in which one or more multidentate ligands are chelated to a metal atom.

[0099] By including (E) a metal chelating agent, the surface free energy of the upper surface of the cured film can be set to 10 mN / m or more and 29 mN / m or less, even when (iv) the heating step is performed at a low temperature of 80 to 100° C. This is because all or part of (E) the metal chelating agent is incorporated into the film, and the (E) metal chelating agent can promote the condensation reaction between unreacted silanol groups remaining in component (a).

[0100] The (E) metal chelating agent is preferably a metal chelating agent represented by the following general formula (5):

[0101] [ka]

[0102] (M represents a metal atom, R5 are each independently a hydrogen atom, an alkyl group, an aryl group, or an alkenyl group, and R 6 and R 7 are each independently a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, or an alkoxy group, j is an integer of 0 to 8, and k is an integer of 1 to 4. Examples of the metal atom M include titanium, zirconium, aluminum, zinc, cobalt, molybdenum, lanthanum, barium, strontium, magnesium, and calcium, from the viewpoint of low coloration of the formed cured film. Among these, from the viewpoint of low coloration of the cured film and low surface free energy, zirconium or aluminum is preferred as the metal atom M, and aluminum is more preferred. That is, as the (E) metal chelating agent, it is preferred to use an aluminum chelate compound or a zirconium chelate compound, and it is more preferred to use an aluminum chelate compound.

[0103] R of the metal chelating agent represented by general formula (5) 5 The alkyl, aryl and alkenyl groups in R 6 and R 7 The alkyl group, aryl group, alkenyl group and alkoxy group in the formula (I) may each be substituted with another substituent.

[0104] In general formula (5), R 5Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, an octadecanyl group, a phenyl group, a vinyl group, an allyl group, and an oleyl group. Among these, from the viewpoint of the stability of the metal chelating agent, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-octadecyl group, and a phenyl group are preferred. Examples of R6 and R7 include hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, phenyl, vinyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-octadecyl, and benzyloxy. Among these, from the viewpoint of ease of synthesis and stability of the metal chelating agent, methyl, t-butyl, phenyl, methoxy, ethoxy, and n-octadecyl are preferred.

[0105] Examples of aluminum chelate compounds in which the metal atom M is aluminum include aluminum trisisopropoxide, aluminum tris-n-propoxide, aluminum tris-sec-butoxide, aluminum tris-n-butoxide, aluminum trisphenoxide, aluminum trisacetylacetonate, aluminum tris(2,2,6,6-tetramethyl-3,5-heptanedionate), aluminum trisethylacetoacetate, aluminum trismethylacetoacetate, aluminum trismethylmalonate, aluminum trisethylmalonate, aluminum ethylacetate di(isopropoxide), aluminum acetylacetonate di(isopropoxide), aluminum methylacetoacetate di(isopropoxide), aluminum octadecylacetoacetate di(isopropylate), and aluminum monoacetylacetonate bis(ethylacetoacetate).

[0106] Examples of zirconium chelate compounds in which the metal atom M is zirconium include zirconium tetra-n-propoxide, zirconium tetra-n-butoxide, zirconium tetra-sec-butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, zirconium tetra(2,2,6,6-tetramethyl-3,5-heptanedionate), zirconium tetramethylacetoacetate, zirconium tetraethylacetoacetate, zirconium tetramethylmalonate, zirconium tetraethylmalonate, zirconium tetrabenzoylacetonate, zirconium tetradibenzoylmethanate, and zirconium mono-n-butoxy. Examples of the acetylacetonate include acetylacetonate bis(ethyl acetoacetate), zirconium mono-n-butoxyethyl acetoacetate bis(acetylacetonate), zirconium mono-n-butoxytris(acetylacetonate), zirconium mono-n-butoxytris(acetylacetonate), zirconium di(n-butoxy)bis(ethyl acetoacetate), zirconium di(n-butoxy)bis(acetylacetonate), zirconium di(n-butoxy)bis(ethyl malonate), zirconium di(n-butoxy)bis(benzoylacetonate), zirconium di(n-butoxy)bis(dibenzoylmethanate), and zirconium tetraacetylacetonate.

[0107] Among these, from the viewpoints of low coloration of the cured film and low surface free energy, zirconium tetra-normal propoxide, zirconium tetra-normal butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, zirconium tetraacetylacetonate, aluminum trisacetylacetonate, and aluminum tris(2,2,6,6-tetramethyl-3,5-heptanedionate) are preferred, and aluminum trisacetylacetonate is more preferred.

[0108] The content of the (E) metal chelating agent is preferably 0.1 wt % or more, more preferably 0.5 wt % or more, of the total solid content of the resin composition from the viewpoint of reducing the surface free energy, while from the viewpoint of low coloration of the cured film, it is preferably 5 wt % or less, more preferably 3 wt % or less.

[0109] The resin composition that forms the cured film in the laminate of the present invention may contain components other than the above (A) to (E), and may optionally contain ultraviolet absorbers, polymerization inhibitors, surfactants, adhesion improvers, particles, dispersants, resins other than polysiloxanes, etc. However, for the same reasons as those explained for the liquid-repellent compound (D), it is preferable that the resin composition does not contain a compound containing a fluorine atom.

[0110] The resin composition forming the cured film in the laminate of the present invention can improve light resistance by containing an ultraviolet absorber. As the ultraviolet absorber, from the viewpoint of transparency and non-coloring, benzotriazole compounds such as 2-(2H-benzotriazol-2-yl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-tert-pentylphenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole, benzophenone compounds such as 2-hydroxy-4-methoxybenzophenone, and triazine compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol are preferably used.

[0111] The resin composition forming the cured film in the laminate of the present invention may contain a polymerization inhibitor to further improve resolution during pattern formation. Examples of polymerization inhibitors include di-t-butylhydroxytoluene, butylhydroxyanisole, 4-methoxyphenol, 1,4-benzoquinone, and t-butylcatechol. Commercially available polymerization inhibitors include "IRGANOX" (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565, and 295 (all trade names, manufactured by BASF Japan Ltd.). Two or more of these may be contained.

[0112] The resin composition forming the cured film in the laminate of the present invention contains, in addition to the liquid-repellent compound (D), a surfactant without a photopolymerizable group, thereby improving leveling properties during application. While fluorine-based surfactants are known as surfactants that improve leveling properties, for the reasons mentioned above, this composition does not contain fluorine-based surfactants. Suitable surfactants include, for example, silicone-based surfactants such as "BYK" (registered trademark)-333, 301, 331, 345, and 307 (all trade names, manufactured by BYK Japan KK); polyalkylene oxide-based surfactants; and poly(meth)acrylate-based surfactants. Two or more of these may be contained.

[0113] The resin composition forming the cured film in the laminate of the present invention can improve adhesion to the base substrate by containing an adhesion promoter, such as an alicyclic epoxy compound or a silane coupling agent.

[0114] Examples of alicyclic epoxy compounds include 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate, 1,2-epoxy-4-vinylcyclohexane, butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone, 3,4-epoxycyclohexylmethyl methacrylate, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol E diglycidyl ether, hydrogenated bisphenol A bis(propylene glycol glycidyl ether) ether, hydrogenated bisphenol A bis(ethylene glycol glycidyl ether) ether, 1,4-cyclohexanedicarboxylate diglycidyl, and 1,4-cyclohexanedimethanol diglycidyl ether. Two or more of these may be used.

[0115] As the silane coupling agent, the organosilane compounds exemplified as raw materials for (A) polysiloxane can be suitably used.

[0116] The content of the adhesion promoter is preferably 0.1% by mass or more, more preferably 1% by mass or more, of the total solid content from the viewpoint of further improving adhesion to the base substrate, while the content of the adhesion promoter is preferably 20% by mass or less, more preferably 10% by mass or less, of the total solid content from the viewpoint of pattern processability.

[0117] The resin composition that forms the cured film in the laminate of the present invention contains particles, which makes it possible to adjust the optical properties of the cured film, such as reflectance, OD value (light blocking ability), and refractive index.

[0118] When it is desired to improve the reflectivity of the cured film, it is preferable to contain a white pigment as particles. Examples of the white pigment include particles having an average primary particle diameter of 100 nm or more and less than 500 nm, and examples of the type of particles include titanium oxide, zirconium oxide, zinc oxide, barium sulfate, and composite compounds thereof. Two or more of these may be contained.

[0119] When it is desired to improve the light-shielding properties of the cured film at a specific wavelength, it is preferable to contain a light-shielding pigment such as a red pigment, blue pigment, black pigment, green pigment or yellow pigment as particles.

[0120] When it is desired to achieve both reflectivity and light-blocking properties, it is preferable to contain both a white pigment and a light-blocking pigment.

[0121] Examples of red pigments include Pigment Red (hereinafter abbreviated as PR) PR177, PR179, PR180, PR192, PR209, PR227, PR228, PR240, and PR254. Two or more of these may be contained.

[0122] Examples of blue pigments include Pigment Blue (hereinafter abbreviated as PB) 15, PB15:3, PB15:4, PB15:6, PB22, PB60, PB64, etc. Two or more of these may be contained.

[0123] Examples of black pigments include black organic pigments, mixed-color organic pigments, and black inorganic pigments. Examples of black organic pigments include carbon black, perylene black, aniline black, and benzofuranone-based pigments. These may be coated with a resin. Examples of mixed-color organic pigments include pseudo-black pigments obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, magenta, and cyan. Among these, a mixed pigment of a red pigment and a blue pigment is preferred from the viewpoint of achieving both a moderately high OD value and pattern processability. The mass ratio of the red pigment to the blue pigment in the mixed pigment is preferably 20 / 80 to 80 / 20, and more preferably 30 / 70 to 70 / 30. Examples of black inorganic pigments include graphite, fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zirconium, zinc, calcium, silver, gold, platinum, and palladium, metal oxides, metal composite oxides, metal sulfides, metal nitrides, metal oxynitrides, and metal carbides. Two or more of these may be contained.

[0124] Examples of green pigments include CI Pigment Green (hereinafter abbreviated as PG) 7, PG36, PG58, PG37, PG59, etc. Two or more of these may be contained.

[0125] Examples of yellow pigments include pigment yellow (hereinafter abbreviated as PY) PYPY150, PY153, PY154, PY166, PY168, PY185, etc. Two or more of these may be contained.

[0126] When it is desired to increase the refractive index of the cured film, it is preferable to contain high refractive index particles. Examples of high refractive index particles include oxide particles having an average primary particle diameter of 1 nm or more and less than 100 nm, and examples of particle types include titanium oxide, zirconium oxide, and zinc oxide. Two or more of these may be contained.

[0127] When it is desired to lower the refractive index of the cured film, it is preferable to contain low refractive index particles. Examples of low refractive index particles include oxide particles having an average primary particle diameter of 1 nm or more and less than 100 nm, and examples of particle types include solid silica particles and hollow particles. Examples of hollow particles include hollow silica and hollow organic particles. From the viewpoint of lowering the refractive index, hollow silica and hollow organic particles are preferred. Two or more of these may be contained.

[0128] The resin composition is preferably prepared by dispersing the particles in a mixture of a dispersant and a solvent, which will be described later. Therefore, the resin composition that forms the cured film in the laminate of the present invention may contain a dispersant.

[0129] Examples of dispersants include polyoxyethylene, polyacrylic acid, polyphosphoric acid, phosphate polyester, and polyacrylamide.

[0130] The resin composition forming the cured film in the laminate of the present invention may further contain a resin other than (A) polysiloxane. The use of a resin other than (A) polysiloxane can, for example, improve tackiness after pre-baking, thereby complementing the film properties that are insufficient with (A) polysiloxane. Examples of resins other than (A) polysiloxane include polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, (meth)acrylic polymer, and cardo resin.

[0131] The resin composition forming the cured film in the laminate of the present invention preferably further contains a solvent. The solvent adjusts the viscosity of the resin composition to a range suitable for coating and improves coating uniformity. As the solvent, a combination of a solvent having a boiling point of more than 150°C and not more than 250°C at atmospheric pressure and a solvent having a boiling point of not more than 150°C is preferred.

[0132] Examples of the solvent include alcohols such as isopropanol and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and diethylene glycol ethyl methyl ether; methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, and acetylacetone. Examples of suitable solvents include ketones such as clopentanone; amides such as dimethylformamide and dimethylacetamide; acetates such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, and butyl lactate; aromatic or aliphatic hydrocarbons such as toluene, xylene, hexane, and cyclohexane; γ-butyrolactone, N-methyl-2-pyrrolidone, and dimethyl sulfoxide. Two or more of these may be used.

[0133] The content of the solvent can be set arbitrarily depending on the application method, etc. For example, when forming a film by spin coating, the content of the solvent in the resin composition is generally 50% by weight or more and 95% by weight or less.

[0134] The resin composition that forms the cured film in the laminate of the present invention can be produced, for example, by mixing the aforementioned (A) polysiloxane, (B) photopolymerization initiator, (C) photopolymerizable compound, (D) liquid-repellent compound, solvent, and, if necessary, other components.

[0135] Next, the resin composition of the present invention will be described. The resin composition of the present invention can be suitably used for the purpose of obtaining a cured film that does not contain fluorine atoms and has low surface free energy, like the cured film in the laminate of the present invention.

[0136] The resin composition of the present invention is characterized by containing (A) a polysiloxane and (D) a liquid-repellent compound. When used as the aforementioned thermosetting resin composition, the resin composition can be suitably used in applications such as antireflection layers for low-reflection films that require water repellency and antifouling properties.

[0137] The polysiloxane (A) is as described above and preferably contains at least a styryl group. The polysiloxane (A) preferably contains 10 to 60 mol % of repeating units having a styryl group based on all repeating units.

[0138] The liquid repellent compound (D) is as described above, and is preferably a silicone surfactant.

[0139] The resin composition of the present invention preferably further contains (B) a photopolymerization initiator and (C) a photopolymerizable compound. The (B) photopolymerization initiator is as described above, and the (C) photopolymerizable compound is as described above. By containing (B) a photopolymerization initiator and (C) a photopolymerizable compound, the resin composition can be used as the photocurable resin composition described above, and can be suitably used for applications such as antireflection layers of low-reflection films that require water repellency and antifouling properties, as described above, particularly for films with low heat resistance. Furthermore, by containing (B) a photopolymerization initiator and (C) a photopolymerizable compound, the resin composition can also be used as the negative-type photosensitive resin composition described above, and can be suitably used as a material for forming the partition wall pattern that separates the wavelength conversion layers described above.

[0140] The resin composition of the present invention preferably further contains (E) a metal chelating agent, which is as described above.

[0141] The resin composition of the present invention may contain components other than the above (A) to (E), and may contain, as necessary, ultraviolet absorbers, polymerization inhibitors, surfactants, adhesion improvers, particles, dispersants, resins other than polysiloxanes, etc. However, it is preferable that the resin composition does not contain a compound containing a fluorine atom.

[0142] Resins other than the components (A) to (E), the ultraviolet absorber, the polymerization inhibitor, the surfactant, the adhesion improver, the particles, the dispersant, and the polysiloxane contained in the resin composition of the present invention can be used within the above-mentioned suitable ranges and addition amount ranges for the resin composition that forms the cured film in the laminate of the present invention.

[0143] The resin composition of the present invention can be produced, for example, by mixing the aforementioned (A) polysiloxane, (B) photopolymerization initiator, (C) photopolymerizable compound, (D) liquid-repellent compound, solvent, and, if necessary, other components.

[0144] Next, the display device of the present invention will be described.

[0145] The display device of the present invention comprises the laminate of the present invention described above and a light source selected from a liquid crystal cell, an organic electroluminescent (EL) cell, a mini LED cell, and a micro LED cell. Because of their excellent light-emitting properties, organic electroluminescent (EL) cells, mini LED cells, and micro LED cells are more preferred as light sources. A mini LED cell refers to a cell in which a large number of LEDs, each measuring approximately 100 μm to 1 mm in length and width, are arranged. A micro LED cell refers to a cell in which a large number of LEDs, each measuring less than 100 μm in length and width, are arranged. The light sources may be separated by partition walls in the laminate of the present invention. It is preferable to provide the wavelength conversion layer described above on the light source. That is, it is preferable that the laminate of the present invention includes a wavelength conversion layer in a cell separated by partition walls.

[0146] 10 shows a cross-sectional view of one embodiment of a display device of the present invention having light-emitting sources and pixels selected from organic EL cells, mini LED cells, and micro LED cells. Light-emitting sources 9 selected from organic EL cells, mini LED cells, and micro LED cells are placed between partition walls 3 patterned on a base substrate 1, and a wavelength conversion layer 4 is further placed thereon.

[0147] The manufacturing method of the display device of the present invention will be described using an example of a display device having the laminate of the present invention and an organic EL cell. A photosensitive polyimide resin is applied to a glass substrate, and an insulating film with an opening is formed using photolithography. Aluminum is sputtered onto the polyimide resin, and then patterned using photolithography to form a back electrode layer made of aluminum in the openings where there was no insulating film. Next, tris(8-quinolinolato)aluminum (hereinafter abbreviated as Alq3) is deposited on the polyimide resin by vacuum deposition as an electron transport layer, and then a white light-emitting layer is formed by doping Alq3 with dicyanomethylenepyran, quinacridone, and 4,4'-bis(2,2-diphenylvinyl)biphenyl as an emissive layer. Next, N,N'-diphenyl-N,N'-bis(α-naphthyl)-1,1'-biphenyl-4,4'-diamine is deposited by vacuum deposition as a hole transport layer. Finally, an ITO film is formed as a transparent electrode by sputtering to produce an organic EL cell having a white light-emitting layer. A display device can be produced by bonding the laminate having the cured film and the organic EL cell thus obtained opposite each other with a sealant.

[0148] Next, the information terminal of the present invention will be described.

[0149] The information terminal of the present invention is an information terminal having the display device of the present invention described above, and is, for example, an electronic device used as a display, such as a personal computer, a smartphone, a tablet, a smart watch, smart glasses, smart home appliances, etc. [Example]

[0150] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The names of the compounds used, for which abbreviations are used, are shown below. PGMEA: Propylene glycol monomethyl ether acetate DAA: Diacetone alcohol IPA: Isopropyl alcohol MIBK: Methyl isobutyl ketone BHT: dibutylhydroxytoluene.

[0151] The solids concentration of the polysiloxane solution in Synthesis Examples 1 to 9 was determined by the following method. 1.00 g of the polysiloxane solution was weighed into an aluminum cup and heated on a hot plate at 250°C for 30 minutes to evaporate the liquid. The weight of the solids remaining in the aluminum cup after heating was weighed, and the solids concentration was determined as a ratio to the weight before heating.

[0152] The weight average molecular weight of the polysiloxane solutions in Synthesis Examples 1 to 11 was measured as polystyrene equivalent weight average molecular weight by the following method. Apparatus: Waters GPC measurement device with RI detector (2695) Column: PLgel MIXED-C column (Polymer Laboratories, 300 mm) x 2 (connected in series) Measurement temperature: 40℃ Flow rate: 1mL / min Solvent: tetrahydrofuran (THF) 0.5% by mass solution Standard material: polystyrene Detection mode: RI.

[0153] The content ratio of each repeating unit in the polysiloxane in Synthesis Examples 1 to 9 was determined by the following method. The polysiloxane solution was poured into an NMR sample tube made of "Teflon" (registered trademark) with a diameter of 10 mm. 29 Si-NMR measurements were performed, and the content ratio of each repeating unit was calculated from the ratio of the integral value of Si derived from a specific organosilane to the integral value of all Si derived from organosilanes.29 The Si-NMR measurement conditions are as follows: Equipment: Nuclear magnetic resonance apparatus (JNM-GX270; manufactured by JEOL Ltd.) Measurement method: Gated decoupling method Measurement nuclear frequency: 53.6693MHz ( 29 Si nucleus) Spectral width: 20000Hz Pulse width: 12 μs (45° pulse) Pulse repetition time: 30.0 seconds Solvent: acetone-d6 Reference material: tetramethylsilane Measurement temperature: 23℃ Sample rotation speed: 0.0 Hz.

[0154] Synthesis Example 1 Polysiloxane (PSL-1) solution A 1000 ml three-neck flask was charged with 71.16 g (0.306 mol) of 3-methacryloxypropylmethyldimethoxysilane, 78.52 g (0.35 mol) of styryltrimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 113.22 g (0.83 mol) of methyltrimethoxysilane, 45.87 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.07 g of BHT, and 308.28 g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 3.30 g of phosphoric acid (1.0 wt % based on the charged monomers) in 92.14 g of water was added thereto over 30 minutes with stirring at 40°C. The flask was then immersed in a 70°C oil bath and stirred for 60 minutes, after which the oil bath was heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature 100-110°C), yielding a polysiloxane solution. During the temperature increase and heating and stirring, a gas mixture of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 L / min. A total of 210 g of by-products, methanol and water, was distilled during the reaction. PGMEA was added to the resulting polysiloxane solution to adjust the solids concentration to 40% by weight, yielding a polysiloxane (PSL-1) solution. The weight-average molecular weight of the resulting polysiloxane (PSL-1) was 5,000. In addition, the molar ratios of repeating units derived from 3-methacryloxypropylmethyldimethoxysilane, styryltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-1) were 17.5 mol%, 20 mol%, 5 mol%, 47.5 mol%, and 10 mol%, respectively.

[0155] Synthesis Example 2 Polysiloxane (PSL-2) solution A 1000 ml three-neck flask was charged with 71.16 g (0.306 mol) of 3-methacryloxypropylmethyldimethoxysilane, 157.0 g (0.70 mol) of styryltrimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 65.55 g (0.48 mol) of methyltrimethoxysilane, 45.87 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.24 g of BHT, and 345.67 g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 3.61 g of phosphoric acid (1.0 wt % based on the charged monomers) in 92.14 g of water was added thereto over 30 minutes with stirring at 40°C. The flask was then immersed in a 70°C oil bath and stirred for 60 minutes, after which the oil bath was heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature 100-110°C) to obtain a polysiloxane solution. During the temperature increase and heating and stirring, a gas mixture of 95% nitrogen by volume and 5% oxygen by volume was flowed at 0.05 L / min. A total of 210 g of by-product methanol and water was distilled during the reaction. PGMEA was added to the resulting polysiloxane solution to adjust the solids concentration to 40% by weight, yielding a polysiloxane (PSL-2) solution. The weight-average molecular weight of the resulting polysiloxane (PSL-2) was 5,000. In addition, the molar ratios of repeating units derived from 3-methacryloxypropylmethyldimethoxysilane, styryltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-2) were 17.5 mol%, 40 mol%, 5 mol%, 27.5 mol%, and 10 mol%, respectively.

[0156] Synthesis Example 3 Polysiloxane (PSL-3) solution A 1000 ml three-necked flask was charged with 71.16 g (0.306 mol) of 3-methacryloxypropylmethyldimethoxysilane, 235.6 g (1.1 mol) of styryltrimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 17.88 g (0.13 mol) of methyltrimethoxysilane, 45.87 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.39 g of BHT, and 383.06 g of PGMEA. A phosphoric acid aqueous solution prepared by dissolving 3.92 g of phosphoric acid (1.0 wt% relative to the charged monomer) in 92.14 g of water was added over 30 minutes while stirring at 40 ° C. The flask was then immersed in a 70 ° C. oil bath and stirred for 60 minutes, after which the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the mixture was then heated and stirred for two hours (internal temperature 100-110°C), yielding a polysiloxane solution. During the temperature increase and heating and stirring, a mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 L / min. A total of 210 g of by-products, methanol and water, was distilled during the reaction. PGMEA was added to the resulting polysiloxane solution to adjust the solids concentration to 40% by weight, yielding a polysiloxane (PSL-3) solution. The weight-average molecular weight of the resulting polysiloxane (PSL-3) was 4,000. In addition, the molar ratios of repeating units derived from 3-methacryloxypropylmethyldimethoxysilane, styryltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-3) were 17.5 mol%, 60 mol%, 5 mol%, 7.5 mol%, and 10 mol%, respectively.

[0157] Synthesis Example 4 Polysiloxane (PSL-4) solution A 1000 ml three-necked flask was charged with 71.16 g (0.306 mol) of 3-methacryloxypropylmethyldimethoxysilane, 255.2 g (1.1 mol) of styryltrimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 5.96 g (0.04 mol) of methyltrimethoxysilane, 45.87 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.43 g of BHT, and 392.41 g of PGMEA. A phosphoric acid aqueous solution prepared by dissolving 4.00 g of phosphoric acid (1.0 wt% relative to the charged monomer) in 92.14 g of water was added over 30 minutes while stirring at 40 ° C. The flask was then immersed in a 70 ° C. oil bath and stirred for 60 minutes, after which the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the mixture was then heated and stirred for two hours (internal temperature 100-110°C), yielding a polysiloxane solution. During the temperature increase and heating and stirring, a mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed in at 0.05 L / min. A total of 210 g of by-products, methanol and water, was distilled during the reaction. PGMEA was added to the resulting polysiloxane solution to adjust the solids concentration to 40% by weight, yielding a polysiloxane (PSL-4) solution. The weight-average molecular weight of the resulting polysiloxane (PSL-4) was 3,000. In addition, the molar ratios of repeating units derived from 3-methacryloxypropylmethyldimethoxysilane, styryltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-3) were 17.5 mol%, 65 mol%, 5 mol%, 2.5 mol%, and 10 mol%, respectively.

[0158] Synthesis Example 5 Polysiloxane (PSL-5) solution A 1000 ml three-neck flask was charged with 71.16 g (0.306 mol) of 3-methacryloxypropylmethyldimethoxysilane, 58.89 g (0.26 mol) of styryltrimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 125.1 g (0.92 mol) of methyltrimethoxysilane, 45.87 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.04 g of BHT, and 298.93 g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 3.23 g of phosphoric acid (1.0 wt % based on the charged monomers) in 92.14 g of water was added thereto over 30 minutes with stirring at 40°C. The flask was then immersed in a 70°C oil bath and stirred for 60 minutes, after which the oil bath was heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature 100-110°C), yielding a polysiloxane solution. During the temperature increase and heating and stirring, a gas mixture of 95% nitrogen by volume and 5% oxygen by volume was passed through at 0.05 L / min. A total of 210 g of by-product methanol and water was distilled during the reaction. PGMEA was added to the resulting polysiloxane solution to adjust the solids concentration to 40% by weight, yielding a polysiloxane (PSL-5) solution. The resulting polysiloxane (PSL-5) had a weight-average molecular weight of 5,000. In addition, the molar ratios of repeating units derived from 3-methacryloxypropylmethyldimethoxysilane, styryltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-5) were 17.5 mol%, 15 mol%, 5 mol%, 52.5 mol%, and 10 mol%, respectively.

[0159] Synthesis Example 6 Polysiloxane (PSL-6) solution A 1000 ml three-neck flask was charged with 71.16 g (0.306 mol) of 3-methacryloxypropylmethyldimethoxysilane, 39.26 g (0.18 mol) of styryltrimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 137.1 g (1.01 mol) of methyltrimethoxysilane, 45.87 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.00 g of BHT, and 289.58 g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 3.15 g of phosphoric acid (1.0 wt % based on the charged monomers) in 92.14 g of water was added thereto over 30 minutes with stirring at 40°C. The flask was then immersed in a 70°C oil bath and stirred for 60 minutes, after which the oil bath was heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature 100-110°C), yielding a polysiloxane solution. During the temperature increase and heating and stirring, a gas mixture of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 L / min. A total of 210 g of by-products, methanol and water, was distilled during the reaction. PGMEA was added to the resulting polysiloxane solution to adjust the solids concentration to 40% by weight, yielding a polysiloxane (PSL-6) solution. The weight-average molecular weight of the resulting polysiloxane (PSL-6) was 6,000. In addition, the molar ratios of repeating units derived from 3-methacryloxypropylmethyldimethoxysilane, styryltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-6) were 17.5 mol%, 10 mol%, 5 mol%, 57.5 mol%, and 10 mol%, respectively.

[0160] Synthesis Example 7 Polysiloxane (PSL-7) solution A 1000 ml three-neck flask was charged with 71.16 g (0.306 mol) of 3-methacryloxypropylmethyldimethoxysilane, 19.63 g (0.09 mol) of styryltrimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 149.0 g (1.09 mol) of methyltrimethoxysilane, 45.87 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 0.963 g of BHT, and 280.24 g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 3.07 g of phosphoric acid (1.0 wt % based on the charged monomers) in 92.14 g of water was added thereto over 30 minutes with stirring at 40°C. The flask was then immersed in a 70°C oil bath and stirred for 60 minutes, after which the oil bath was heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature 100-110°C), yielding a polysiloxane solution. During the temperature increase and heating and stirring, a gas mixture of 95% nitrogen by volume and 5% oxygen by volume was flowed at 0.05 L / min. A total of 210 g of by-product methanol and water was distilled during the reaction. PGMEA was added to the resulting polysiloxane solution to adjust the solids concentration to 40% by weight, yielding a polysiloxane (PSL-7) solution. The weight-average molecular weight of the resulting polysiloxane (PSL-7) was 6,500. In addition, the molar ratios of repeating units derived from 3-methacryloxypropylmethyldimethoxysilane, styryltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-7) were 17.5 mol%, 5 mol%, 5 mol%, 62.5 mol%, and 10 mol%, respectively.

[0161] Synthesis Example 8 Polysiloxane (PSL-8) solution A 1000 ml three-necked flask was charged with 152.5 g (0.656 mol) of 3-methacryloxypropylmethyldimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 113.2 g (0.831 mol) of methyltrimethoxysilane, 45.87 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.13 g of BHT, and 317.98 g of PGMEA. A phosphoric acid aqueous solution prepared by dissolving 3.07 g of phosphoric acid (1.0 wt% based on the charged monomer) in 92.14 g of water was added over 30 minutes while stirring at 40 ° C. The flask was then immersed in a 70 ° C. oil bath and stirred for 60 minutes, after which the oil bath was heated to 115 ° C. over 30 minutes. One hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the mixture was then heated and stirred for two hours (internal temperature 100-110°C), yielding a polysiloxane solution. During the temperature increase and heating and stirring, a mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 L / min. A total of 196 g of by-products, methanol and water, was distilled during the reaction. PGMEA was added to the resulting polysiloxane solution to adjust the solids concentration to 40% by weight, yielding a polysiloxane (PSL-8) solution. The weight-average molecular weight of the resulting polysiloxane (PSL-8) was 2,500. In addition, the molar ratios of repeating units derived from 3-methacryloxypropylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-8) were 37.5 mol%, 5 mol%, 47.5 mol%, and 10 mol%, respectively.

[0162] Synthesis Example 9 Polysiloxane (PSL-9) solution Synthesis was carried out in the same manner as in Synthesis Example 8. After the internal temperature reached 100°C, the mixture was heated and stirred for 3 hours (internal temperature: 100-110°C) to obtain a polysiloxane solution. During the temperature increase and heating and stirring, a mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 L / min. A total of 200 g of by-products, methanol and water, was distilled off during the reaction. PGMEA was added to the obtained polysiloxane solution to adjust the solids concentration to 40% by weight, to obtain a polysiloxane (PSL-9) solution. The weight-average molecular weight of the obtained polysiloxane (PSL-9) was 3,600. In addition, the molar ratios of repeating units derived from 3-methacryloxypropylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-9) were 37.5 mol%, 5 mol%, 47.5 mol%, and 10 mol%, respectively.

[0163] Synthesis Example 10 Polysiloxane (PSL-10) solution Synthesis was carried out in the same manner as in Synthesis Example 8. After the internal temperature reached 100°C, the mixture was heated and stirred for 4 hours (internal temperature: 100-110°C) to obtain a polysiloxane solution. During the temperature increase and heating and stirring, a mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 L / min. A total of 210 g of by-products, methanol and water, was distilled off during the reaction. PGMEA was added to the obtained polysiloxane solution to adjust the solids concentration to 40% by weight, to obtain a polysiloxane (PSL-10) solution. The weight-average molecular weight of the obtained polysiloxane (PSL-10) was 4,300. In addition, the molar ratios of repeating units derived from 3-methacryloxypropylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-10) were 37.5 mol%, 5 mol%, 47.5 mol%, and 10 mol%, respectively.

[0164] Synthesis Example 11 Polysiloxane (PSL-11) solution A 1000 ml three-neck flask was charged with 71.16 g (0.306 mol) of 3-methacryloxypropylmethyldimethoxysilane, 160.4 g (0.656 mol) of diphenyldimethoxysilane, 21.56 g (0.088 mol) of 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, 71.51 g (0.525 mol) of methyltrimethoxysilane, 45.87 g (0.175 mol) of 3-trimethoxysilylpropylsuccinic anhydride, 1.36 g of BHT, and 368.78 g of PGMEA, and an aqueous phosphoric acid solution prepared by dissolving 3.71 g of phosphoric acid (1.0 wt % based on the charged monomers) in 80.33 g of water was added thereto over 30 minutes with stirring at 40°C. The flask was then immersed in a 70°C oil bath and stirred for 60 minutes, after which the oil bath was heated to 115°C over 30 minutes. One hour after the start of the temperature increase, the solution temperature (internal temperature) reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature 100-110°C), yielding a polysiloxane solution. During the temperature increase and heating and stirring, a gas mixture of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 L / min. A total of 183 g of by-products, methanol and water, was distilled during the reaction. PGMEA was added to the resulting polysiloxane solution to adjust the solids concentration to 40% by weight, yielding a polysiloxane (PSL-11) solution. The weight-average molecular weight of the resulting polysiloxane (PSL-11) was 1,500. In addition, the molar ratios of repeating units derived from 3-methacryloxypropylmethyldimethoxysilane, diphenylditrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-11) were 17.5 mol%, 37.5 mol%, 5 mol%, 30 mol%, and 10 mol%, respectively. The compositions of Synthesis Examples 1 to 11 are shown in Table 1.

[0165] [Table 1-1]

[0166] [Table 1-2]

[0167] Synthesis Example 12: Synthesis of (meth)acrylic polymer solution (PAL-1) A 500 mL flask was charged with 3.00 g of 2,2'-azobis(isobutyronitrile) and 50.0 g of PGMEA, followed by 30.0 g (0.349 mol) of methacrylic acid, 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. The mixture was stirred at room temperature for a while, purged with nitrogen, and then heated and stirred at 70 °C for 5 hours. Next, 15.00 g (0.106 mol) of glycidyl methacrylate, 1.00 g of triphenylphosphine, 0.200 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90 °C for 4 hours to obtain a (meth)acrylic polymer solution. PGMEA was added to the obtained (meth)acrylic polymer solution so that the solid content concentration became 40% by weight, to obtain (meth)acrylic polymer solution (PAL-1). The weight average molecular weight of the (meth)acrylic polymer was 16,000.

[0168] Example 1 Resin composition (P-1) 5.00 g of titanium oxide white pigment (CR-97; manufactured by Ishihara Sangyo Kaisha, Ltd. (hereinafter referred to as "CR-97")) was used as particles, 0.50 g of phosphate polyester ("DISPERBYK" (registered trademark)-111; manufactured by BYK Japan K.K. (hereinafter referred to as "DISPERBYK-111")) was used as a dispersant, and 4.50 g of PGMEA was used as a solvent. The mixture was dispersed using a mill-type disperser filled with zirconia beads to obtain a particle dispersion (MW-1). Next, 6.35 g of the polysiloxane (PSL-1) solution obtained in Synthesis Example 1, 5.00 g of the particle dispersion (MW-1), and 0.150 g of ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (“Irgacure” (registered trademark) OXE-02, manufactured by BASF Japan Ltd. (hereinafter referred to as “OXE-02”)) as a photopolymerization initiator were mixed. g, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide ("Irgacure" 819, manufactured by BASF Japan Ltd. (hereinafter referred to as "Omnirad-819")) 0.0500 g, dipentaerythritol hexaacrylate ("KAYARAD" (registered trademark) DPHA, manufactured by Shin-Nihon Yakugyo Co., Ltd. (hereinafter referred to as "DPHA")) 1.60 g as a photopolymerizable compound, "Megafac" (registered trademark) RS-57 (20 wt% MIBK diluted solution, manufactured by DIC Corporation (hereinafter referred to as "RS-57")) 0.125 g as a liquid-repellent compound, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ("Celloxide" (registered trademark) 2021P, manufactured by Daicel Corporation (hereinafter referred to as "Celloxide 2021P")) 0.100 g as an adhesion promoter, and "I 0.100 g of Irganox® 1010 manufactured by BASF Japan Ltd. (hereinafter referred to as "Irganox 1010") and 0.100 g of a 10 wt% diluted solution of an acrylic surfactant (BYK® 352 manufactured by BYK Japan Ltd. (hereinafter referred to as "BYK-352") in PGMEA (corresponding to a concentration of 500 ppm) were dissolved in a solvent of 1.00 g of PGMEA and 0.500 g of DAA, and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a resin composition (P-1).

[0169] Example 2 Resin composition (P-2) A resin composition (P-2) was obtained in the same manner as in Example 1, except that 6.35 g of the polysiloxane (PSL-2) solution was added instead of the polysiloxane (PSL-1) solution.

[0170] Example 3 Resin composition (P-3) A resin composition (P-3) was obtained in the same manner as in Example 1, except that 6.35 g of the polysiloxane (PSL-3) solution was added instead of the polysiloxane (PSL-1) solution.

[0171] Example 4 Resin composition (P-4) A resin composition (P-4) was obtained in the same manner as in Example 1, except that 6.35 g of the polysiloxane (PSL-4) solution was added instead of the polysiloxane (PSL-1) solution.

[0172] Example 5 Resin composition (P-5) A resin composition (P-5) was obtained in the same manner as in Example 1, except that 6.35 g of the polysiloxane (PSL-5) solution was added instead of the polysiloxane (PSL-1) solution.

[0173] Example 6 Resin composition (P-6) A resin composition (P-6) was obtained in the same manner as in Example 1, except that 6.35 g of the polysiloxane (PSL-6) solution was added instead of the polysiloxane (PSL-1) solution.

[0174] Example 7 Resin composition (P-7) A resin composition (P-7) was obtained in the same manner as in Example 1, except that 6.35 g of the polysiloxane (PSL-7) solution was added instead of the polysiloxane (PSL-1) solution.

[0175] Example 8 Resin composition (P-8) A resin composition (P-8) was obtained in the same manner as in Example 1, except that 6.35 g of the polysiloxane (PSL-8) solution was added instead of the polysiloxane (PSL-1) solution.

[0176] Example 9 Resin composition (P-9) A resin composition (P-9) was obtained in the same manner as in Example 1, except that 6.35 g of the polysiloxane (PSL-9) solution was added instead of the polysiloxane (PSL-1) solution.

[0177] Example 10 Resin composition (P-10) A resin composition (P-10) was obtained in the same manner as in Example 1, except that 6.35 g of the polysiloxane (PSL-10) solution was added instead of the polysiloxane (PSL-1) solution.

[0178] Example 11 Resin composition (P-11) A resin composition (P-11) was obtained in the same manner as in Example 1, except that 6.35 g of the polysiloxane (PSL-11) solution was added instead of the polysiloxane (PSL-1) solution.

[0179] Example 12 Resin composition (P-12) A resin composition (P-12) was obtained in the same manner as in Example 1, except that the amount of liquid-repellent compound RS-57 added was changed to 0.250 g and the amount of polysiloxane (PSL-1) solution added was changed to 6.29 g.

[0180] Example 13 Resin composition (P-13) A resin composition (P-13) was obtained in the same manner as in Example 1, except that the amount of liquid-repellent compound RS-57 added was changed to 0.500 g and the amount of polysiloxane (PSL-1) solution added was changed to 6.16 g.

[0181] Example 14 Resin composition (P-14) A resin composition (P-14) was obtained in the same manner as in Example 13, except that 6.35 g of the polysiloxane (PSL-11) solution was added instead of the polysiloxane (PSL-1) solution.

[0182] Example 15 Resin composition (P-15) A resin composition (P-15) was obtained in the same manner as in Example 1, except that 0.125 g of a 20 wt % diluted solution of "BYK" (registered trademark) UV3510, manufactured by BYK Japan K.K. (hereinafter referred to as "BYK-UV3510") in PGMEA was added instead of the liquid-repellent compound RS-57.

[0183] Example 16 Resin composition (P-16) A resin composition (P-16) was obtained in the same manner as in Example 1, except that 0.125 g of a 20 wt % diluted solution of "BYK" (registered trademark) UV3530, manufactured by BYK Japan K.K. (hereinafter referred to as "BYK-UV3530") in PGMEA was added instead of the liquid-repellent compound RS-57.

[0184] Example 17 Resin composition (P-17) A resin composition (P-17) was obtained in the same manner as in Example 1, except that 0.125 g of a 20 wt % diluted solution of "BYK" (registered trademark) UV3575, manufactured by BYK Japan K.K. (hereinafter referred to as "BYK-UV3575") in PGMEA was added instead of the liquid-repellent compound RS-57.

[0185] Example 18 Resin composition (P-18) 16.1 g of polysiloxane (PSL-1) solution, 0.120 g of OXE-02 as a photopolymerization initiator, 0.0400 g of Omnirad-819 as a photopolymerizable compound, 1.28 g of DPHA as a photopolymerizable compound, 0.100 g of RS-57 as a liquid repellent compound, 0.0800 g of Celloxide 2021P as an adhesion promoter, 0.0200 g of Irganox 1010 as a polymerization inhibitor, and 0.100 g of a 10 wt% PGMEA diluted solution of acrylic surfactant BYK-352 (corresponding to a concentration of 500 ppm) were dissolved in 1.59 g of PGMEA solvent and 0.600 g of DAA and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain resin composition (P-18).

[0186] Example 19 Resin composition (P-19) 5.00 g of titanium nitride black pigment was mixed as particles, 0.50 g of phosphoric acid polyester DISPERBYK-111 was mixed as a dispersant, and 4.50 g of PGMEA was mixed as a solvent. The mixture was dispersed using a mill-type disperser filled with zirconia beads to obtain a particle dispersion (MW-2). Next, 15.0 g of polysiloxane (PSL-1) solution, 0.120 g of OXE-02 as a photopolymerization initiator, 0.0400 g of Omnirad-819 as a photopolymerizable compound, 1.28 g of DPHA as a photopolymerizable compound, 0.100 g of RS-57 as a liquid-repellent compound, 0.0800 g of Celloxide 2021P as an adhesion promoter, 0.0200 g of Irganox 1010 as a polymerization inhibitor, and 0.100 g of a 10 wt% diluted solution of acrylic surfactant BYK-352 in PGMEA (corresponding to a concentration of 500 ppm) were dissolved in 1.89 g of solvent PGMEA and 0.600 g of DAA and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain resin composition (P-19).

[0187] Example 20 Resin composition (P-20) As particles, 5.00 g of titanium oxide white pigment, 0.0188 g of titanium nitride black pigment, 0.50 g of phosphate polyester DISPERBYK-111 as a dispersant, and 4.48 g of PGMEA as a solvent were mixed and dispersed using a mill-type disperser filled with zirconia beads to obtain particle dispersion (MW-3). 3.20 g of particle dispersion (MW-3) was added instead of particle dispersion (MW-2), and the amount of polysiloxane (PSL-1) solution added was changed to 7.25 g, and the amount of PGMEA added was changed to 4.00 g. A resin composition (P-20) was obtained in the same manner as in Example 19.

[0188] Example 21 Resin composition (P-21) A resin composition (P-21) was obtained in the same manner as in Example 1, except that 0.100 g (corresponding to a concentration of 500 ppm) of a 10 wt % diluted solution of a fluorochemical surfactant "Megafac" (registered trademark) F-477 (manufactured by DIC Corporation (hereinafter referred to as "F-477") in PGMEA was added instead of the 10 wt % diluted solution of the acrylic surfactant BYK-352 in PGMEA.

[0189] Example 22 Resin composition (P-22) A resin composition (P-22) was obtained in the same manner as in Example 1, except that the amount of polysiloxane (PSL-1) solution added was changed to 6.10 g, the amount of solvent PGMEA added was changed to 1.15 g, and 0.10 g of zirconium tetraacetylacetonate (trade name "Orgatix" (registered trademark) ZC-150, manufactured by Matsumoto Fine Chemical Co., Ltd. (hereinafter referred to as "ZC-150")) was added as a metal chelating agent.

[0190] Example 23 Resin composition (P-23) A resin composition (P-23) was obtained in the same manner as in Example 22, except that 0.10 g of aluminum tris(acetylacetonate) (trade name Aluminum Chelate A(a), manufactured by Kawaken Fine Chemicals Co., Ltd. (hereinafter referred to as "AL-A(a)")) was added instead of ZC-150 as the metal chelating agent.

[0191] Example 24 Resin composition (P-24) A resin composition (P-24) was obtained in the same manner as in Example 22, except that 0.10 g of aluminum tris(ethyl acetoacetate) (ALCH-TR, manufactured by Kawaken Fine Chemicals Co., Ltd. (hereinafter referred to as "ALCH-TR")) was added as the metal chelating agent instead of ZC-150.

[0192] Example 25 Resin composition (P-25) A resin composition (P-25) was obtained in the same manner as in Example 22, except that 0.10 g of aluminum alkyl acetoacetate diisopropylate (trade name Aluminum Chelate M, manufactured by Kawaken Fine Chemicals Co., Ltd. (hereinafter referred to as "AL-M")) was added instead of ZC-150 as the metal chelating agent.

[0193] Example 26 Resin composition (P-26) A resin composition (P-25) was obtained in the same manner as in Example 22, except that 0.10 g of bisacetylacetonatozinc (hereinafter, "Zn(acac)2") was added as a metal chelating agent instead of ZC-150.

[0194] Example 27 Resin composition (P-27) A resin composition (P-27) was obtained in the same manner as in Example 23, except that the amount of polysiloxane (PSL-1) solution added was changed to 6.33 g, the amount of solvent PGMEA added was changed to 1.01 g, and the amount of AL-A(a) added was changed to 0.007 g.

[0195] Example 28 Resin composition (P-28) A resin composition (P-28) was obtained in the same manner as in Example 23, except that the amount of polysiloxane (PSL-1) solution added was changed to 6.33 g, the amount of solvent PGMEA added was changed to 1.02 g, and the amount of AL-A(a) added was changed to 0.010 g.

[0196] Example 29 Resin composition (P-29) A resin composition (P-29) was obtained in the same manner as in Example 23, except that the amount of polysiloxane (PSL-1) solution added was changed to 4.98 g, the amount of solvent PGMEA added was changed to 1.83 g, and the amount of AL-A(a) added was changed to 0.550 g.

[0197] Example 30 Resin composition (P-30) 14.9 g of polysiloxane (PSL-1) solution, 0.15 g of RS-57 as a liquid-repellent compound, and 0.100 g of a 10 wt% diluted solution of acrylic surfactant BYK-352 in PGMEA (corresponding to a concentration of 500 ppm) were dissolved in 4.15 g of solvent PGMEA and 0.700 g of DAA and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain resin composition (P-30).

[0198] Example 31 Resin composition (P-31) 14.6 g of polysiloxane (PSL-1) solution, 0.090 g of OXE-02 as a photopolymerization initiator, 0.0300 g of Omnirad-819, 0.15 g of RS-57 as a liquid-repellent compound, and 0.100 g of a 10 wt% diluted solution of acrylic surfactant BYK-352 in PGMEA (corresponding to a concentration of 500 ppm) were dissolved in 4.33 g of solvent PGMEA and 0.700 g of DAA and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain resin composition (P-31).

[0199] Example 32 Resin composition (P-32) 10.1 g of polysiloxane (PSL-1) solution, 0.090 g of OXE-02 as a photopolymerization initiator, 0.0300 g of Omnirad-819, 0.15 g of RS-57 as a liquid-repellent compound, 9.00 g of a 20 wt% hollow silica IPA solution (trade name Sururia 4110, manufactured by JGC Catalysts and Chemicals Co., Ltd. (hereinafter referred to as "Sururia 4110")), and 0.100 g of a 10 wt% diluted solution of acrylic surfactant BYK-352 in PGMEA (corresponding to a concentration of 500 ppm) were dissolved in 7.03 g of solvent PGMEA and 0.700 g of DAA and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a resin composition (P-32).

[0200] Example 33 Resin composition (P-33) A resin composition (P-33) was obtained in the same manner as in Example 15, except that the polysiloxane (PSL-7) solution was used instead of the polysiloxane (PSL-1) solution.

[0201] Example 34 Resin composition (P-34) A resin composition (P-34) was obtained in the same manner as in Example 16, except that the polysiloxane (PSL-7) solution was used instead of the polysiloxane (PSL-1) solution.

[0202] Example 35 Resin composition (P-35) A resin composition (P-35) was obtained in the same manner as in Example 17, except that the polysiloxane (PSL-7) solution was used instead of the polysiloxane (PSL-1) solution.

[0203] Example 36 Resin composition (P-36) A resin composition (P-36) was obtained in the same manner as in Example 15, except that the polysiloxane (PSL-3) solution was used instead of the polysiloxane (PSL-1) solution.

[0204] Example 37 Resin composition (P-37) A resin composition (P-37) was obtained in the same manner as in Example 16, except that the polysiloxane (PSL-3) solution was used instead of the polysiloxane (PSL-1) solution.

[0205] Example 38 Resin composition (P-38) A resin composition (P-38) was obtained in the same manner as in Example 17, except that the polysiloxane (PSL-3) solution was used instead of the polysiloxane (PSL-1) solution.

[0206] Comparative Example 1 Resin composition (P-39) A resin composition (P-39) was obtained in the same manner as in Example 1, except that 6.35 g of the (meth)acrylic polymer solution (PAL-1) was added instead of the polysiloxane (PSL-1) solution.

[0207] Comparative Example 2 Resin composition (P-40) A resin composition (P-40) was obtained in the same manner as in Example 1, except that 6.35 g of a 40 wt % PGMEA solution of cardo polymer V-259ME (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) was added instead of the polysiloxane (PSL-1) solution.

[0208] Comparative Example 3 Resin composition (P-41) A resin composition (P-41) was obtained in the same manner as in Example 1, except that the liquid-repellent compound RS-57 was not added and the amount of polysiloxane (PSL-1) solution added was changed to 6.41 g.

[0209] Comparative Example 4 Resin Composition (P-42) A resin composition (P-42) was obtained in the same manner as in Example 13, except that 6.35 g of the (meth)acrylic polymer solution (PAL-1) was added instead of the polysiloxane (PSL-1) solution.

[0210] Comparative Example 5 Resin composition (P-43) A resin composition (P-43) was obtained in the same manner as in Example 13, except that 6.35 g of a 40 wt % solution of cardo polymer V-259ME in PGMEA was added instead of the polysiloxane (PSL-1) solution.

[0211] Comparative Example 6 Resin composition (P-44) A resin composition (P-44) was obtained in the same manner as in Example 1, except that 0.125 g of "Megafac" (registered trademark) RS-75-A (20 wt % PGMEA diluted solution, manufactured by DIC Corporation: fluorochemical surfactant with photopolymerizable group (hereinafter referred to as "RS-75-A")) was added instead of the liquid-repellent compound RS-57.

[0212] Comparative Example 7 Resin composition (P-45) A resin composition (P-45) was obtained in the same manner as in Comparative Example 6, except that the amount of liquid-repellent compound RS-75-A added was changed to 0.025 g and the amount of polysiloxane (PSL-1) solution added was changed to 6.40 g.

[0213] Comparative Example 8 Resin Composition (P-46) A resin composition (P-46) was obtained in the same manner as in Example 31, except that the (meth)acrylic polymer solution (PAL-1) was added instead of the polysiloxane (PSL-1) solution.

[0214] Comparative Example 9 Resin composition (P-47) A resin composition (P-47) was obtained in the same manner as in Example 31, except that a 40 wt% PGMEA solution of Cardo polymer V-259ME was added instead of the polysiloxane (PSL-1) solution. Comparative Example 10 Resin composition (P-48) 15.06 g of the polysiloxane (PSL-1) solution and 0.100 g of a 10 wt% PGMEA solution of the acrylic surfactant BYK-352 (corresponding to a concentration of 500 ppm) were dissolved in 4.23 g of PGMEA and 0.700 g of DAA solvent and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a resin composition (P-48).

[0215] The compositions of Examples 1 to 38 and Comparative Examples 1 to 10 are shown in Table 2.

[0216] [Table 2-1]

[0217] [Table 2-2]

[0218] [Table 2-3]

[0219] [Table 2-4]

[0220] Preparation Example 1 Color-changing light-emitting material composition (CL-1) 20 parts by weight of a 0.5 wt% toluene solution of green quantum dot material (Lumidot 640 CdSe / ZnS, average particle size 6.3 nm: manufactured by Aldrich), 45 parts by weight of DPHA, 5 parts by weight of "Irgacure" (registered trademark) 907 (manufactured by BASF Japan Ltd.), 166 parts by weight of a 30 wt% PGMEA solution of acrylic resin (SPCR-18 (trade name), manufactured by Showa Denko K.K.), and 97 parts by weight of toluene were mixed and stirred to dissolve uniformly. The resulting mixture was filtered through a 0.45 μm syringe filter to prepare a color-converting luminescent material composition (CL-1).

[0221] Preparation Example 2 Color-changing light-emitting material composition (CL-2) A color-converting light-emitting material composition (CL-2) was prepared in the same manner as in Preparation Example 1, except that a red quantum dot material (InP / ZnS: manufactured by Aldrich Chemical Co.) was used instead of the green quantum dot material.

[0222] Preparation Example 3 Black Matrix Material Composition (BM-1) A slurry was prepared by mixing 150 g of carbon black (MA100 (trade name) manufactured by Mitsubishi Chemical Corporation), 75 g of polymer dispersant BYK-6919, 100 g of P(ACA)Z250, and 675 g of PGMEA. The beaker containing the slurry was connected to a Dyno-Mill via a tube, and dispersion treatment was carried out for 8 hours at a peripheral speed of 14 m / s using 0.5 mm diameter zirconia beads as media to produce pigment dispersion (MB-1).

[0223] A black matrix material composition (BM-1) was prepared by mixing 56.54 g of the pigment dispersion (MB-1), 3.14 g of P(ACA)Z250, 2.64 g of DPHA, 0.330 g of NCI-831, 0.04 g of BYK-333, 0.01 g of tert-butylcatechol as a polymerization inhibitor, and 37.30 g of PGMEA.

[0224] Preparation Example 4 Color filter material (CF-1) A slurry was prepared by mixing 90 g of CI Pigment Green 59, 60 g of CI Pigment Yellow 150, 75 g of a polymer dispersant ("BYK" (registered trademark)-6919 (trade name) manufactured by BYK-Chemie (hereinafter referred to as "BYK-6919")), 100 g of a binder resin ("ADEKA ARCLES" (registered trademark) WR301 (trade name) manufactured by ADEKA Corporation), and 675 g of PGMEA. The beaker containing the slurry was connected to a Dyno-Mill via a tube, and dispersion treatment was carried out for 8 hours at a peripheral speed of 14 m / s using 0.5 mm diameter zirconia beads as media to prepare Pigment Green 59 dispersion (GD-1).

[0225] A color filter material (CF-1) was prepared by mixing 56.54 g of C.I. Pigment Green 59 dispersion (GD-1), 3.14 g of acrylic resin ("CYCLOMER" (registered trademark) P(ACA) Z250 (trade name) manufactured by Daicel-Allnex Corporation (hereinafter referred to as "P(ACA) Z250")), 2.64 g of DPHA, 0.330 g of photopolymerization initiator ("OPTOMER" (registered trademark) NCI-831 (trade name) manufactured by ADEKA Corporation (hereinafter referred to as "NCI-831")), 0.04 g of surfactant (BYK" (registered trademark) -333 (trade name) manufactured by BYK-Chemie KK (hereinafter referred to as "BYK-333")), 0.01 g of BHT as a polymerization inhibitor, and 37.30 g of PGMEA as a solvent.

[0226] Examples 39 to 71, Comparative Examples 11 to 25 A 10 cm square alkali-free glass substrate (AGC Technoglass Co., Ltd., thickness 0.7 mm; the same applies hereinafter) or a Si wafer (6 inches) was used as the base substrate. The resin compositions shown in Tables 3 to 5 were applied thereon by spin coating, and dried for 3 minutes at 90°C using a hot plate (trade name SCW-636, Dainippon Screen Mfg. Co., Ltd.; the same applies hereinafter) to produce a dried film. The dried film thus produced was then irradiated partially through a photomask with an ultra-high pressure mercury lamp (g, h, i lines) as the light source using a parallel light mask aligner (trade name PLA-501F, Canon Inc.; the same applies hereinafter) at an exposure dose of 300 mJ / cm. 2 The film was exposed to 100 Hz (i-line equivalent). It was then shower-developed for 100 seconds using an automatic developing apparatus (Takizawa Sangyo Co., Ltd., "AD-2000 (trade name)"; the same applies hereinafter) with a 0.045 wt % potassium hydroxide aqueous solution, followed by rinsing with water for 30 seconds. It was then heated in air at 150°C for 60 minutes using an oven (trade name IHPS-222, Espec Corp.; the same applies hereinafter) to form a 10 μm high solid film (cured film) and a lattice-like barrier rib pattern (cured film) with a height of 10 μm, a width of 10 μm, and an opening pitch of 40 μm x 140 μm on the glass substrate or Si wafer, thereby producing a laminate.

[0227] Examples 72 to 104, Comparative Examples 26 to 40 A 10 cm square alkali-free glass substrate was used as the base substrate, and the resin compositions shown in Tables 6 to 8 were applied thereon by spin coating, and a lattice-shaped barrier rib pattern was formed and a cured film was provided to produce a laminate in the same manner as in Examples 39 to 71 and Comparative Examples 11 to 25.

[0228] Next, a color-converting luminescent material composition (CL-1) was applied to a part of the region separated by the partition wall of the obtained laminate using an inkjet method under a nitrogen atmosphere, and dried at 100°C for 30 minutes to form a wavelength-converting layer with a thickness of 10 μm, thereby obtaining a laminate having a cured film and a wavelength-converting layer as shown in FIG. 7.

[0229] The obtained laminate was then placed in a sputtering apparatus SH-450 (manufactured by ULVAC, Inc.), and a silicon oxide was used as a sputtering target to form an SiO layer as an inorganic protective layer with a thickness of 0.1 μm from the top, thereby obtaining a laminate having a cured film, a wavelength conversion layer, and an inorganic protective layer as shown in FIG.

[0230] Examples 105 to 122, Comparative Examples 41 to 50 A 10 cm square alkali-free glass substrate or a Si wafer (6 inches) was used as the base substrate. The resin compositions shown in Tables 9 and 10 were applied thereon by spin coating, and dried on a hot plate at a temperature of 90°C for 3 minutes to produce a dried film. The dried film thus produced was then exposed to light of 300 mJ / cm2 on the entire surface using a parallel light mask aligner and an ultra-high pressure mercury lamp (g, h, i lines) as the light source. 2 The film was exposed to 100 uV (equivalent to i-line). It was then developed using an automatic developer with a 0.045 wt% potassium hydroxide aqueous solution for 100 seconds by shower development, followed by rinsing with water for 30 seconds. It was then heated in an oven at 90°C for 60 minutes in air to form a 10 μm-thick solid film (cured film) on the glass substrate or Si wafer, producing a laminate.

[0231] Example 123 A 10 cm square alkali-free glass substrate or a Si wafer (6 inches) was used as the base substrate. The resin composition (P-31) was applied thereon by spin coating and dried for 3 minutes at 90°C using a hot plate to produce a dry film. The dry film thus produced was then exposed to light of 300 mJ / cm2 on the entire surface using a parallel light mask aligner and an ultra-high pressure mercury lamp (g, h, i lines) as the light source. 2 (i-line equivalent value) After that, without development, the film was heated in an oven in air at 90°C for 60 minutes to form a solid film (cured film) with a height of 10 μm on the glass substrate or Si wafer, thereby producing a laminate.

[0232] The configurations and evaluation results of each of the examples and comparative examples are shown in Tables 3 to 10.

[0233] [Table 3]

[0234] [Table 4]

[0235] [Table 5]

[0236] [Table 6]

[0237] [Table 7]

[0238] [Table 8]

[0239] [Table 9]

[0240]

Table 10

[0241] The evaluation methods of the laminated films provided with the cured films in each of the examples and comparative examples are shown below.

[0242] <Height> Regarding the cured films in the laminates obtained in each of the examples and comparative examples, the film thickness of the partition wall portion was measured using a Surfcom stylus type film thickness measuring device, and the height was measured by calculating the difference between the top of the partition wall and the surface of the glass substrate.

[0243] <XPS analysis> Regarding the solid film portions of the cured films in the laminates obtained in each of the examples and comparative examples, analysis was requested from the Shiga Prefectural Industrial Technology Center, and using an X-ray photoelectron spectroscopy apparatus PHI5000 Versa Probe2 (manufactured by ULVAC-PHI, Inc.), fluorine atoms, carbon atoms, oxygen atoms, silicon atoms, and nitrogen atoms were analyzed from the upper surface of the film. When the presence of a peak was not recognized at 691 eV and it was below the detection limit of the measuring device and the peak derived from fluorine atom F1S was not observed, it was judged as "without F", and when the presence of a peak was recognized at 691 eV and the peak derived from fluorine atom F1S was observed, it was judged as "with F". As an example, the XPS analysis results of Example 39 judged as "without F" are shown in FIG. 12, and the XPS analysis results of Comparative Example 21 judged as "with F" are shown in FIG. 13.

[0244] <Surface free energy> Regarding the glossy film portion of the cured film in the laminate obtained in each example and comparative example, using a microsyringe DM-700 (manufactured by Kyowa Interface Science Co., Ltd.) and a Teflon (registered trademark)-coated needle 22G for a contact angle meter, at 25 °C in the atmosphere, in accordance with the wettability test method for the substrate glass surface specified in JIS R3257 (date of enactment = 1999 / 04 / 20), the contact angle of the film surface was measured. However, in addition to water, diiodomethane was also used, and the contact angles of water and diiodomethane on the glossy film surface were measured. Based on the theoretical formula of Owens and Wendt, the surface free energy (mN / m) was calculated from each measured value.

[0245] <FT-IR Analysis> Regarding the glossy film portion of the cured film in the laminate obtained in each example and comparative example, it was measured by total reflection infrared spectroscopy (ATR) using a Fourier transform infrared spectrometer Avatar360 (manufactured by Nicolet Corporation). As an accessory for total reflection measurement, the company's single reflection type horizontal ATR measurement device (OMNISampler) and a diamond ATR crystal were used to measure the sample surface. As measurement conditions, the resolution was set to 4 cm -1 , the number of scan times was set to 32 times, and the measurement was performed. After performing slope correction on the obtained spectrum in the range of 950 to 1780 cm -1 , the absorption intensity (E -1 ) at the peak top of 950 to 1250 cm SiO derived from the siloxane bond (Si-O) and the absorption intensity (E -1 ) at the peak top of 1650 to 1750 cm CO derived from the carbonyl group (C=O group) were calculated. The ratio (E SiO / E CO ) was calculated. Regarding the peak top, E SiO , E CO , it is as described above.

[0246] <Inkjet Test> "Spreading property during small amount coating" For the partition wall pattern portion of the cured film in the laminate obtained in each Example and Comparative Example, 11 pL of 1,6-hexanediol diacrylate (HDDA) was dropped onto the center of the cell separated by the partition wall using an inkjet coating device (InkjetLabo, manufactured by Cluster Technology Co., Ltd.). After dropping, the laminate was observed from above using an optical microscope (100x magnification), and the "spreadability when a small amount is applied" was evaluated according to the following criteria. As examples, the results of Example 39, which was rated "A," are shown in Figure 3, the results of Example 48, which was rated "B," are shown in Figure 4-1, the results of Example 49, and the results of Example 50 in Figure 4-3. Furthermore, cases where a partition wall pattern could not be formed are marked with "-." A: The applied 1,6-hexanediol diacrylate is not unevenly distributed in the center of the compartment or around sides 1 to 3 of a certain partition wall, but is present and spreads around all four sides of the partition wall, and "the coating spreads well throughout the entire cell." B: The applied 1,6-hexanediol diacrylate is unevenly distributed in the center of the compartment or around one to three sides of a partition wall, and "the coating does not spread well throughout the entire cell." "Liquid repellency at the top of the partition when excessive application occurs" Similarly, 84 pL of 1,6-hexanediol diacrylate was dropped into the center of another cell. After dropping, the laminate was observed from above using an optical microscope (100x magnification), and the "liquid repellency of the top of the partition wall when excessively applied" was evaluated according to the following criteria. As examples, the results of Example 39, which was rated "A," are shown in Figure 5, and the results of Comparative Example 11, which was rated "B," are shown in Figure 6. In addition, cases where a partition wall pattern could not be formed are marked with "-." A: The applied 1,6-hexanediol diacrylate does not climb onto the top of the partition wall, and the top liquid repellency is good. B: The applied 1,6-hexanediol diacrylate is on top of the partition wall, and the liquid repellency at the top is not good. <Reflectance> For the solid film portion of the cured film in the laminates obtained in each of the examples and comparative examples, using a spectrocolorimeter CM-2600d (manufactured by Konica Minolta Co., Ltd.), the reflectance in the wavelength range of 360 nm to 740 nm was measured in the SCI mode from the solid film side. The value at a wavelength of 550 nm was defined as the "reflectance".

[0247] <OD value> For the solid film portion of the cured film in the laminates obtained in each of the examples and comparative examples, using a spectrophotometer U-4100 (manufactured by Hitachi High-Tech Science Corporation), the transmittance in the wavelength range of 300 nm to 800 nm was measured. The "OD value" was calculated by substituting the value at a wavelength of 450 nm into T in the above formula (1).

[0248] <Crack resistance> For the laminates provided with the cured films obtained in each of the examples and comparative examples, using an oven IHPS-222 (manufactured by Espec Corporation), additional heating was performed in air under the following conditions, followed by visual observation to evaluate the presence or absence of cracks in the solid film portion of the cured film. A: No cracks were confirmed after heating at a temperature of 230 °C for 30 minutes. B: No cracks were confirmed after heating at a temperature of 180 °C for 30 minutes, but one or more cracks were confirmed after heating at a temperature of 230 °C for 30 minutes. C: One or more cracks were confirmed after heating at a temperature of 180 °C for 30 minutes.

[0249] <Uneven coating of the wavelength conversion layer> For the partition pattern portion of the cured film in the laminates obtained in each of the examples and comparative examples, at the center of the cell separated by the partition, a color conversion luminescent material composition (CL-1) was applied in the same manner as evaluated in the <Inkjet test> the previous day so that the thickness after curing would be 10 μm, to form a wavelength conversion layer. Then, the color conversion luminescent material composition (CL-2) was dropped to the center of the adjacent cell in the range of 11 pL to 84 pL in the same manner so that the thickness after curing would be 10 μm, and the uneven coating of the wavelength conversion layer was evaluated according to the following criteria. When the partition pattern could not be formed, it was described as "-". A: When 11 pL of color-converting luminescent material composition (CL-2) was dropped, it spread well throughout the entire cell, and even after 84 pL was dropped, the cell was filled with no gaps, and CL-2 did not climb onto the top of the partition wall at all. CL-2 did not overflow into or mix with the cells in which the wavelength-converting layer was formed using color-converting luminescent material composition (CL-1), and the wavelength-converting layer was easily coated. B: When 11 pL of color-converting luminescent material composition (CL-2) was dropped, CL-2 was unevenly distributed around sides 1 to 3 of the partition walls, and the coating spreadability was poor. However, after 84 pL was dropped, the cells were filled with no gaps, and CL-2 did not climb onto the tops of the partition walls at all. CL-2 did not overflow into or mix with the cells in which the wavelength-converting layer was formed using color-converting luminescent material composition (CL-1), and the wavelength-converting layer was relatively well coated. C: When 11 pL of color-converting luminescent material composition (CL-2) was dropped, it spread well throughout the cell, and even after 84 pL was dropped, the cell was filled with no gaps. Although CL-2 partially climbed onto the top of the partition wall, it did not overflow into or mix with the cell in which the wavelength-converting layer was formed using color-converting luminescent material composition (CL-1), and the wavelength-converting layer was relatively easily coated. D: When 11 pL of color-converting luminescent material composition (CL-2) was dropped, CL-2 was unevenly distributed around sides 1 to 3 of the partition walls and did not spread well, but after 84 pL was dropped, it filled the cells without any gaps. CL-2 partially climbed onto the tops of the partition walls, but did not overflow or mix with the cells where the wavelength-converting layer was formed using color-converting luminescent material composition (CL-1), and the wavelength-converting layer was relatively well coated. E: When 11 pL of the color-converting luminescent material composition (CL-2) was dropped, CL-2 was unevenly distributed around sides 1 to 3 of the partition wall, and the coating spreadability was poor. Even when 84 pL was dropped, the cell was not completely filled, resulting in gaps, and the wavelength-converting layer was not well coated. F: When 11 pL of the color-converting luminescent material composition (CL-2) was dropped, it spread well throughout the entire cell, and even after 84 pL was dropped, the cell was filled with no gaps. However, CL-2 completely climbed onto the top of the partition wall, and overflowed and mixed into the cell in which the wavelength-converting layer had been formed using the color-converting luminescent material composition (CL-1), resulting in poor coating ability of the wavelength-converting layer.

[0250] <Adhesion to inorganic protective layer> The laminates obtained in each Example and Comparative Example were placed in a sputtering apparatus SH-450 (manufactured by ULVAC, Inc.), and silicon oxide was used as the sputtering target to form an SiO2 layer as an inorganic protective layer with a thickness of 0.1 μm from the top. This laminate was placed in a thermo-hygrostat chamber at a temperature of 85°C and a humidity of 85% for 100 hours. Thereafter, an adhesion test was performed on the solid portion of the cured film on which the SiO2 layer was laminated in the laminate taken out of the thermo-hygrostat chamber. The adhesion test was performed by drawing 11 parallel lines, 11 in each direction, at 1mm intervals on the surface of the SiO2 layer with a cutter knife, reaching the substrate's base material, to create 100 1mm x 1mm grids. Cellophane adhesive tape (width = 18mm, adhesive strength = 3.7N / 10mm) was then attached to the cut SiO2 layer surface and rubbed with an eraser (JIS S6050 compliant) to adhere it. One end of the tape was held perpendicular to the plate and instantly peeled off, and the number of remaining grids was counted visually. The "adhesion to the inorganic protective layer" of the cured film was evaluated based on the peeled area of ​​the grids according to the following criteria. 5B: Peeling area = 0% 4B: Peeled area = more than 0% and less than 5%. 3B: Peeled area = 5% or more but less than 15%. 2B: Peeled area = 15% or more and less than 35%. 1B: Peeled area = 35% or more but less than 65%. 0B: Peeled area = 65% or more.

[0251] The evaluation methods for the laminates provided with the cured film, the wavelength converting layer, and the inorganic protective layer in each of the examples and comparative examples are described below.

[0252] <Brightness> A surface light-emitting device equipped with a commercially available LED backlight (peak wavelength 465 nm) was used as a light source, and the laminates obtained in each of Examples 72 to 104 and Comparative Examples 26 to 40 were placed so that the pixel portion faced the light source. A current of 30 mA was passed through this surface light-emitting device to light up the LED elements, and the luminance (unit: cd / m ) based on the CIE 1931 standard was measured using a spectroradiometer (CS-1000, manufactured by Konica Minolta). 2 ) was measured and used as the initial luminance. The luminance was evaluated as a relative value, with the initial luminance of Example 85 being set as the standard 100. In addition, when a barrier rib pattern could not be formed, it was recorded as "-".

[0253] <Color mixture> Blue organic EL cells with the same width and in the same locations as the wavelength conversion layer portions partially formed within the grid-like partition walls were fabricated. The laminates obtained in Examples 72 to 104 and Comparative Examples 26 to 40 were then bonded to the blue organic EL cells facing each other using a sealant, resulting in a display device with the configuration shown in Figure 11. Of the blue organic EL cells 10 in Figure 11, only the blue organic EL cell bonded directly below the wavelength conversion layer formed from the color-converting light-emitting material composition (CL-1) was turned on. In this state, the absorbance intensity A (540 nm) at a wavelength of 540 nm was measured for the adjacent cell portion where the wavelength conversion layer was not formed using a microspectrophotometer LVmicro-V (manufactured by Lambda Vision Co., Ltd.). The smaller the absorbance intensity A (540 nm), the less likely color mixing occurred. Color mixing was evaluated according to the following criteria. Note that when a partition wall pattern could not be formed, a "-" was recorded. A:A(540nm)<0.01 B: 0.01≦A(540nm)≦0.5 C:0.5 <A(540nm)。

[0254] <Refractive index> Using a Si wafer (6 inches) as the base substrate, the laminates obtained in Examples 120 to 123 and Comparative Examples 48 to 50 were measured for their refractive index by irradiating the cured film surface with light of 633 nm wavelength from the perpendicular direction at atmospheric pressure and 20°C using a prism coupler (PC-2000 (Metricon Co., Ltd.)), and the refractive index was rounded to two decimal places. When measurement was not possible due to strong reflection or shading, a "-" was entered.

[0255] <Stain resistance> A non-alkali glass substrate was used as the base substrate. For the laminates obtained in Examples 120-123 and Comparative Examples 48-50, a 1-cm linear line was drawn on the surface of the cured film using a black oil-based pen "Mackie Extra Fine Point" (manufactured by Zebra Corporation) and left for 1 minute in a room at room temperature of 25°C. A 500-g standard weight (International Organization for Metrology F2 Class, manufactured by Murakami Scale Manufacturing Co., Ltd.) wrapped in a cleaning cloth "Toraysee MK" (manufactured by Toray Industries, Inc.) was then placed on the cured film and wiped back and forth at a speed of 1 stroke per second 30 times. The appearance of the line after wiping was visually inspected, and the stain resistance was evaluated according to the following criteria. A: After wiping, the lines disappeared. B: After wiping, the color of the line was lighter than before wiping, but it remained. C: After wiping, the lines remained the same as before wiping.

[0256] <Chemical resistance (low temperature curing)> A non-alkali glass substrate was used as the base substrate, and the laminates obtained in Examples 120 to 123 and Comparative Examples 48 to 50 were subjected to a chemical resistance test by immersing them in PGMEA at 25° C. for 5 minutes. The film thickness was measured before and after the test, and the chemical resistance was evaluated based on the film thickness change rate ({|film thickness after test - film thickness before test| / film thickness before test} × 100) according to the following criteria. A: Film thickness change rate less than 1% B: Film thickness change rate 1% or more but less than 5% C: Film thickness change rate is 5% or more. [Explanation of symbols]

[0257] 1 board 2 Cured film H Bulkhead height L Bulkhead width θ Tapered angle of partition wall 3 Bulkhead HDDA 1,6-Hexanediol Diacrylate 4 Wavelength conversion layer 4 (CL-1) Wavelength conversion layer formed from color-converting luminescent material composition (CL-1) 5 Inorganic protective layer 6 color filter layer 7 Black Matrix 8 Color filter sections 9. Light source selected from OLED cells, mini LED cells and micro LED cells 10 Blue organic EL cells

Claims

1. A laminate having a substrate and a cured film obtained by curing a resin composition, wherein in X-ray photoelectron spectroscopy (XPS analysis) of the upper surface of the cured film, no peak derived from fluorine atoms F1s is observed, and the surface free energy of the upper surface of the cured film is 10 mN / m or more and 29 mN / m or less.

2. 2. The laminate according to claim 1, wherein the surface free energy of the upper surface of the cured film is 10 mN / m or more and 25 mN / m or less.

3. The cured film has a siloxane bond (Si—O)-derived IR spectrum of 950 to 1250 cm in FT-IR analysis (ATR). －１ The absorption intensity of the peak top (E ＳｉＯ ) and 1650-1750 cm resulting from the carbonyl group (C═O group). －１ The absorption intensity of the peak top (E ＣＯ ) ratio (E ＳｉＯ / E ＣＯ 3. The laminate according to claim 1, wherein the following relational expression (I) is satisfied: 1.2≦ E ＳｉＯ / E ＣＯ ≦20 ・・・(I)

4. 3. The laminate according to claim 1, wherein the cured film is a patterned partition wall.

5. 5. The laminate according to claim 4, wherein the partition walls have a reflectance of 20% or more and 85% or less at a wavelength of 550 nm per 10 [mu]m of film thickness.

6. 5. The laminate according to claim 4, wherein the partition walls have an optical density (OD) per 10 [mu]m film thickness at a wavelength of 450 nm of 1.5 or more and 3.0 or less.

7. 3. The laminate according to claim 1, wherein the cured film is a cured film obtained by curing a resin composition containing (A) a polysiloxane, (B) a photopolymerization initiator, (C) a photopolymerizable compound, and (D) a liquid-repellent compound.

8. 8. The laminate according to claim 7, wherein the polysiloxane (A) contains at least a styryl group.

9. 9. The laminate according to claim 8, wherein the polysiloxane (A) contains 10 to 60 mol % of repeating units having a styryl group based on all repeating units.

10. 8. The laminate according to claim 7, wherein the liquid-repellent compound (D) is a silicone surfactant.

11. 8. The laminate according to claim 7, wherein the content of the liquid-repellent compound (D) is 0.05% by weight to 2.00% by weight based on the total solid content of the resin composition.

12. 8. The laminate according to claim 7, wherein the resin composition does not contain a compound containing a fluorine atom.

13. The laminate according to claim 7 , wherein the resin composition further contains (E) a metal chelating agent.

14. 14. The laminate according to claim 13, wherein the metal chelating agent (E) is an aluminum chelate compound.

15. A resin composition comprising (A) a polysiloxane and (D) a liquid-repellent compound.

16. 16. The resin composition according to claim 15, wherein the polysiloxane (A) contains at least a styryl group.

17. 17. The resin composition according to claim 16, wherein the polysiloxane (A) contains 10 to 60 mol % of repeating units having a styryl group based on all repeating units.

18. 17. The resin composition according to claim 15, wherein the liquid-repellent compound (D) is a silicone surfactant.

19. 5. The laminate according to claim 4, further comprising a wavelength conversion layer in each of the cells partitioned by the partition walls.

20. A display device comprising the laminate according to claim 1 or 2 and a light emitting source selected from a liquid crystal cell, an organic EL cell, a mini LED cell, and a micro LED cell.

21. An information terminal comprising the display device according to claim 20.

Images