Laminate, resin composition, display device, and information terminal

Abstract

The purpose of the present invention is to provide a laminate having a cured film which has high adhesion to an inorganic film made of SiO2, SiN, or the like in an upper layer and has high liquid repellency, and with which it is easy to separately coat wavelength conversion layers after being formed as a partition wall pattern. The present invention is a laminate having a substrate and a cured film obtained by curing a resin composition. The laminate is characterized in that the cured film is configured such that, in an X-ray photoelectron spectroscopy (XPS analysis) on the upper surface of the cured film, a peak derived from a fluorine atom F1s is not observed, and the surface free energy on the upper surface of the cured film is 10-29 mN / m.

Description

Laminate, resin composition, display device and information terminal

[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.

[0002] In recent years, in order 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 riding on 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 their narrow half-width of emission spectrum (see, for example, Patent Documents 1 to 3). However, quantum dots have the drawback that their emission life is easily deteriorated by the presence of moisture and oxygen. Therefore, after filling the pixel with ink containing quantum dots and curing it, a protective film made of SiO ２ It is necessary to form an inorganic film such as SiN by sputtering or the like.

[0005] JP 2021-111681 A JP 2023-98817 A JP 2022-33154 A

[0006] The inventors, referring 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 conversion phosphor ink and a light-diffusing particle ink, and finally formed a SiO 2 layer as an inorganic protective film. ２ The film was formed by sputtering and evaluated. ２ After forming the film, a moist heat resistance test (temperature 85°C, humidity 85%) was carried out for 100 hours, and a cross-cut tape peeling test (a test for adhesion to an inorganic protective layer described later) was carried out. ２ Peeling occurred at the interface of the film, and it was found that there were issues with adhesion.

[0007] Therefore, the present invention provides a method for forming a partition wall pattern using a SiO 2 film having high liquid repellency and easily applying a wavelength conversion layer thereto after the partition wall pattern is formed. ２ The present invention aims to provide a laminate having a cured film that has high adhesion to an inorganic film such as silicon dioxide or SiN.

[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 has a fluorine atom-containing functional group such as a fluoroalkyl group, the SiO ２ In other words, it was found that the desired cured film can be obtained by not including fluorine atoms in the cured film and by having low surface free energy.

[0009] That is, the objects of the present invention are achieved by the following configurations: 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.

[0010] The laminate of the present invention has high liquid repellency, and after being formed into a partition wall pattern, it is easy to apply wavelength conversion layers separately. ２It is possible to provide a laminate having a cured film that has high adhesion to an inorganic film such as silicon dioxide or SiN.

[0011] 1 is a cross-sectional view showing one embodiment of a laminate of the present invention having a cured film, and FIG. 2 is a cross-sectional view showing one embodiment of a laminate of the present invention having partition walls patterned as a cured film. 1 is a top view micrograph of a state in which a small amount of 1,6-hexanediol diacrylate is applied to the center of a cell by inkjet, resulting in "good spreadability throughout the cell." 2 is a top view micrograph of a state in which a small amount of 1,6-hexanediol diacrylate is applied to the center of a cell by inkjet, resulting in "poor spreadability throughout the cell." 3 is a top view micrograph of a state in which a small amount of 1,6-hexanediol diacrylate is applied to the center of a cell by inkjet, resulting in "poor spreadability throughout the cell." 4 is a top view micrograph of a state in which a small amount of 1,6-hexanediol diacrylate is applied to the center of a cell by inkjet, resulting in "poor spreadability throughout the cell." 5 is a top view micrograph of a state in which a small amount of 1,6-hexanediol diacrylate is applied to the center of a cell by inkjet, resulting in "good top liquid repellency." 6 is a top view micrograph of a state in which a large amount of 1,6-hexanediol diacrylate is applied to the center of a cell by inkjet, resulting in "poor top liquid repellency." 7 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. 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 an inorganic protective layer. FIG. 2 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, an inorganic protective layer, and a color filter layer. FIG. 3 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. FIG. 4 is a cross-sectional view showing the configuration of a display device used for color mixing evaluation in the examples. FIG. 5 is an example of an XPS analysis result in which a peak derived from atom F1S was not observed. FIG. 6 is an example of an XPS analysis result in which a peak derived from atom F1S was observed.

[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, wherein the cured film 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.

[0014] The substrate in the laminate of the present invention refers to the 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. The laminate has a cured film 2 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 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 photosensitive resin composition and no pattern is 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 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 machines and reduction projection exposure devices. (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 development method in the development 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 and a hot plate. The atmosphere of the heating device is not particularly limited, and examples include nitrogen and air. 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 the XPS analysis of the upper surface of the cured film, "no peak due to fluorine atoms F1S is observed" means that no peak is observed at 691 eV, which is below the detection limit of the measuring device. When a peak due to fluorine atoms F1S is not observed, it is possible to determine whether the SiO ２ It can have high adhesion to inorganic films such as silicon dioxide and silicon nitride.

[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, an example of 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 is to form a cured film using a preferred composition of the resin composition described below.

[0030] The cured film of the laminate of the present invention has a siloxane bond (Si—O)-derived peak at 950 to 1250 cm in FT-IR analysis (ATR method). －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 ) preferably satisfies the following relational expression (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. －１ The absorption intensity of the peak top (E ＳｉＯ) is the wave number in the spectrum of 950 cm －１ point and 1250 cm －１ Connect the points with a straight line and measure the distance between 950 and 1250 cm. －１ When a perpendicular line is dropped from the peak top to this line, it represents the distance from the peak top to the intersection of the line and the perpendicular line. －１ The absorption intensity of the peak top (E ＣＯ ) is a wave number between 1650 and 1750 cm －１ It represents the distance measured in the same way within the range.

[0032] E ＳｉＯ / E ＣＯ When E is 1.2 or more, the liquid repellency and weather resistance can be improved by the siloxane bond components in the cured film. 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 crack resistance of the cured film can be improved by the organic components in 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 later, 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 wall preferably has a reflectance of 20% or more and 85% or less at a wavelength of 550 nm per 10 μm thickness. The thickness of the partition wall refers to the height and / or width of the partition wall described above. The height of the partition wall refers to the length of the partition wall 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 wall 3 is represented by the symbol H. The width of the partition wall refers to the length of the partition wall in a direction horizontal to the underlying surface. In the case of the laminate shown in FIG. 2, the width of the partition wall 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 wall contributes to improving the light extraction efficiency, and the OD value (light blocking property) contributes to suppressing color mixing between adjacent pixels. On the other hand, since the reflectance and OD value per thickness are believed to be the same regardless of the height direction or width direction, the present invention focuses on the reflectance and OD value per thickness of the partition wall. As described 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 of 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%, reflection at the side walls of the partition wall is reduced, light extraction efficiency is reduced, and the brightness of the display device is 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 walls of the partition wall, and the more improved the light extraction efficiency. However, if the reflectance at a wavelength of 550 nm per 10 μm of thickness exceeds 85%, color mixing of light occurs 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's ability to block blue light is insufficient. For example, when used as a partition wall separating wavelength conversion layers described below, blue light, which is excitation light, leaks into adjacent pixels, causing emission from 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, thereby 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 becomes 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 (for example, 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 may be determined by preparing a 10 μm-thick solid film having the same composition as the partition wall and measuring the transmittance of the solid film instead of the partition wall, as in the case of measuring the reflectance. 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, and the partition wall width can be easily formed 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 portions. 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 (for example, 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 order to set 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 resin composition as described below.

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

[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 by inkjet to the center of the cell, if the 1,6-hexanediol diacrylate has good coating spreadability throughout the cell, the wavelength-converting layer described below can be filled into the partition walls without gaps. "Good coating spreadability throughout the cell" refers to a 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 unevenly distributed in the center of the compartment or around sides one to three of the partition walls, but is present and spread around all four sides of the partition walls. For example, the state where "the coating spreadability over the entire cell is good" is shown in FIG. 3, and the state where "the coating spreadability over the entire cell is not good" is shown in FIGS. 4-1, 4-2, and 4-3, respectively.

[0046] Furthermore, when 1.5XYpL of 1,6-hexanediol diacrylate is dropped onto the center of a cell by inkjet 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 a 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 is contained within the cells. For example, a state in which "good top liquid repellency" is shown in Figure 5 and a state in which "good top liquid repellency" is shown in Figure 6.

[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 that separates cells with a width of 10 μm and an opening of 140 μm × 40 μm on a glass substrate, when 11 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 84 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 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] As the inorganic phosphor, those which emit colors such as green and red when excited by blue excitation light, that is, those which are excited by excitation light with a wavelength of 400 to 500 nm and have an emission spectrum with a peak in the region of 500 to 700 nm, are preferred. Examples of such inorganic phosphors include YAG-based phosphors, TAG-based phosphors, sialon-based 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 these inorganic semiconductors include Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, Si ３ N ４ , Ge ３ N ４ , Al ２ O ３ Two or more of these may be used.

[0054] As the organic fluorescent material, one that emits various colors such as green and red when excited by blue light is preferred. Examples of organic fluorescent materials 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 2011-241160 A.

[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-converting material coating liquid) into the spaces separated by the partition walls. The wavelength-converting 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 silicon oxide (SiO ２metal oxides such as 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 ２ ) or silicon nitride (SiN) is more preferred.

[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 a "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. The laminate has a color filter layer 6 on a base substrate 1, partition walls 3 formed as a patterned cured film thereon, wavelength conversion layers 4 in the pixels separated by the partition walls, and an inorganic protective layer 5 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 the 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 each color filter section are provided, a preferred configuration is one in which a black matrix 7 is formed under the partition wall and each color filter section 8 is 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 applications such 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 an organosilane compound, and refers to a resin having a siloxane bond (Si—O bond) as the main skeleton and 0 to 3 organic groups on the Si atom. It may have a silicone group (a dimethylsiloxane skeleton having two methyl groups on the Si atom) described below, but a resin having one or more skeletons other than a silicone group at a location other than the terminal 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]

[0072]

[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 ２ The 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 in 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 ３From 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] By including repeating units derived from a bifunctional organosilane compound, excessive thermal polymerization (condensation) of the polysiloxane due to heating can be suppressed, 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 even 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, by including repeating units derived from a trifunctional organosilane compound, the crosslink density of the polysiloxane in the cured film is increased, 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 formula (1) and the general formula (2) are derived from organosilane compounds represented by the following general formula (3) and the general formula (4), respectively. That is, polysiloxanes containing repeating units represented by the general formula (1) and the general formula (2) can be obtained by hydrolyzing and polycondensing organosilane compounds represented by the following general formula (3) and the general formula (4), respectively. Other organosilane compounds may also be used. In addition, in the general formula (3) and the general formula (4), "-(OR ４ ) ２ " and "-(OR ４ ) ３ " is written as "-(OR ４ )) are bonded together, respectively.

[0076]

[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, 3-methylpropyltriethoxy ... Examples 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 of 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, it is preferable that the (A) polysiloxane contains a methacrylic group, an acrylic group, or a styryl group, and it is even more preferable that the (A) polysiloxane contains at least a styryl group. The inclusion of a styryl group can lower 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 can improve 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 partition wall 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, the Mw is more preferably 4,000 or more. When the 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 in the development step, and the surface free energy of the cured film can be further reduced. On the other hand, from the viewpoint of developability and pattern processability, the Mw of the polysiloxane is preferably 500,000 or less, more preferably 300,000 or less. Here, the Mw of the polysiloxane in the present invention refers to the polystyrene equivalent value measured by gel permeation chromatography (GPC). The measurement method is as described in the examples below.

[0085] The polysiloxane (A) can be obtained by hydrolyzing the organosilane compound described above 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 and dehydration condensation reaction.

[0086] The content of the polysiloxane (A) 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-yl-phenyl)-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-(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 preferred 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 preferred 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 wt % or more, more preferably 1 wt % 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 wt % or less, more preferably 10 wt % 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, and not having a siloxane bond (Si—O bond) or a liquid-repellent functional group, which will be described later. In consideration of 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, and more preferably a methacryl group, an acrylic group, or a styryl group.

[0090] Examples of the photopolymerizable compound (C) 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 photopolymerizable compound (C) is preferably 1 wt % or more of the solid content from the viewpoint of effectively promoting radical curing, whereas the content of the photopolymerizable compound (C) is preferably 50 wt % 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 (boundaries between liquids, liquids and solids, liquids and gases, etc.), and here 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] Since the molecule does not contain fluorine atoms, the SiO ２The XPS analysis is an analysis of atoms present on the film surface, and in recent years, there have been concerns about the harmfulness of organic fluorine compounds to the human body due to their persistence in the environment and bioaccumulation, and studies on their regulation are currently underway, primarily in Europe. Therefore, it is possible to obtain a cured film that is excellent in environmental harmony.

[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, more preferably a methacryl group, an acrylic group, or a styryl group, and even more preferably an acrylic group or a styryl group.

[0095] The liquid-repellent compound (D) is preferably a silicone-based surfactant. By using a silicone-based surfactant, high water repellency derived from the silicone group can be imparted to the surface of the cured film. A silicone-based surfactant refers to a surfactant having a resin structure such as an acrylic resin or a polyimide resin as a main skeleton and further containing a silicone group as a liquid-repellent functional group. The silicone group refers to a dimethylsiloxane skeleton having a siloxane bond (Si—O bond) as the main skeleton and 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 silicone surfactants with photopolymerizable groups such as "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). 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 exceeds 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 the (E) 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 the (iv) heating step is performed at a low temperature of 80 to 100° C. This is because all or a part of the (E) metal chelating agent is incorporated into the film, and the (E) metal chelating agent can promote a condensation reaction between unreacted silanol groups remaining in the (a) component.

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

[0101]

[0102] (M represents a metal atom, R ５ are each independently a hydrogen atom, an alkyl group, an aryl group, or an alkenyl group, and R ６ and R ７are each independently hydrogen, 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.) From the viewpoint of low coloration of the formed cured film, examples of the metal atom M include titanium, zirconium, aluminum, zinc, cobalt, molybdenum, lanthanum, barium, strontium, magnesium, and calcium. 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 such 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 an ultraviolet absorber, a polymerization inhibitor, a surfactant, an adhesion improver, particles, a dispersant, a resin other than polysiloxane, 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 viewpoints of transparency and non-coloration, 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, and 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 that forms the cured film in the laminate of the present invention can further improve resolution during pattern formation by containing a polymerization inhibitor. 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 that forms the cured film in the laminate of the present invention can improve leveling properties during application by containing a surfactant that does not have a photopolymerizable group in addition to the liquid-repellent compound (D). Fluorine-based surfactants are known as surfactants that improve leveling properties, but for the reasons mentioned above, this composition does not contain a fluorine-based surfactant. 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 the (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 property), 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, and PB64. 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, mixed pigments of red and blue pigments are preferred from the viewpoint of achieving both a moderately high OD value and pattern processability. The mass ratio of the red and blue pigments 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 C.I. Pigment Green (hereinafter abbreviated as PG) 7, PG 36, PG 58, PG 37, and PG 59. 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, and PY185. 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 inclusion of a resin other than (A) polysiloxane can, for example, improve tacklessness after prebaking, 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 has the function of adjusting the viscosity of the resin composition to a range suitable for coating and improving 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 cyclohexane. 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 set to 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 for applications such as an anti-reflection layer of a low-reflection film that requires water repellency and anti-fouling 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 the (B) photopolymerization initiator and the (C) 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 the (B) photopolymerization initiator and the (C) 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. The (E) metal chelating agent 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 suitable ranges and addition amounts described above as 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 EL cell, a mini LED cell, and a micro LED cell. Because of their excellent light-emitting properties, organic 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 a light emitting source and pixels selected from organic EL cells, mini LED cells, and micro LED cells. The light emitting source 9 selected from organic EL cells, mini LED cells, and micro LED cells is disposed between partition walls 3 patterned on a base substrate 1, and a wavelength conversion layer 4 is further disposed thereon.

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

[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 listed 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 a polystyrene-equivalent weight average molecular weight by the following method: Apparatus: GPC measurement apparatus (2695) equipped with an RI detector, manufactured by Waters Corporation Column: PLgel MIXED-C column (300 mm, manufactured by Polymer Laboratories) x 2 (connected in series) Measurement temperature: 40°C Flow rate: 1 mL / min Solvent: 0.5% by mass solution of tetrahydrofuran (THF) Standard substance: 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 a 10 mm diameter Teflon (registered trademark) NMR sample tube. ２９ Si-NMR measurement was carried out, and the content ratio of each repeating unit was calculated from the ratio of the integrated value of Si derived from a specific organosilane to the integrated value of all Si derived from organosilanes. ２９ The Si-NMR measurement conditions are as follows: Apparatus: Nuclear magnetic resonance apparatus (JNM-GX270; manufactured by JEOL Ltd.) Measurement method: Gated decoupling method Measurement nuclear frequency: 53.6693 MHz ( ２９ Si nucleus) Spectral width: 20,000 Hz Pulse width: 12 μs (45° pulse) Pulse repetition time: 30.0 seconds Solvent: acetone-d6 Reference substance: tetramethylsilane Measurement temperature: 23° C. Sample rotation speed: 0.0 Hz.

[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 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 mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liters / minute. 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 a solids concentration of 40% by weight, yielding a polysiloxane (PSL-1) solution. The weight-average molecular weight of the resulting polysiloxane (PSL-1) was 5,000. Furthermore, 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 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 mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liters / minute. 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. Furthermore, 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-neck 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, and an aqueous phosphoric acid solution prepared by dissolving 3.92 g of phosphoric acid (1.0 wt % based on the charged monomers) in 92.14 g of water was added 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 mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liters / minute. 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 a solids concentration of 40% by weight, yielding a polysiloxane (PSL-3) solution. The weight-average molecular weight of the resulting polysiloxane (PSL-3) was 4,000. Furthermore, 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-neck 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, and an aqueous phosphoric acid solution prepared by dissolving 4.00 g (1.0 wt % based on the charged monomers) in 92.14 g of water was added 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 mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liters / minute. 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-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 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 mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liters / minute. 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 a solids concentration of 40% by weight, yielding a polysiloxane (PSL-5) solution. The weight-average molecular weight of the resulting polysiloxane (PSL-5) was 5,000. Furthermore, 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 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 mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liters / minute. 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 a solids concentration of 40% by weight, yielding a polysiloxane (PSL-6) solution. The weight-average molecular weight of the resulting polysiloxane (PSL-6) was 6,000. Furthermore, 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 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 mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liters / minute. 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. Furthermore, 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, 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 over 30 minutes with stirring at 40 ° C. Thereafter, the flask was immersed in an oil bath at 70 ° C. 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) 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 liters / minute. A total of 196 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, yielding a polysiloxane (PSL-8) solution. The weight-average molecular weight of the obtained 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, and 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 so that the solids concentration was 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, and 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 so that the solids concentration was 40% by weight, to obtain a polysiloxane (PSL-10) solution. The weight-average molecular weight of the obtained polysiloxane (PSL-10) was 4,300. Furthermore, 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 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 mixed gas of 95% by volume of nitrogen and 5% by volume of oxygen was flowed at 0.05 liters / minute. 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 together in Table 1.

[0165]

[0166]

[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, and then 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 were added and stirred at room temperature for a while. The atmosphere in the flask was replaced with nitrogen, and then the mixture was heated and stirred at 70° C. for 5 hours. Next, 15.00 g (0.106 mol) of glycidyl methacrylate, 1.00 g of triphenylphosphine, 0.200 g of p-methoxyphenol, and 100 g of PGMEA were added to the resulting solution, and the mixture was heated and stirred at 90°C for 4 hours to obtain a (meth)acrylic polymer solution. PGMEA was added to the resulting (meth)acrylic polymer solution so that the solids concentration was 40 wt%, to obtain a (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")) as particles, 0.50 g of phosphate polyester ("DISPERBYK" (registered trademark)-111; manufactured by BYK Japan KK (hereinafter referred to as "DISPERBYK-111")) as a dispersant, and 4.50 g of PGMEA as a solvent were mixed and 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, a photopolymerizable compound, dipentaerythritol hexaacrylate ("KAYARAD" (registered trademark) DPHA, manufactured by Shinnihon Pharmaceutical Co., Ltd. (hereinafter referred to as "DPHA")) 1.60 g, a liquid-repellent compound, 0.125 g of "GAFAC" (registered trademark) RS-57 (20 wt % MIBK diluted solution, manufactured by DIC Corporation (hereinafter referred to as "RS-57")), 0.100 g of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate ("CELLOXIDE" (registered trademark) 2021P, manufactured by Daicel Corporation (hereinafter referred to as "CELLOXIDE 2021P")) as an adhesion promoter, and 0.100 g of "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 1.00 g of a solvent 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) Polysiloxane (PSL-1) solution 16.1 g, as a photopolymerization initiator, OXE-02 0.120 g, Omnirad-819 0.0400 g, as a photopolymerizable compound, DPHA "1.28 g, as a liquid-repellent compound, RS-57 0.100 g, as an adhesion improver, Celloxide 2021P 0.0800 g, as a polymerization inhibitor, Irganox 1010 0.0200 g and acrylic surfactant BYK-352 PGMEA 10 wt% diluted solution 0.100 g (equivalent to a concentration of 500 ppm), solvent PGMEA 1.59 g, DAA 0.600 It was dissolved and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a resin composition (P-18).

[0186] Example 19 Resin composition (P-19) 5.00 g of titanium nitride black pigment as particles, 0.50 g of phosphate polyester DISPERBYK-111 as a dispersant, and 4.50 g of PGMEA as a solvent were mixed and 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, as a photopolymerization initiator, 0.120 g of OXE-02, 0.0400 g of Omnirad-819, as a photopolymerizable compound, 1.28 g of DPHA ", as a liquid-repellent compound, 0.100 g of RS-57, as an adhesion improver, 0.0800 g of Celoxide 2021P, as a polymerization inhibitor, 0.0200 g of Irganox 1010 and 0.100 g of a 10 wt% diluted solution of acrylic surfactant BYK-352 PGMEA (equivalent to a concentration of 500 ppm), 1.89 g of solvent PGMEA, DAA 0.600, and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a 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, as a dispersant, 0.50 g of phosphate polyester DISPERBYK-111, as a solvent, 4.48 g of PGMEA was mixed and dispersed using a mill-type disperser filled with zirconia beads to obtain a particle dispersion (MW-3). Particle dispersion (MW-2) instead of particle dispersion (MW-3) 3.20 g was added, the amount of polysiloxane (PSL-1) solution added was 7.25 g, except that 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 PGMEA solvent 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(ethylacetoacetate) (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 as the metal chelating agent instead of ZC-150.

[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 instead of ZC-150 as a metal chelating agent.

[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 DAA and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a 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 of DAA and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a 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 hollow silica 20 wt% IPA solution (trade name Sururia 4110, manufactured by JGC Catalysts and Chemicals Co., Ltd. (hereinafter "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), 7.03 g of solvent PGMEA, 0.700 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 a (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 a (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 % PGMEA solution of cardo polymer V-259ME 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: fluorosurfactant with a 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% diluted solution of acrylic surfactant BYK-352 in PGMEA (corresponding to a concentration of 500 ppm) were dissolved in 4.23 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-48).

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

[0216]

[0217]

[0218]

[0219]

[0220] Preparation Example 1 Color-Converting Luminescent Material Composition (CL-1) 20 parts by weight of a 0.5 wt % toluene solution of a green quantum dot material (Lumidot 640 CdSe / ZnS, average particle size 6.3 nm: manufactured by Aldrich Chemical), 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 an acrylic resin (SPCR-18 (trade name), manufactured by Showa Denko K.K.), and 97 parts by weight of toluene were mixed and stirred to form a uniform solution. 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-Converting Luminescent Material Composition (CL-2) A color-converting luminescent 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 zirconia beads with a diameter of 0.5 mm as media, to prepare a 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) 90 g of C.I. Pigment Green 59, 60 g of C.I. Pigment Yellow 150, 75 g of polymer dispersant ("BYK" (registered trademark) -6919 (trade name) manufactured by BYK-Chemie Co., Ltd. (hereinafter referred to as "BYK-6919")), 100 g of binder resin ("ADEKA ARCLES" (registered trademark) WR301 (trade name) manufactured by ADEKA Corporation), and 675 g of PGMEA were mixed to prepare a slurry. The beaker containing the slurry was connected to a Dyno Mill by a tube, and dispersion treatment was carried out for 8 hours at a peripheral speed of 14 m / s using zirconia beads with a diameter of 0.5 mm as media to prepare a Pigment Green 59 dispersion (GD-1).

[0225] A color filter material (CF-1) was prepared by mixing 56.54 g of CI 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 As the base substrate, a 10 cm square alkali-free glass substrate (manufactured by AGC Technoglass Co., Ltd., thickness 0.7 mm; the same applies hereinafter) or a Si wafer (6 inches) was used. The resin compositions shown in Tables 3 to 5 were applied thereon by spin coating, and dried for 3 minutes at a temperature of 90°C using a hot plate (trade name SCW-636, manufactured by Dainippon Screen Mfg. Co., Ltd.; the same applies hereinafter) to produce a dried film. The produced dried film 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, manufactured by Canon Inc.; the same applies hereinafter) at an exposure dose of 300 mJ / cm. ２ The film was exposed to 100 uV (equivalent to i-line radiation). Thereafter, using an automatic developing apparatus ("AD-2000 (trade name)" manufactured by Takizawa Sangyo Co., Ltd.; the same applies hereinafter), shower development was performed using a 0.045 wt % aqueous potassium hydroxide solution for 100 seconds, followed by rinsing with water for 30 seconds. Furthermore, by heating in an oven (trade name IHPS-222, manufactured by Espec Corporation; the same applies hereinafter) at a temperature of 150°C for 60 minutes in air, 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 openings spaced at a pitch of 40 μm x 140 μm were formed 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 a base substrate, and the resin compositions shown in Tables 6 to 8 were applied thereon by spin coating, and a lattice-like barrier rib pattern was formed in the same manner as in Examples 39 to 71 and Comparative Examples 11 to 25, to prepare laminates provided with a cured film.

[0228] Next, the color-converting light-emitting material composition (CL-1) was applied to 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 resulting laminate was then placed in a sputtering apparatus SH-450 (manufactured by ULVAC, Inc.), and silicon oxide was used as the sputtering target, and SiO was deposited from the top to form an inorganic protective layer with a thickness of 0.1 μm. ２ A layer was formed, and a laminate having the cured film, the wavelength converting layer, and the inorganic protective layer as shown in FIG. 8 was obtained.

[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 a base substrate. The resin compositions shown in Tables 9 to 10 were applied thereon by spin coating, and dried for 3 minutes at 90°C using a hot plate to produce a dried film. The dried film thus produced was exposed to light of 300 mJ / cm2 on the entire surface of the dried film using a parallel light mask aligner and an ultra-high pressure mercury lamp (g, h, i lines) as a light source. ２ (i-line equivalent value). Thereafter, using an automatic developing apparatus, shower development was performed using a 0.045 wt % potassium hydroxide aqueous solution for 100 seconds, followed by rinsing with water for 30 seconds. Further, by heating in an oven at a temperature of 90°C for 60 minutes in air, a solid film (cured film) with a height of 10 µm was formed on the glass substrate or Si wafer, and a laminate was produced.

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

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241] The evaluation methods for the laminated films provided with the cured films in each of the Examples and Comparative Examples are as follows.

[0242] <Height> For the cured film in the laminate obtained in each of the Examples and Comparative Examples, the film thickness of the partition wall portion was measured using a SURFCOM stylus 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> The plain film portion of the cured film in the laminate obtained in each Example and Comparative Example was analyzed by the Shiga Prefectural Industrial Technology Center. Fluorine atoms, carbon atoms, oxygen atoms, silicon atoms, and nitrogen atoms were analyzed from the top surface of the film using an X-ray photoelectron spectrometer PHI5000 Versa Probe2 (manufactured by ULVAC-PHI, Inc.). When no peak was observed at 691 eV, the measurement was below the detection limit of the measuring device, and it was determined that no peak due to fluorine atoms F1S was observed, it was determined that "no F." When a peak was observed at 691 eV, and it was determined that a peak due to fluorine atoms F1S was observed, it was determined that "F was present." As an example, the XPS analysis result of Example 39, which was determined to be "no F," is shown in FIG. 12, and the XPS analysis result of Comparative Example 21, which was determined to be "F present," is shown in FIG. 13.

[0244] <Surface Free Energy> The contact angle of the solid film portion of the cured film in the laminate obtained in each Example and Comparative Example was measured at 25°C in air using a microsyringe DM-700 (manufactured by Kyowa Interface Science Co., Ltd.) and a 22G Teflon (registered trademark) coated needle for a contact angle meter in accordance with the wettability test method for substrate glass surfaces specified in JIS R3257 (established on April 20, 1999). However, diiodomethane was also used in addition to water, and the contact angles of water and diiodomethane on the solid film surface were measured. From each measured value, the surface free energy (mN / m) was calculated based on the theoretical formula of Owents and Wendt.

[0245] <FT-IR Analysis> The solid film portion of the cured film in the laminate obtained in each Example and Comparative Example was measured by total reflection infrared spectroscopy (ATR) using a Fourier transform infrared spectrometer Avatar 360 (manufactured by Nicolet Corporation). The sample surface was measured using a single reflection horizontal ATR measurement device (OMNI Sampler) manufactured by the same company and a diamond ATR crystal as accessories for total reflection measurement. The measurement conditions were a resolution of 4 cm －１ The number of scans was set to 32, and the measurement was performed. The obtained spectrum was recorded from 950 to 1780 cm －１ After performing slope correction in the range of 950 to 1250 cm －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 ) was calculated. ＳｉＯ , E ＣＯ As mentioned above,

[0246] <Inkjet Test> "Spreadability in Spreading a Small Amount of 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 a cell separated by the partition wall using an inkjet coating device (InkjetLabo, manufactured by Cluster Technology Co., Ltd.). After the dropping, the laminate was observed from above with an optical microscope (magnification 100x), and the "spreadability in Spreading a Small Amount of Coating" was evaluated according to the following criteria. As examples, the results of Example 39, which was rated "A," are shown in FIG. 3, the results of Example 48, which was rated "B," are shown in FIG. 4-1, the results of Example 49, and the results of Example 50 are shown in FIG. 4-3. In addition, cases where a partition wall pattern could not be formed were marked with "-." A: The coated 1,6-hexanediol diacrylate was not unevenly distributed in the center of the compartment or around the first to third sides of a certain partition wall, but was present and spread around all four sides of the partition wall, indicating "good coating spreadability throughout the entire cell." B: The coated 1,6-hexanediol diacrylate was unevenly distributed in the center of the compartment or around the first to third sides of a certain partition wall, indicating "poor coating spreadability throughout the entire cell." "Liquid repellency at the top of the partition wall when excessively coated" Similarly, 84 pL of 1,6-hexanediol diacrylate was dropped onto the center of another cell. After the dropping, the laminate was observed from above with an optical microscope (100x magnification), and the "liquid repellency at the top of the partition wall when excessively coated" was evaluated according to the following criteria. For example, 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. Furthermore, cases where a partition wall pattern could not be formed were marked with "-." A: The coated 1,6-hexanediol diacrylate did not climb up onto the top of the partition wall, and "top liquid repellency was good." B: The coated 1,6-hexanediol diacrylate climbed up onto the top of the partition wall, and "top liquid repellency was not good." <Reflectance> For the solid film portion of the cured film in the laminate obtained in each of the Examples and Comparative Examples, the reflectance was measured in SCI mode from the solid film side in the wavelength range of 360 nm to 740 nm using a spectrophotometer CM-2600d (manufactured by Konica Minolta, Inc.). The value at a wavelength of 550 nm was taken as "reflectance."

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

[0248] <Crack Resistance> The laminates provided with the cured films obtained in each of the Examples and Comparative Examples were additionally heated in air under the following conditions using an oven IHPS-222 (manufactured by Espec Corporation), and then visually observed to evaluate the presence or absence of cracks in the solid film portion of the cured film. A: No cracks were observed after 30 minutes of heating at 230°C. B: No cracks were observed after 30 minutes of heating at 180°C, but one or more cracks were observed after 30 minutes of heating at 230°C. C: One or more cracks were observed after 30 minutes of heating at 180°C.

[0249] <Separate Coating of Wavelength Conversion Layer> For the partition wall pattern portion of the cured film in the laminate obtained in each Example and Comparative Example, the color-converting luminescent material composition (CL-1) was applied to the center of the cells separated by the partition walls in the same manner as in the recent <Inkjet Test> to form a wavelength conversion layer, so that the thickness after curing was 10 μm. Then, 11 pL to 84 pL of the color-converting luminescent material composition (CL-2) was similarly dropped into the center of an adjacent cell in the same manner to form a thickness after curing of 10 μm, and the separate coating of the wavelength conversion layer was evaluated according to the following criteria. Note that if a partition wall pattern could not be formed, it was marked with "-". A: When 11 pL of the color-converting luminescent material composition (CL-2) was dropped, the color-converting luminescent material composition spread well throughout the cell, and even after 84 pL was dropped, the cell was filled with the color-converting luminescent material composition (CL-2) without any gaps, and CL-2 did not climb up onto the tops of the partition walls at all, and CL-2 did not overflow into or mix with the cells in which the wavelength-converting layer was formed using the color-converting luminescent material composition (CL-1), resulting in good color-separate coating of the wavelength-converting layer. B: When 11 pL of the color-converting luminescent material composition (CL-2) was dropped, CL-2 was unevenly distributed around sides one to three of the partition walls and did not spread well, but after 84 pL was dropped, the cell was filled with the color-converting luminescent material composition (CL-2) without any gaps, and CL-2 did not climb up onto the tops of the partition walls at all, and CL-2 did not overflow into or mix with the cells in which the wavelength-converting layer was formed using the color-converting luminescent material composition (CL-1), resulting in relatively good color-separate coating of the wavelength-converting layer. C: 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, it was still filled into the cell without any gaps. CL-2 partially ran onto the top of the partition wall, but CL-2 did not overflow into or mix with the cells in which the wavelength-converting layer was formed using the color-converting luminescent material composition (CL-1), and the ability to coat the wavelength-converting layer was relatively good. D: When 11 pL of the color-converting luminescent material composition (CL-2) was dropped, CL-2 was unevenly distributed around sides one to three of the partition wall, and the ability to coat the wavelength-converting layer was poor, but after 84 pL was dropped, it was filled into the cell without any gaps. CL-2 partially ran onto the top of the partition wall, but CL-2 did not overflow into or mix with the cells in which the wavelength-converting layer was formed using the color-converting luminescent material composition (CL-1), and the ability to coat the wavelength-converting layer was relatively good.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 walls and the coating spreadability was poor, and even when 84 pL was dropped, the cell was not completely filled and gaps were generated, and the ability to coat the wavelength-converting layer was poor. F: When 11 pL of the color-converting luminescent material composition (CL-2) was dropped, the coating spreadability was good over the entire cell, and even after 84 pL was dropped, the cell was filled without gaps, but CL-2 completely climbed onto the top of the partition walls and overflowed and mixed into the cells where the wavelength-converting layer had been formed using the color-converting luminescent material composition (CL-1), and the ability to coat the wavelength-converting layer was poor.

[0250] <Adhesion to Inorganic Protective Layer> The laminate obtained in each of the Examples and Comparative Examples was placed in a sputtering device SH-450 (manufactured by ULVAC, Inc.), and silicon oxide was used as a sputtering target to form an inorganic protective layer of SiO 2 having a thickness of 0.1 μm from the top. ２ This laminate was placed in a thermo-hygrostat under conditions of a temperature of 85°C and a humidity of 85% for 100 hours. ２ An adhesion test was carried out on the solid portion of the cured film where the layers were laminated. ２ On the surface of the layer, 11 parallel lines were drawn at 1 mm intervals, each perpendicular to the other, with a cutter knife so as to reach the base of the substrate, creating 100 1 mm x 1 mm grids. ２ A cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) was attached to the surface of the layer and rubbed with an eraser (compliant with JIS S6050) to adhere it. One end of the tape was held perpendicular to the plate and instantly peeled off, and the number of remaining squares was visually counted and tested. The "adhesion to the inorganic protective layer" of the cured film was evaluated based on the peeled area of ​​the squares using the following criteria: 5B: Peeled area = 0% 4B: Peeled area = more than 0% but less than 5% 3B: Peeled area = 5% or more but less than 15% 2B: Peeled area = 15% or more but 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 was on the light source side. A current of 30 mA was passed through this surface light-emitting device to light up the LED elements, and the brightness (unit: cd / m2) 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 taken as the standard 100. In addition, when a barrier rib pattern could not be formed, it was recorded as "-".

[0253] <Color Mixing> A blue organic EL cell having the same width and in the same location as the wavelength conversion layer partially formed within the grid-shaped partition wall was prepared. The laminate obtained in each of Examples 72 to 104 and Comparative Examples 26 to 40 was then bonded to the blue organic EL cell with a sealant, facing each other, to obtain a display device having the configuration shown in FIG. 11 . Of the blue organic EL cells 10 in FIG. 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 Corporation). 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 irradiated with light having a wavelength of 633 nm from the direction perpendicular to the cured film surface using a prism coupler (PC-2000 (manufactured by Metricon Co., Ltd.) under atmospheric pressure and at 20°C, and the refractive index was measured, rounding to two decimal places. Note that when measurement was not possible due to strong reflection or light blocking, the value was recorded as "-".

[0255] <Stain Resistance> A non-alkali glass substrate was used as the base substrate. For the laminates obtained in Examples 120 to 123 and Comparative Examples 48 to 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 to stand for 1 minute in a room at room temperature of 25°C. A 500 g standard weight (International Organization for Metrology Class F2, 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 reciprocation per second 30 times. The condition of the line after wiping was visually confirmed, and stain resistance was evaluated according to the following evaluation criteria: A: The line had disappeared after wiping. B: The line remained after wiping, although its color was lighter than before wiping. C: The line remained after wiping, unchanged from before wiping.

[0256] <Chemical Resistance (Low-Temperature Curing Property)> 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} x 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 5% or more.

[0257] REFERENCE SIGNS LIST 1 substrate 2 cured film H partition wall height L partition wall width θ partition wall taper angle 3 partition wall HDDA 1,6-hexanediol diacrylate 4 wavelength conversion layer 4 (CL-1) wavelength conversion layer formed from color conversion light emitting material composition (CL-1) 5 inorganic protective layer 6 color filter layer 7 black matrix 8 color filter portion of each color 9 light emitting source selected from organic EL cell, mini LED cell and micro LED cell 10 blue organic EL cell

Claims

1. A laminate comprising a substrate and a cured film obtained by curing a resin composition, wherein in X-ray photoelectron spectroscopy (XPS analysis) of an upper surface of the cured film, no peak derived from fluorine atoms F1s is observed, 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, and the cured film is a patterned partition wall, and the partition wall has an OD value of 1.5 or more and 3.0 or less at a wavelength of 450 nm per 10 μm of film thickness.

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. 2. The laminate according to claim 1, wherein the partition walls have a reflectance of 20% or more and 85% or less at a wavelength of 550 nm per 10 μm of film thickness.

5. 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.

6. 6. The laminate according to claim 5, wherein the polysiloxane (A) contains at least a styryl group.

7. 7. The laminate according to claim 6, wherein the polysiloxane (A) contains 10 to 60 mol % of repeating units having a styryl group based on all repeating units.

8. 6. The laminate according to claim 5, wherein the liquid-repellent compound (D) is a silicone surfactant.

9. 6. The laminate according to claim 5, 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.

10. 6. The laminate according to claim 5, wherein the resin composition does not contain a compound containing a fluorine atom.

11. The laminate according to claim 5 , wherein the resin composition further contains (E) a metal chelating agent.

12. 12. The laminate according to claim 11, wherein the metal chelating agent (E) is an aluminum chelate compound.

13. 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, and the cured film is a patterned partition wall, and the laminate has a wavelength conversion layer within a cell partitioned by the partition wall.

14. A display device comprising: a substrate; a laminate having a cured film formed by curing a resin composition, wherein the cured film is characterized in that no peak derived from fluorine atoms F1s is observed in X-ray photoelectron spectroscopy analysis (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; and an emission light source selected from a liquid crystal cell, an organic EL cell, a mini LED cell, and a micro LED cell.

15. An information terminal comprising the display device according to claim 14.