Laminate, resin composition, display device, and information terminal

Abstract

The present invention aims to provide a laminate having a cured film with high liquid repellency, easy separation coating of a wavelength conversion layer after being formed into a partition wall pattern, and high adhesion to an inorganic film such as SiO2, SiN of an upper layer. The present invention is a laminate characterized by being 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 atom 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.

Description

Technical Field

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

[0002] In recent years, to achieve wide color gamut / high contrast in displays, display devices have been proposed that use a blue light source as backlight and employ color filters (wavelength conversion sections) filled with wavelength-converting phosphors and / or light-diffusing particles in pixels separated by spacers for color conversion (for example, see Patent Document 1). A method has been proposed to form wavelength conversion sections by separately coating wavelength-converting phosphor ink in green / red pixels and light-diffusing particle ink in blue pixels using inkjet coating after forming spacers using a resin composition via photolithography (for example, see Patent Documents 2 and 3). To accurately separate the inks during coating, the ink must not climb onto the top of the spacers; therefore, the top of the spacers must be ink-repellent. Conversely, the interior of the pixels must be hydrophilic for ink application.

[0003] As a method for imparting liquid repellency to the top of the spacer wall, a method has been proposed for forming the spacer wall using a resin composition containing a liquid-repellent compound. For example, in Patent Document 3, liquid repellency is imparted to the top of the spacer wall by photocuring a resin composition containing a liquid-repellent compound having a photopolymerizable group and a fluoroalkyl group onto a substrate and then photocuring it.

[0004] In recent years, the emission spectrum of phosphors used for wavelength conversion has become narrow, leading to the widespread use of quantum dots, which are inorganic particles of nanoscale size (see, for example, Patent Documents 1-3). However, quantum dots have the disadvantage that their emission lifetime is easily degraded by the presence of moisture and oxygen. Therefore, after filling the pixel with ink containing quantum dots and allowing it to solidify, it is necessary to form an inorganic film such as SiO2 or SiN as a protective film by sputtering or other methods.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2021-111681

[0008] Patent Document 2: Japanese Patent Application Publication No. 2023-98817

[0009] Patent Document 3: Japanese Patent Application Publication No. 2022-33154 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] Referring to Patent Document 3, the inventors formed a spacer using a resin composition containing a liquid-repellent compound with photopolymerizable groups and fluoroalkyl groups. They then used a wavelength-converting phosphor ink and a light-diffusing particle ink for inkjet coating / photocuring to form a wavelength-converting layer. Finally, they formed a SiO2 film as an inorganic protective film using a sputtering method and conducted an evaluation study. However, after forming the SiO2 film, a 100-hour damp heat resistance test (temperature 85°C, humidity 85%) and a cross-cut tape peel test (described later in the <Adhesion to Inorganic Protective Layer> test) were performed. The results showed that peeling occurred at the interface between the spacer and the SiO2 film, indicating a problem with adhesion.

[0012] Therefore, the present invention aims to provide a laminate with a cured film, wherein the cured film has high liquid repellency, is easy to separately coat the wavelength conversion layer after being formed into a spacer pattern, and has high adhesion to the upper inorganic film such as SiO2 or SiN.

[0013] Methods for solving problems

[0014] The inventors of this application conducted in-depth research and discovered that if the cured liquid-repellent compound in the film contains functional groups containing fluorine atoms, such as fluoroalkyl groups, the adhesion to the upper SiO2 or SiN film decreases. In other words, they discovered that a desired cured film can be obtained by ensuring that the cured film does not contain fluorine atoms and has a low surface free energy.

[0015] That is, the objective of the present invention is achieved through the following configuration.

[0016] A laminate comprising a substrate and a cured film formed by curing a resin composition, wherein no peak originating from fluorine atoms F1s is observed in X-ray photoelectron spectroscopy (XPS analysis) of the cured film surface, and the surface free energy of the cured film surface is 10 mN / m or more and 29 mN / m or less.

[0017] A resin composition characterized by containing (A) a polysiloxane and (D) a liquid-repellent compound.

[0018] The effects of the invention

[0019] According to the present invention, a laminate with a cured film can be provided, wherein the cured film has high liquid repellency, the wavelength conversion layer is easy to separate after being formed into a spacer pattern, and has high adhesion to the upper inorganic film such as SiO2 or SiN. Attached Figure Description

[0020] Figure 1A cross-sectional view showing one embodiment of the laminate of the present invention having a cured film.

[0021] Figure 2 A cross-sectional view showing one embodiment of the laminate of the present invention having spacers formed by patterning as a cured film.

[0022] Figure 3 Microscopic photograph of the upper surface showing "good spreadability throughout the unit" when a small amount of 1,6-hexanediol diacrylate is applied to the center of the unit by inkjet printing.

[0023] Figure 4-1 Microscopic image of the upper surface showing poor spreadability throughout the unit when a small amount of 1,6-hexanediol diacrylate was applied to the center of the unit by inkjet printing.

[0024] Figure 4-2 Microscopic image of the upper surface showing poor spreadability throughout the unit when a small amount of 1,6-hexanediol diacrylate was applied to the center of the unit by inkjet printing.

[0025] Figure 4-3 Microscopic image of the upper surface showing poor spreadability throughout the unit when a small amount of 1,6-hexanediol diacrylate was applied to the center of the unit by inkjet printing.

[0026] Figure 5 Microscopic image of the top surface in a "good liquid repellency" state when 1,6-hexanediol diacrylate is overcoated in the center of the cell by inkjet printing.

[0027] Figure 6 Microscopic image of the top surface showing "poor liquid repellency" when 1,6-hexanediol diacrylate is overcoated in the center of the cell by inkjet printing.

[0028] Figure 7 A cross-sectional view showing one embodiment of the laminate of the present invention having spacers and a wavelength conversion layer formed by patterning as a curing film.

[0029] Figure 8 A cross-sectional view showing one embodiment of the laminate of the present invention having spacers, a wavelength conversion layer and an inorganic protective layer formed by patterning as a curing film.

[0030] Figure 9 A cross-sectional view showing one embodiment of the laminate of the present invention having a spacer wall, a wavelength conversion layer, an inorganic protective layer and a color filter layer formed by patterning as a cured film.

[0031] Figure 10A cross-sectional view showing one embodiment of the stack of the present invention having a spacer wall formed by patterning as a curing film, a wavelength conversion layer, and a light source selected from organic EL units, mini LED units, and micro LED units.

[0032] Figure 11 A cross-sectional view showing the configuration of the display device used for color mixing evaluation in the embodiment.

[0033] Figure 12 Example of XPS analysis results where no peak originating from the F1S atom was observed.

[0034] Figure 13 Example of XPS analysis results for observing peaks originating from the F1S atom. Detailed Implementation

[0035] The present invention will now be described in further detail. Hereinafter, suitable embodiments of the laminate, resin composition, display device, and information terminal of the present invention will be specifically described, but the present invention is not limited to these embodiments and can be implemented with various modifications according to purpose and application.

[0036] The laminate of the present invention is a laminate having a substrate and a cured film formed by curing a resin composition. The laminate is characterized in that no peak originating from fluorine atom F1S is observed in the 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.

[0037] The term "substrate" in the laminate of the present invention refers to the base material in the laminate of the present invention. Examples of substrates include glass substrates, resin plates, resin films, TFTs, PCBs, and other driving substrates. Alkali-free glass is preferably used as the material for the glass substrate. Polyester, (meth)acrylate polymers, transparent polyimide, polyethersulfone, etc., are preferably used as the materials for the resin plate and resin film. The thickness of the glass plate and resin plate is preferably 1 mm or less, and more preferably 0.8 mm or less. Polyethylene terephthalate, TAC (triacetyl cellulose), polyimide, cyclic olefin polymers, polycarbonate, etc., are preferably used as the material for the resin film. The thickness of the resin film is preferably 100 μm or less.

[0038] It should be noted that when using a driving substrate such as a TFT or PCB as the substrate, it is preferable to further have a light source selected from organic EL units, mini LED units and micro LED units, as described later, on the substrate.

[0039] The so-called cured film in the laminate of the present invention refers to a cured film formed by curing a resin composition, which is a film formed by curing a resin composition by means of, for example, heat and / or light.

[0040] exist Figure 1 The image shows a cross-sectional view of one embodiment of the laminate of the present invention having a substrate and a cured film. A cured film 2 is provided on the substrate 1.

[0041] Examples of resin compositions include, for instance, thermosetting resin compositions that cure by heat, photocurable resin compositions that cure by light irradiation, negative photosensitive resin compositions that cure by heat and light irradiation and allow the exposed or unexposed portions to be removed in the subsequent development process, thereby enabling pattern formation, and positive photosensitive resin compositions that cure primarily by heat and allow the exposed portions to be removed in the subsequent development process, thereby enabling pattern formation. The resin composition described later is preferred.

[0042] As a method for forming the cured film in the laminate of the present invention, for example, it is selected from (i) a coating step of coating a resin composition on a substrate and drying it to obtain a dried film, (ii) an exposure step of irradiating the obtained dried film with light, (iii) a development step of dissolving and removing the portion of the exposed dried film that is soluble in the developer, and (iv) a heating step of curing the developed film.

[0043] 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 developing step, and (iv) a heating step. When the resin composition is a positive photosensitive resin composition and pattern formation is not performed, it is preferable to have at least (i) a coating step, (iii) a developing step, (ii) an exposure step, and (iv) a heating step in sequence; when pattern formation is performed, it is preferable to have at least (i) a coating step, (ii) an exposure step, (iii) a developing step, and (iv) a heating step in sequence.

[0044] Examples of coating methods in the coating process (i) include slot coating and spin coating. Examples of drying methods in the coating process (i) include drying apparatus such as an oven or a hot plate. The atmosphere of the drying apparatus is not particularly limited and examples include nitrogen or air. The drying temperature is preferably 80–120°C, and the drying time is preferably 1–60 minutes.

[0045] Examples of exposure apparatus used in the exposure step (ii) include proximity exposure machines and reduced-projection exposure devices. Examples of active light used for irradiation in the exposure step (ii) include near-infrared light, visible light, and ultraviolet light, with ultraviolet light being preferred. Among ultraviolet light, wavelengths selected from i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) are more preferred, and a mixture of i-rays, h-rays, and g-rays is even more preferred. 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 based on the thickness of the dried film being exposed. Generally, 1–100 mW / cm² is preferred. 2 The output of the ultra-high pressure mercury lamp is 1–10,000 mJ / cm. 2 Exposure is performed using the specified exposure amount. It should be noted that in the exposure process (ii), in order to form patterns such as the spacer described later, exposure can be performed through a photomask with a specified opening, or an arbitrary pattern can be drawn directly using a laser or the like without using a photomask.

[0046] Examples of development methods in the (iii) developing process include, for example, immersion, spraying, and brushing. The developing solution used can be a solvent capable of dissolving unwanted portions of the exposed film, preferably an aqueous solution with water as the main component. Examples of developing solutions include, for example, 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. From the viewpoint of improving resolution, potassium hydroxide aqueous solution or tetramethylammonium hydroxide aqueous solution is preferred. From the viewpoint of improving developability, the concentration of the alkaline aqueous solution is preferably 0.01% by weight or more, more preferably 0.03% by weight or more. On the other hand, from the viewpoint of suppressing the peeling and etching of the pattern before heating, the concentration of the alkaline aqueous solution is preferably 5% by weight or less, more preferably 1% by weight or less. Furthermore, from the viewpoint of improving resolution, a surfactant can be included in the developing solution. To facilitate process management, the developing temperature is preferably 20–50°C.

[0047] Examples of heating devices used in the heating process (iv) include, for example, an oven or a hot plate. The atmosphere of the heating device is not particularly limited, and examples include nitrogen or air. The heating temperature is preferably 80–250°C, and the drying time is preferably 1–60 minutes.

[0048] The cured film in the laminate of the present invention is characterized in that, in the X-ray photoelectron spectroscopy (XPS analysis) of the upper surface of the cured film, no peak originating from fluorine atom F1S is observed, and the surface free energy of the upper surface of the cured film is more than 10 mN / m and less than 29 mN / m.

[0049] XPS analysis can be performed as described in the examples below. In XPS analysis of the surface of the cured film, "no peak from fluorine atom F1S was observed" means that no peak was detected at 691 eV, which is below the detection limit of the measuring device. By not observing the peak from fluorine atom F1S, high adhesion to the upper inorganic film such as SiO2 and SiN can be achieved.

[0050] 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 making the surface free energy within this range, after the spacer pattern described later is formed, when inkjet coating wavelength-converting phosphor ink and light-diffusing particle ink is performed, the ink does not climb to the top of the spacer and can be coated separately.

[0051] As described in the examples described later, the surface free energy can be obtained by measuring the contact angle between water and diiodomethane on the cured film, and the result can be calculated based on the measured value using the theoretical formula of Owent and Wendt.

[0052] It should be noted that, as a means to ensure that peaks originating from fluorine atoms F1S are not observed in XPS analysis and that the surface free energy is within the aforementioned range, examples include forming a cured film using a preferred composition of the resin composition described later.

[0053] The cured film in the laminate of the present invention preferably has a 950-1250 cm⁻¹ region derived from siloxane bonds (Si-O) in FT-IR analysis (ATR method). -1 The absorption intensity at the peak (E) SiO ) and 1650–1750 cm from carbonyl (C=O) groups -1 The absorption intensity at the peak (E) CO The ratio of (E) SiO / E CO It satisfies the following relation (I).

[0054] 1.2≤ E SiO / E CO ≤20 (I)

[0055] FT-IR analysis can be performed as described in the examples described later.

[0056] The term "peak" refers to the position of the peak with the greatest height within a given wavenumber range. The range is typically 950–1250 cm. -1 The absorption intensity at the peak (E) SiO ), indicating that the wavenumber in the spectrum is 950cm. -1 The point and 1250cm -1 Connect the points with straight lines, from 950 to 1250 cm. -1 When a perpendicular line is drawn from the peak to the straight line, the distance from the peak to the intersection of the straight line and the perpendicular line is taken as 1650–1750 cm. -1 The absorption intensity at the peak (E) CO This indicates a wavenumber range of 1650–1750 cm⁻¹. -1 The distances were measured similarly within the same range.

[0057] via E SiO / E CO With a value above 1.2, the liquid repellency and weather resistance can be improved through the siloxane bond components in the cured film. SiO / E CO Preferably, it is 1.5 or higher, and more preferably 2.0 or higher. (via E) SiO / E CO With a value below 20, the crack resistance of the cured film can be improved through the organic components in the cured film. SiO / E CO Preferably, it is 15 or less, and more preferably 10 or less.

[0058] It should be noted that E in relation (I) is used to... SiO / E CO Examples of means within the scope described above include forming a cured film using a preferred composition of the resin composition described later.

[0059] The cured film in the laminate of the present invention is preferably a spacer formed by patterning. A spacer is, for example, a layer that separates the wavelength conversion layers from each other, the light-emitting layers from each other, etc. Examples of repeating patterns of the formed spacers include, for example, grid-like, striped, and perforated shapes.

[0060] exist Figure 2 The image shows a cross-sectional view of one embodiment of the laminate of the present invention, having a substrate and spacers 3 formed by patterning as a curing film. The substrate 1 has spacers 3 formed by patterning.

[0061] The height of the spacer is not particularly limited, but when used as a spacer to separate the wavelength conversion layer and the light emitter described later, it is preferably 5 μm or more and 50 μm or less. By setting the height of the spacer within this range, good light extraction efficiency can be achieved. The height of the spacer is preferably 8 μm or more, more preferably 10 μm or more. Furthermore, it is preferably 30 μm or less, more preferably 20 μm or less.

[0062] The spacer wall preferably has a reflectance of 20% or more and 85% or less per 10 μm of thickness at a wavelength of 550 nm. The thickness of the spacer wall refers to its height and / or width. The height of the spacer wall refers to its length in the direction perpendicular to the substrate (height direction). Figure 2 In the case of the laminated structure shown, the height of the spacer wall 3 is represented by the symbol H. Furthermore, the width of the spacer wall refers to its length in the direction horizontal to the base of the spacer wall. Figure 2 In the case of the stacked structure shown, the width of the spacer wall 3 is represented by the symbol L. It should be noted that in this specification, "height" is sometimes also referred to as "thickness". In this invention, it can be considered that the reflectivity of the spacer wall side helps to improve light extraction efficiency, and the OD value (light-blocking property) helps to suppress color mixing between adjacent pixels. On the other hand, since the reflectivity and OD value per unit thickness are considered to be the same regardless of the height and width directions, this invention focuses on the reflectivity and OD value per unit thickness of the spacer wall. It should be noted that, as described above, the height of the spacer 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 this invention, 10 μm is selected as a representative value for the thickness of the spacer wall, focusing on the reflectivity and OD value per 10 μm thickness.

[0063] If the reflectance at a wavelength of 550 nm per 10 μm thickness is less than 20%, the reflection in the sidewalls of the spacer becomes smaller, the light extraction efficiency deteriorates, and the brightness of the display device becomes insufficient. More preferably, the reflectance at a wavelength of 550 nm per 10 μm thickness is 25% or more, and even more preferably 30% or more. Higher reflectance results in greater reflection in the sidewalls of the spacer, thus improving light extraction efficiency; however, if the reflectance at a wavelength of 550 nm per 10 μm thickness exceeds 85%, color mixing occurs between adjacent pixels.

[0064] The reflectance at a wavelength of 550 nm per 10 μm thickness of the spacer wall can be measured as described in the examples described later.

[0065] The spacer wall preferably has an OD value of 1.5 or higher and 3.0 or lower per 10 μm of thickness at a wavelength of 450 nm. If the OD value at a wavelength of 450 nm per 10 μm of thickness is less than 1.5, the light-blocking ability of the blue light in the spacer wall is insufficient. For example, when used as a spacer wall separating the wavelength conversion layer described later, the blue light used as excitation light leaks into adjacent pixels, resulting in light emission from adjacent pixels and color mixing. The OD value at a wavelength of 450 nm per 10 μm of thickness is more preferably 1.7 or higher, and even more preferably 2.0 or higher. The higher the OD value, the greater the light-blocking ability of the blue light in the spacer wall, thus 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.

[0066] The OD value at a wavelength of 450 nm per 10 μm thickness of the spacer can be calculated by measuring the transmittance of a 10 μm thick spacer from its top surface using a densitometer / spectrophotometer (e.g., Hitachi Hytek Symance U-4100) and using the following formula (1). However, if a sufficient area for measurement cannot be guaranteed, or if a 10 μm thick sample cannot be taken, and the composition of the spacer is known, a 10 μm thick full-coverage film with the same composition as the spacer can be prepared, similar to the reflectance measurement. The transmittance of the full-coverage film can then be measured instead of the spacer, thereby obtaining the OD value per 10 μm thickness.

[0067] OD value = -log10(T / 100) (1)

[0068] T: Transmittance.

[0069] The cone angle of the partition wall is preferably 45° to 110°. The cone angle of the partition wall refers to the angle formed by the side edge and the bottom edge of the partition wall's cross-section. Figure 2 In the case of the stacked structure shown, the cone angle of the spacer wall 3 is represented by the symbol θ. By making the cone angle 45° or more, the difference in width between the upper and lower parts of the spacer wall is reduced, and the width of the spacer wall is easily formed within the aforementioned preferred range. The cone angle is more preferably 80° or more. On the other hand, by making the cone angle 110° or less, ink overflow can be suppressed when forming the color conversion phosphor described later by inkjet coating, thereby improving inkjet coating performance. Here, ink overflow refers to the phenomenon that ink overflows across the spacer wall and mixes into the adjacent pixel portion. The cone angle is more preferably 95° or less. The cone angle of the spacer wall can be determined by observing any cross-section of the spacer wall using a scanning electron microscope (FE-SEM (e.g., Hitachi S-4800 manufactured by Hitachi, Ltd.)) at an accelerating voltage of 3.0 kV and a magnification of 2,500x, and measuring the angle between the side and bottom edges of the cross-section of the spacer wall.

[0070] It should be noted that, as a means of making the reflectivity, OD value, and cone angle of the spacer wall within the above-mentioned range, examples include forming the spacer wall using a preferred composition of the resin composition described later.

[0071] The spacer is preferably formed on a glass substrate as a spacer with a height of 10 μm, dividing a unit with a width of 10 μm and an opening of (X×10) μm×(Y×10) μm. When a small amount of 1,6-hexanediol diacrylate is applied to the center of the unit by inkjet printing, the 1,6-hexanediol diacrylate spreads well throughout the unit. Furthermore, when an excess amount of 1,6-hexanediol diacrylate is applied to the center of the unit by inkjet printing, the 1,6-hexanediol diacrylate does not climb to the top of the spacer and exhibits good liquid repellency at the top.

[0072] When a spacer wall with a height of 10 μm is formed on a glass substrate as a unit with a width of 10 μm / opening (X×10) μm×(Y×10) μm, the volume of the space separated by the spacer wall is XY pL. When a small amount of 1,6-hexanediol diacrylate is applied to the center of this unit by inkjet printing (0.2XY pL), if the 1,6-hexanediol diacrylate spreads well throughout the unit, the wavelength conversion layer (described later) can be filled seamlessly into the spacer wall region. "Good spreadability throughout the unit" means that when the laminate coated with 1,6-hexanediol diacrylate is observed from the top surface using an optical microscope, the coated 1,6-hexanediol diacrylate is not biased towards the center of the region or around the 1st to 3rd sides of a certain spacer wall, but rather spreads around the 4th side of the spacer wall. For example, the state of "good spreadability throughout the unit" is shown in... Figure 3 The text describes a condition where "the coating properties within the unit are not good as a whole." Figure 4-1 , Figure 4-2 , Figure 4-3 middle.

[0073] Furthermore, when overcoating is performed in the center of the cell by inkjet printing 1.5 x Y pL of 1,6-hexanediol diacrylate, if the 1,6-hexanediol diacrylate does not adhere to the top of the spacer wall and exhibits good top liquid repellency, the wavelength conversion layer described later can be accurately coated separately within the spacer wall region. "Good top liquid repellency" refers to the state where, when the laminate coated with 1,6-hexanediol diacrylate is observed from the top surface using an optical microscope, the coated 1,6-hexanediol diacrylate does not adhere to the spacer wall and remains contained within the cell. For example, the state of "good top liquid repellency" is shown in... Figure 5In the middle, the "good liquid repellency at the top" status is shown. Figure 6 middle.

[0074] The inkjet coating of 1,6-hexanediol diacrylate can be performed as described in the examples below. Preferably, for example, after forming a spacer wall with a height of 10 μm on a glass substrate as a unit dividing a width of 10 μm / an opening of 140 μm × 40 μm, a small amount of 1,6-hexanediol diacrylate is applied to the center of the unit by inkjet printing. In this case, the 1,6-hexanediol diacrylate spreads well throughout the unit. Furthermore, when an excess coating is applied to the center of the unit by inkjet printing with 84 pL of 1,6-hexanediol diacrylate, the 1,6-hexanediol diacrylate does not climb to the top of the spacer wall, and the top liquid repellency is good.

[0075] It should be noted that, as a means to achieve good spreadability and top liquid repellency throughout the unit, examples include forming a spacer wall using a preferred composition of the resin composition described later.

[0076] The cured film in the laminate of the present invention is preferably a spacer obtained by patterning, and preferably has a wavelength conversion layer in the unit divided by the spacer.

[0077] Figure 7 A cross-sectional view showing one embodiment of the stacked body of the present invention having a wavelength conversion layer is shown. A spacer wall 3, which is a pattern formed as a curing film, is provided on a substrate 1, and a wavelength conversion layer 4 is provided in each pixel separated by the spacer wall.

[0078] A wavelength conversion layer is a cured layer containing phosphors that are excited by the wavelength of the backlight and emit light of different wavelengths, and / or light-diffusing particles that diffuse the wavelength of the backlight. Different phosphors and / or light-diffusing particles may be contained in each pixel. For example, when used in conjunction with a backlight that emits blue light, it is preferable to contain a red phosphor that emits red fluorescence when excited by blue excitation light in the region corresponding to a red pixel. Similarly, it is preferable to contain a green phosphor that emits green fluorescence when excited by blue excitation light in the region corresponding to a green pixel. It is preferable that the region corresponding to a blue pixel 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 and organic phosphors.

[0079] As inorganic phosphors, substances that emit green, red, or other colors upon excitation by blue light are preferred; that is, substances that, when excited by excitation light with a wavelength of 400–500 nm, have a peak in the emission spectrum in the region of 500–700 nm. Examples of such inorganic phosphors include, for instance, YAG-based phosphors, TAG-based phosphors, silane-based phosphors, and Mn-based phosphors. 4＋ Activated fluoride coordination compound phosphors, inorganic semiconductors known as quantum dots, etc., can be used. Two or more of these can be used. Among them, quantum dots are preferred. Because quantum dots have a smaller average particle size compared to other phosphors, they can smooth the surface of the (B) pixel and suppress surface light scattering, thereby improving light extraction efficiency and increasing brightness.

[0080] Examples of materials that can be used as quantum dots include semiconductors of groups II-IV, III-V, IV-VI, and IV. Examples of inorganic semiconductors include Si, Ge, Sn, Se, Te, B, C (including diamond), P, BN, BP, BAs, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdSeZn, CdTe, HgS, HgSe, HgTe, BeS, BeSe, BeTe, MgS, MgSe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbO, PbS, PbSe, PbTe, Si3N4, Ge3N4, and Al2O3. Two or more of these materials can be used.

[0081] As organic phosphors, substances that emit green, red, or other colors upon blue excitation light are preferred. Examples of organic phosphors include, for instance, pyrrole derivatives, perylene derivatives, and porphyrin derivatives. Zine derivatives, pyrazine derivatives, etc. Two or more of these may be contained. Among them, pyrrolomethylcarbamate derivatives are preferred for high quantum yield. Pyrrolomethylcarbamate derivatives can be obtained, for example, by the method described in Japanese Patent Application Publication No. 2011-241160.

[0082] From the viewpoint of improving color characteristics, the thickness of the wavelength conversion layer is preferably 0.5 μm or more, and more preferably 1 μm or more. On the other hand, from the viewpoint of making the display device thinner and more adaptable to curved surfaces, the thickness of the wavelength conversion layer is preferably 30 μm or less, and more preferably 20 μm or less.

[0083] Wavelength conversion layers are preferably arranged with spacers separating them. By placing spacers between pixels, the diffusion and color mixing of emitted light can be further suppressed.

[0084] One method for forming a wavelength conversion layer is, for example, filling a coating solution containing phosphors and / or light-diffusing particles (hereinafter, wavelength conversion material coating solution) into a space separated by a spacer wall. The wavelength conversion material coating solution may further contain resin and solvent.

[0085] Methods for filling wavelength conversion material coating liquids include photolithography and inkjet printing, but from the viewpoint of easily coating different types of color conversion light-emitting materials separately for each pixel, inkjet printing is preferred.

[0086] The laminate of the present invention may further have an inorganic protective layer on the wavelength conversion layer. The inorganic protective layer protects the wavelength conversion layer from the influence of oxygen and water.

[0087] Figure 8 A cross-sectional view showing one embodiment of the laminate of the present invention having an inorganic protective layer is shown. A spacer wall 3, which is a pattern formed as a curing film, is provided on a substrate 1. Each pixel separated by the spacer wall has a wavelength conversion layer 4, on which an inorganic protective layer 5 is provided.

[0088] Examples of materials constituting the inorganic protective layer include metal oxides such as silicon oxide (SiO2), indium tin oxide, and zinc gallium oxide; and metal nitrides such as silicon nitride (SiN). Two or more of these materials may be included. Among them, silicon oxide (SiO2) or silicon nitride (SiN) is more preferred considering low water vapor permeability and high transmittance.

[0089] Examples of methods for forming the inorganic protective layer include sputtering. From the viewpoint of sufficiently suppressing the permeation of substances such as water vapor, the thickness of the inorganic protective layer is preferably 50 nm or more. On the other hand, from the viewpoint of suppressing the decrease in transmittance, the thickness of the inorganic protective layer is preferably 800 nm or less. It should be noted that the thickness of the inorganic protective layer can be measured by using a polishing device such as a cross-section polisher to expose a cross-section perpendicular to the substrate, and then observing the cross-section under magnification using a scanning electron microscope or a transmission electron microscope.

[0090] The laminate of the present invention may further include a color filter layer (hereinafter, sometimes referred to as "color filter"). The color filter has the function of allowing visible light in a specific wavelength range to pass through, resulting in transmitted light of a desired hue. By including the color filter, the color purity of the display device can be improved.

[0091] Figure 9A cross-sectional view showing one embodiment of the stack of the present invention having a color filter layer is shown. A color filter layer 6 is provided on a substrate 1, and spacers 3, which are patterned as curing films, are provided thereon. Each pixel separated by the spacers has a wavelength conversion layer 4, and an inorganic protective layer 5 is provided thereon.

[0092] Examples of color filters include, for instance, those used in flat panel displays such as liquid crystal displays (LCDs) that utilize pigment-dispersed materials obtained by dispersing pigments in photoresist. More specifically, examples include blue color filters that selectively transmit wavelengths of 400 nm to 550 nm, green color filters that selectively transmit wavelengths of 500 nm to 600 nm, yellow color filters that selectively transmit wavelengths of 500 nm and above, and red color filters that selectively transmit wavelengths of 600 nm and above. The black matrix separating each color filter section may contain a black material. Furthermore, by coating each color filter section and the black matrix with a transparent outer coating material, an outer coating portion can be formed. In the case of having a black matrix and color filter sections of various colors, for example, as... Figure 9 As shown, it is preferable to form a black matrix 7 under the spacer wall and color filter sections 8 under the wavelength conversion layer.

[0093] The cured film in the laminate of the present invention may not be the spacer obtained by patterning as described above, but rather a full-coverage film without patterning. When the cured film is a full-coverage film, it is suitable for applications such as anti-reflective layers of low-reflection films that require water repellency and stain resistance.

[0094] Next, the resin composition for forming the cured film in the laminate of the present invention will be described.

[0095] The cured film in the laminate of the present invention is preferably a cured film obtained by curing a resin composition containing (A) polysiloxane, (B) photopolymerization initiator, (C) photopolymerizable compound, and (D) liquid-repellent compound, wherein the liquid-repellent compound (D) is a surfactant that does not contain fluorine atoms in its molecule and contains photopolymerizable groups.

[0096] (A) Polysiloxane

[0097] Polysiloxanes are hydrolysis / dehydration condensates of organosilane compounds, referring to resins with siloxane bonds (Si-O bonds) as the main backbone and 0 to 3 organic groups at the Si atom. They may also have organosilicon groups (dimethylsiloxane backbones with 2 methyl groups at the Si atom), but resins with more than one backbone other than organosilicon groups at the ends are defined as (A) polysiloxanes.

[0098] The organosilane compound preferably comprises repeating units derived from difunctional organosilane compounds as shown in general formula (1) and / or repeating units derived from trifunctional organosilane compounds as shown in general formula (2), and more preferably comprises repeating units derived from both difunctional organosilane compounds and trifunctional organosilane compounds.

[0099]

[0100] In the above general formula (1), R 1 and R 2 These can be the same or different, representing monovalent organic groups with 1 to 20 carbon atoms. Polysiloxanes can contain two or more different R groups. 1 and R 2 The repeating unit shown in general formula (1). From the viewpoint of facilitating the adjustment of the molecular weight of polysiloxane during polymerization, R 1 and R 2 Preferably, the group is selected from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 12 carbon atoms. However, at least a portion of the hydrogen atoms of the alkyl and aryl groups may be replaced by a free radical polymerizable group, which can be free radical polymerized in the cured product. In the above general formula (2), R 3 Represents a monovalent organic group with 1 to 20 carbon atoms. Polysiloxanes can contain two or more different R groups. 3 The repeating unit is shown in general formula (2). From the viewpoint of facilitating the adjustment of the molecular weight of polysiloxane during polymerization, R 3 Preferably, it contains groups selected from alkyl groups having 1 to 6 carbon atoms and aryl groups having 6 to 12 carbon atoms. However, at least a portion of the hydrogen atoms of the alkyl and aryl groups may be replaced by free radical polymerizable groups, which can be free radical polymerized in the cured product.

[0101] By including repeating units derived from difunctional organosilane compounds, excessive thermal polymerization (condensation) of the polysiloxane caused by heating can be suppressed, thereby improving the crack resistance of the cured film. Preferably, the polysiloxane contains 10 to 70 mol% of repeating units derived from difunctional organosilane compounds. From the viewpoint of combining crack resistance and liquid repellency of the cured film, it is further preferred that the polysiloxane contains 15 to 35 mol% of repeating units derived from difunctional organosilane compounds. On the other hand, by including repeating units derived from trifunctional organosilane compounds, the crosslinking density of the polysiloxane in the cured film increases, thereby improving the film's hardness and chemical resistance. Preferably, the polysiloxane contains 30 to 90 mol% of repeating units derived from trifunctional organosilane compounds.

[0102] The repeating units shown in general formulas (1) and (2) above are derived from organosilane compounds shown in general formulas (3) and (4) below, respectively. That is, polysiloxanes containing repeating units shown in general formulas (1) and (2) above can be obtained by hydrolyzing and polycondensing organosilane compounds shown in general formulas (3) and (4) below, respectively. Other organosilane compounds can be further used. It should be noted that in general formulas (3) and (4), "-(OR)" is used. 4 )2” and “-(OR) 4 The expression ")3" refers to two or three "-(OR)" symbols. 4 )" respectively combine with Si atoms.

[0103]

[0104] In the above general formula (3), R 1 ~R 2 R represents the expression in the above general formula (1). 1 ~R 2 The same group. In the above general formula (4), R 3 R represents the expression in the above general formula (2). 3 The same group. In the above general formulas (3) and (4), R 4 They can be the same or different, representing a monovalent organic group or hydrogen with 1 to 20 carbon atoms, preferably an alkyl group with 1 to 6 carbon atoms.

[0105] Examples of organosilane compounds represented by general formula (3) include, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenylsilanediol, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, γ-methacryloylpropylmethyldimethoxysilane, γ-methacryloylpropylmethyldiethoxysilane, γ-acryloylpropylmethyldimethoxysilane, γ-acryloylpropylmethyldiethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane Oxy-hydroxysilanes, 3-epoxypropoxypropylmethyldiethoxysilane, 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 can be used.

[0106] Examples of organosilane compounds represented by general formula (4) include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, 3-epoxypropoxypropyltriethoxysilane. oxysilanes, 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, 2-naphthyltrimethoxysilane, 2-naphthyl Trimethoxysilane, Tolyltrimethoxysilane, Tolyltriethoxysilane, Styreltrimethoxysilane, Styreltriethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Allyltrimethoxysilane, Allyltriethoxysilane, γ-Acryloylpropyltrimethoxysilane, γ-Acryloylpropyltriethoxysilane, γ-Methacrylpropyltrimethoxysilane, γ-Methacrylpropyltriethoxysilane, 3-Trimethoxysilylpropionic acid, 3-Triethoxy Silyopropyl propionic acid, 4-trimethoxysilylbutyric acid, 4-triethoxysilylbutyric acid, 5-trimethoxysilylvaleric acid, 5-triethoxysilylvaleric acid, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-trimethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-triethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylphthalic anhydride, 3-triethoxysilylpropylphthalic anhydride, etc. Two or more of these can be used.

[0107] It may also contain other organosilane compounds. Examples of other organosilane compounds include tetramethoxysilane, tetraethoxysilane, silicate 51 (a tetramethoxysilane oligomer), and other tetrafunctional organosilane compounds. Two or more of these may be used.

[0108] The polysiloxane (A) described above preferably contains at least one free radical polymerizable group. That is, as an organosilane compound represented by general formula (3) and / or (4), it is preferable to contain at least one organosilane compound containing a free radical polymerizable group. By containing an organosilane compound with a free radical polymerizable group in the polysiloxane (A), crosslinking reaction can be carried out by free radicals generated from the photopolymerization initiator (B) described later through light irradiation, thereby improving the curing degree of the exposed portion. In addition, the reaction with the liquid-repellent compound (D) described later can be carried out efficiently, improving the liquid repellency of the cured film and reducing the surface free energy. Examples of free radical polymerizable groups include vinyl, methacryl, acryloyl, allyl, styrene, etc. Two or more of these can be contained. Among them, from the viewpoint of photoreactivity, it is preferable that the polysiloxane (A) contains methacryl, acryloyl, or styrene, and it is even more preferable that the polysiloxane (A) contains at least a styrene group. By containing styrene groups, the surface free energy of the cured film can be lowered due to its high reactivity with (D) liquid-repellent compounds and its post-reaction structure. Furthermore, by containing styrene groups, the curability (low-temperature curing) is improved when the (iv) heating process is performed at low temperatures of 80–100°C, thereby enhancing the chemical resistance of the cured film.

[0109] The polysiloxane (A) described above preferably contains 10 to 60 mol% of styrene-based repeating units in all repeating units. When the styrene-based repeating units are less than 10 mol% in all repeating units, the photoreactivity is insufficient, resulting in a higher surface free energy of the cured film; furthermore, low-temperature curability deteriorates. When the styrene-based repeating units exceed 60 mol% in all repeating units, the film stress caused by photocuring increases, and the crack resistance of the cured film deteriorates. More preferably, the styrene-based repeating units in all repeating units are 15 to 40 mol%.

[0110] The polysiloxane (A) described above preferably contains at least one carboxyl group. That is, as an organosilane compound represented by general formula (3) and / or (4), it preferably contains at least one organosilane compound containing a carboxyl group and / or a carboxylic anhydride group. By including an organosilane compound containing a carboxyl group and / or a carboxylic anhydride group, the developability can be improved during the formation of the spacer wall pattern.

[0111] From the viewpoint of coatability, the weight-average molecular weight (Mw) of (A) polysiloxane is preferably 1,000 or more, more preferably 2,000 or more. In particular, when (A) polysiloxane does not contain styrene groups, Mw is more preferably 4,000 or more. When Mw is 4,000 or more, after reacting with the liquid-repellent compound (D) in the exposure process, the surface is less likely to be dissolved by development during the development process, resulting in a lower surface free energy of the cured film. On the other hand, from the viewpoint of developability / patterning processability, the Mw of the polysiloxane is preferably 500,000 or less, more preferably 300,000 or less. Here, the so-called Mw of the polysiloxane in this invention refers to the polystyrene equivalent value determined by gel permeation chromatography (GPC). The determination method is as described in the examples described later.

[0112] (A) Polysiloxanes can be obtained by hydrolyzing the above-mentioned organosilane compounds and then subjecting the hydrolysate to a dehydration condensation reaction in the presence of a solvent or under solvent-free conditions. Catalysts such as acids and bases can be used in the hydrolysis / dehydration condensation reaction.

[0113] From the viewpoint of ensuring good liquid repellency and pattern processing properties of the cured film, the content of (A) polysiloxane is preferably 10% by weight or more in the solid component.

[0114] (B) Photopolymerization initiator

[0115] (B) The photopolymerization initiator can be any substance that is decomposed and / or reacted by active light irradiated in the exposure process described in (ii) above, and generates free radicals. It is preferably a substance that is decomposed and / or reacted by at least one of i-rays, h-rays, and g-rays, and generates free radicals. Examples of photopolymerization initiators (B) include, for instance, α-aminoalkyl phenyl ketone compounds such as 2-methyl-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholino-4-yl-phenyl)-butane-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)-phosphine oxide; 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, and 1,2-octanedione-1-[4-(phenylthio)-2-(O- Benzoyl oxime, 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, acetone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) and other oxime esters; 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4 α-hydroxy ketone compounds such as (-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, and 1-hydroxycyclohexyl-phenyl ketone; acetophenone compounds such as 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-tert-butyldichloroacetophenone, benzylacetophenone, and 4-azidobenzylideneacetophenone. Two or more of these compounds may be contained. From the viewpoint of reducing the free radical damage caused by oxygen, improving the reactivity of the liquid-repellent compound (D) on the surface of the cured film, and lowering the surface free energy of the cured film, it is preferable that the photopolymerization initiator (B) contains at least an oxime ester compound. Furthermore, from the viewpoint of absorbing long-wavelength light and achieving excellent thick-film curing properties, it is preferable to further contain an acylphosphine oxide compound.

[0116] From the viewpoint of effectively carrying out free radical curing, the content of (B) photopolymerization initiator in the solid component is preferably 0.5% by weight or more, more preferably 1% by weight or more. On the other hand, from the viewpoint of suppressing the dissolution of residual (B) photopolymerization initiator, the content of (B) photopolymerization initiator in the solid component is preferably 20% by weight or less, more preferably 10% by weight or less.

[0117] (C) Photopolymerizable compounds

[0118] The term (C) photopolymerizable compound refers to a compound having two or more olefinic unsaturated double bonds in its molecule, and lacking siloxane bonds (Si-O bonds) and the liquid-repellent functional groups described later. Considering the ease of free radical polymerization, the (C) photopolymerizable compound preferably contains vinyl, allyl, methacryloyl, acryloyl, or styrene groups, and more preferably methacryloyl, acryloyl, or styrene groups.

[0119] Examples of photopolymerizable compounds (C) include 1,6-hexanediol diacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethyloltricyclodecane 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 compounds may be present.

[0120] From the viewpoint of effectively carrying out free radical curing, the content of (C) photopolymerizable compound in the solid component is preferably 1% by weight or more. On the other hand, from the viewpoint of suppressing excessive free radical reaction and improving resolution, the content of (C) photopolymerizable compound in the solid component is preferably 50% by weight or less.

[0121] (D) Liquid-repellent compounds

[0122] In this invention, (D) the liquid-repellent compound refers to a surfactant that does not contain fluorine atoms within its molecule and contains a photopolymerizable group. A surfactant is a compound that reduces surface tension or interfacial tension at the interface (the boundary between liquids, liquids and solids, liquids and gases, etc.), and here it refers to a compound having a liquid-repellent functional group. Examples of liquid-repellent functional groups include, for example, hydrocarbon groups and organosilicon groups.

[0123] By eliminating fluorine atoms within the molecule, the adhesion between the formed cured film and the upper inorganic layers such as SiO2 and SiN can be improved. XPS analysis is always related to the atoms present on the film surface. Furthermore, in recent years, due to concerns about the environmental residues and ecological accumulation of organofluorine compounds, their harmful effects on human health have been studied, mainly in Europe. Therefore, it is possible to obtain cured films with excellent environmental compatibility.

[0124] Furthermore, by using a surfactant containing a photopolymerizable group, the liquid-repellent compound (D) is locally present on the film surface after the coating step (i). The photopolymerizable group in the liquid-repellent compound (D) reacts with free radicals generated from the photopolymerization initiator (B) during the exposure step (ii), thereby efficiently improving the liquid repellency of the cured film surface. As the photopolymerizable group, it is preferable, for example, to contain vinyl, allyl, methacryl, acryloyl, or styrene; more preferably, methacryl, acryloyl, or styrene; and even more preferably, acryloyl or styrene.

[0125] (D) The liquid-repellent compound is preferably an organosilicon surfactant. By using an organosilicon surfactant, the surface of the cured film can be endowed with high water repellency derived from the organosilicon group. An organosilicon surfactant refers to a surfactant with a resin structure such as acrylic resin or polyimide resin as its main framework, further containing organosilicon groups as liquid-repellent functional groups. The term "organosilicon group" refers to a dimethylsiloxane skeleton with a siloxane bond (Si-O bond) as its main framework and two methyl groups on the Si atom.

[0126] (D) The liquid-repellent compound can be a synthetic product or a commercially available product. Examples of commercially available (D) liquid-repellent compounds include organosilicon surfactants with photopolymerizable groups, such as "BYK" (registered trademark)-UV3500, UV3510, UV3530, UV3519, UV3575, UV3576 (and above, trade name, manufactured by Bickkemijapan Co., Ltd.) and "RS" (registered trademark)-57 (trade name, manufactured by DIC Co., Ltd.). Among these, RS-57 is preferred from the viewpoint of reducing surface free energy.

[0127] (D) The content of the liquid-repellent compound is preferably 0.05% to 2.00% by weight of the total solids of the resin composition. If the content of the liquid-repellent compound is less than 0.05% by weight of the total solids, the amount of the liquid-repellent compound cured on the film surface becomes insufficient, and the surface free energy cannot be sufficiently reduced. If the content of the liquid-repellent compound exceeds 2.00% by weight of the total solids, the uncured liquid-repellent compound on the film surface peels off within the pixels of the spacer wall during the (iii) developing process, resulting in the aforementioned "poor spreadability throughout the unit" when forming the wavelength conversion layer by inkjet coating. The content of the liquid-repellent compound is more preferably 0.10% to 1.00% by weight of the total solids, and even more preferably 0.15% to 0.50% by weight of the total solids.

[0128] The cured film in the laminate of the present invention is preferably a cured film obtained by curing a resin composition further containing an (E) metal chelating agent. The (E) metal chelating agent refers to a coordination compound having a structure that chelates and coordinates one or more polydentate ligands to metal atoms.

[0129] By including the (E) metal chelating agent, even at the low temperature of 80–100°C in the (iv) heating process, the surface free energy of the cured film can be above 10 mN / m and below 29 mN / m. This is because all or part of the (E) metal chelating agent is introduced into the film, and furthermore, the (E) metal chelating agent can promote the condensation reaction between the unreacted silanol groups remaining in component (a).

[0130] (E) The metal chelating agent is preferably the metal chelating agent shown in the following general formula (5).

[0131]

[0132] (M represents a metal atom, R) 5 Each is independently hydrogen, alkyl, aryl, or alkenyl, R 6 and R 7 Each is independently hydrogen, alkyl, aryl, alkenyl, or alkoxy, j is an integer from 0 to 8, and k is an integer from 1 to 4.

[0133] From the viewpoint of minimizing the coloration of the cured film, the metal atom M can be represented by titanium, zirconium, aluminum, zinc, cobalt, molybdenum, lanthanum, barium, strontium, magnesium, or calcium. Among these, zirconium or aluminum is preferred as the metal atom M from the viewpoint of minimizing the coloration of the cured film and minimizing the surface free energy; aluminum is more preferred. That is, as the (E) metal chelating agent, aluminum chelates or zirconium chelates are preferred; aluminum chelates are more preferred.

[0134] The metal chelating agent represented by general formula (5) has R 5 Alkyl, aryl, and alkenyl groups, in addition to R 6 and R 7 The alkyl, aryl, alkenyl, and alkoxy groups can all be substituted with other substituents.

[0135] In general formula (5), as R 5Examples of suitable metal chelating agents include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, octadecyl, phenyl, vinyl, allyl, or oleyl. Among these, from the viewpoint of the stability of the metal chelating agent, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-octadecyl, or phenyl are preferred. Examples of suitable metal chelating agents R6 and R7 include hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-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, or benzyloxy. Among these, from the viewpoint of ease of synthesis and stability of the metal chelating agent, methyl, tert-butyl, phenyl, methoxy, ethoxy, or n-octadecyl are preferred.

[0136] Examples of aluminum chelates with aluminum as the metal atom M include, for example, aluminum triisopropoxide, aluminum tri-n-propoxide, aluminum trisec-butoxide, aluminum tri-n-butoxide, aluminum triphenol, aluminum triacetylacetone, aluminum tri(2,2,6,6-tetramethyl-3,5-heptadecanoate), aluminum triethylacetoacetate, aluminum trimethylacetoacetate, aluminum trimethylmalonate, aluminum triethylmalonate, aluminum di(isopropanol) ethylacetate, aluminum di(isopropanol) acetylacetone, aluminum di(isopropanol) methylacetylacetone, aluminum di(isopropanol) octadecylacetylacetone, and aluminum monoacetylacetone bis(ethylacetylacetone).

[0137] Examples of zirconium chelates with zirconium as the metal atom M include: zirconium tetra-n-propoxide, zirconium tetra-n-butoxide, zirconium tetra-sec-butoxide, zirconium tetraphenolate, zirconium tetraacetylacetone, zirconium tetra(2,2,6,6-tetramethyl-3,5-heptadecanoate), zirconium tetramethylacetoacetate, zirconium tetraethylacetoacetate, zirconium tetramethylmalonate, zirconium tetraethylmalonate, zirconium tetrabenzoylacetone, zirconium tetra(dibenzoylmethane), and zirconium monobutoxyacetylacetone bis(ethylacetyl)acetone. Zirconium acetate, bis(acetylacetone) zirconium ...

[0138] Among them, from the viewpoint of low coloration of the cured film and low surface free energy, zirconium tetrapropoxide, zirconium tetrabutoxide, zirconium tetraphenolate, zirconium tetraacetylacetonate, zirconium tetraacetylacetonate, aluminum triacetylacetonate, aluminum tri(2,2,6,6-tetramethyl-3,5-heptadecanoate)acetic acid, and more preferably aluminum triacetylacetonate.

[0139] From the viewpoint of minimizing surface free energy, the content of the (E) metal chelating agent is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, in the total solid components of the resin composition. On the other hand, from the viewpoint of minimizing the colorfastness of the cured film, it is preferably 5% by weight or less, more preferably 3% by weight or less.

[0140] The resin composition forming the cured film in the laminate of the present invention may also contain components other than those described in (A) to (E) above. Depending on the requirements, it may contain ultraviolet absorbers, polymerization inhibitors, surfactants, adhesion modifiers, particles, dispersants, resins other than polysiloxanes, etc. However, for the same reasons explained in (D) above regarding liquid-repellent compounds, it is preferable not to contain compounds containing fluorine atoms.

[0141] The resin composition forming the cured film in the laminate of the present invention can improve lightfastness by containing an ultraviolet absorber. From the viewpoint of transparency and non-coloring, the following are preferred ultraviolet absorbers: benzotriazole compounds such as 2-(2H-benzotriazole-2-yl)phenol, 2-(2H-benzotriazole-2-yl)-4,6-tert-amylphenol, 2-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazole-2-yl)-6-dodecyl-4-methylphenol, and 2-(2'-hydroxy-5'-methacryloyloxyethylphenyl)-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.

[0142] The resin composition forming the cured film in the laminate of the present invention contains a polymerization inhibitor, thereby improving the resolution during pattern formation. Examples of polymerization inhibitors include, for example, di-tert-butylhydroxytoluene, butylated hydroxyanisole, 4-methoxyphenol, 1,4-benzoquinone, and tert-butylcatechol. Furthermore, 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 Co., Ltd.). Two or more of these inhibitors may be included.

[0143] The resin composition forming the cured film in the laminate of the present invention contains a surfactant that does not have a photopolymerizable group, in addition to the (D) liquid-repellent compound, thereby improving the leveling properties during coating. Fluorinated surfactants are known as surfactants for improving leveling properties, but for the reasons mentioned above, fluorinated surfactants are not included. Suitable surfactants include, for example, silicone surfactants such as "BYK" (registered trademark)-333, 301, 331, 345, 307 (all trade names, manufactured by Bickkemijapan Co., Ltd.); polyoxyethylene surfactants; and poly(meth)acrylate surfactants. Two or more of these may be included.

[0144] The resin composition forming the cured film in the laminate of the present invention can improve its adhesion to the substrate by containing an adhesion modifier. Examples of adhesion modifiers include alicyclic epoxy compounds and silane coupling agents.

[0145] Examples of alicyclic epoxides include, for instance, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 1,2-epoxy-4-vinylcyclohexane, and tetramethyl butane. The product may contain 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-cyclohexanedicarboxylic acid diglycidyl ether, 1,4-cyclohexanediethanol diglycidyl ether, etc. It may contain two or more of these.

[0146] As a silane coupling agent, organosilane compounds, exemplified as raw materials for (A) polysiloxanes, can be used.

[0147] From the viewpoint of improving adhesion to the substrate, the content of the adhesion modifier is preferably 0.1% by mass or more of the total solid components, more preferably 1% by mass or more. On the other hand, from the viewpoint of pattern processability, the content of the adhesion modifier is preferably 20% by mass or less of the total solid components, more preferably 10% by mass or less.

[0148] The resin composition forming the cured film in the laminate of the present invention contains particles, thereby adjusting the optical properties of the cured film such as reflectivity, OD value (light-shielding property), and refractive index.

[0149] When it is desired to improve the reflectivity of the cured film, it is preferable to contain white pigment as particles. Examples of white pigments include particles with an average primary particle size of 100 nm or more and less than 500 nm. Examples of particle types include titanium oxide, zirconium oxide, zinc oxide, barium sulfate, and their composite compounds. Two or more of these may be contained.

[0150] When it is desired to improve the light-blocking properties of the cured film at a specific wavelength, the particles preferably contain light-blocking pigments such as red pigment, blue pigment, black pigment, green pigment, and yellow pigment.

[0151] Furthermore, when both reflective and opaque properties are desired, it is preferable to contain both white pigment and opaque pigment.

[0152] Examples of red pigments include Pigment Red (hereinafter abbreviated as PR) PR177, PR179, PR180, PR192, PR209, PR227, PR228, PR240, PR254, etc. A product may contain two or more of these pigments.

[0153] Examples of blue pigments include Pigment Blue (hereinafter abbreviated as PB) 15, PB15:3, PB15:4, PB15:6, PB22, PB60, PB64, etc. A product may contain two or more of these pigments.

[0154] Examples of black pigments include, for example, black organic pigments, mixed organic pigments, and black inorganic pigments. Examples of black organic pigments include, for example, carbon black, perylene black, aniline black, and benzofuranone pigments. These can be coated with resin. Examples of mixed organic pigments include, for example, substances that have been made by mixing two or more pigments selected from red, blue, green, purple, yellow, magenta, and cyan to achieve a black-like appearance. Among these, a mixture of red and blue pigments is preferred from the viewpoint of having both a moderately high OD value and good pattern processing properties. The mass ratio of red to blue pigment in the mixed pigment is preferably 20 / 80 to 80 / 20, more preferably 30 / 70 to 70 / 30. Examples of black inorganic pigments include, for example, graphite; microparticles 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. It can contain more than two of them.

[0155] Examples of green pigments include CI Pigment Green (hereinafter abbreviated as PG) 7, PG36, PG58, PG37, and PG59. A product may contain two or more of these pigments.

[0156] Examples of yellow pigments include Pigment Yellow (hereinafter abbreviated as PY), PY150, PY153, PY154, PY166, PY168, PY185, etc. A pigment may contain two or more of these.

[0157] When a high refractive index is desired in the cured film, it is preferable to include high refractive index particles. Examples of high refractive index particles include oxide particles with an average primary particle size of 1 nm or more and less than 100 nm. Examples of particle types include titanium oxide, zirconium oxide, and zinc oxide. Two or more of these particles may be included.

[0158] When a low refractive index is desired in the cured film, it is preferable to include low-refractive-index particles. Examples of low-refractive-index particles include, for instance, oxide particles with an average primary particle size of 1 nm or more and less than 100 nm; 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 achieving a low refractive index, hollow silica and hollow organic particles are preferred. Two or more of these particles may be included.

[0159] The aforementioned particles are preferably used in the form of a dispersion in which a dispersant and a solvent (described later) are dispersed, in order to prepare the resin composition. Therefore, the resin composition forming the cured film in the laminate of the present invention may contain a dispersant.

[0160] Examples of dispersants include, for example, polyethylene oxide, polyacrylic acid, polyphosphate, phosphate polyester, and polyacrylamide.

[0161] The resin composition forming the cured film in the laminate of the present invention may further contain a resin other than (A) polysiloxane. By using a resin other than (A) polysiloxane, for example, the non-stickiness after pre-baking can be improved, compensating for the insufficient film properties when using (A) polysiloxane. Examples of resins other than (A) polysiloxane include, for example, polyimide, polyimide precursors, and polybenzo[a]benzene. azole, polybenzo[a] Azole precursors, (meth)acrylic polymers, cardo resins, etc.

[0162] 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, thereby improving the coating uniformity. As a solvent, it is preferable to combine a solvent with a boiling point of more than 150°C and less than 250°C at atmospheric pressure with a solvent with a boiling point of less than 150°C.

[0163] Examples of solvents include, for instance, 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; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclopentanone; and dimethylformamide, diethyl ethyl ketone, diethyl ethyl ketone, diethyl ethyl ketone, diethyl ethyl ketone, and diethyl ethyl ketone. Amides such as methylacetamide; 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. It may contain two or more of these.

[0164] The solvent content can be arbitrarily set depending on the coating method, etc. For example, in the case of film formation by spin coating, the solvent content is generally 50% by weight or more and 95% by weight or less in the resin composition.

[0165] The resin composition forming the cured film in the laminate of the present invention can be manufactured, for example, by mixing the above-mentioned (A) polysiloxane, (B) photopolymerization initiator, (C) photopolymerizable compound, (D) liquid-repellent compound, solvent, and other components as needed.

[0166] Next, the resin composition of the present invention will be described. The resin composition of the present invention, like the cured film in the laminate of the present invention, does not contain fluorine atoms and is suitable for use in order to obtain a cured film having a low surface free energy.

[0167] The resin composition of the present invention is characterized by containing (A) a polysiloxane and (D) a liquid-repellent compound. By using the resin composition as the aforementioned thermosetting resin composition, it is suitable for applications such as antireflective layers for low-reflection films requiring water repellency and stain resistance.

[0168] The polysiloxane (A) described above preferably contains at least a styrene group. Furthermore, the polysiloxane (A) described above preferably contains 10 to 60 mol% of repeating units having a styrene group in all repeating units.

[0169] The liquid-repellent compound described above (D) is preferably an organosilicon surfactant.

[0170] 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 (C) photopolymerizable compound, it can be used as the aforementioned photocurable resin composition, and similarly, it is suitable for use in applications such as antireflective layers for low-reflection films requiring water repellency and stain resistance, particularly for films with particularly low heat resistance. Furthermore, by containing the (B) photopolymerization initiator and (C) photopolymerizable compound, it can also be used as the aforementioned negative photosensitive resin composition, and is suitable as a material for forming spacer patterns separating the aforementioned wavelength conversion layers.

[0171] The resin composition of the present invention preferably further contains an (E) metal chelating agent. The above-mentioned (E) metal chelating agent is as described above.

[0172] Furthermore, the resin composition of the present invention may also contain components other than those described in (A) to (E) above. Depending on the requirements, it may contain ultraviolet absorbers, polymerization inhibitors, surfactants, adhesion modifiers, particles, dispersants, resins other than polysiloxanes, etc. However, it is preferable that it does not contain compounds containing fluorine atoms.

[0173] The resin composition of the present invention contains the above-mentioned components (A) to (E), ultraviolet absorber, polymerization inhibitor, surfactant, adhesion modifier, particles, dispersant, and resin other than polysiloxane, which can be used to form a resin composition that forms a cured film in the laminate of the present invention within the range of the above-mentioned suitable range of addition amount.

[0174] The resin composition of the present invention can be manufactured, for example, by mixing the above-mentioned (A) polysiloxane, (B) photopolymerization initiator, (C) photopolymerizable compound, (D) liquid-repellent compound, solvent, and other components as needed.

[0175] Next, the display device of the present invention will be described.

[0176] The display device of the present invention includes the stacked body described above and a light-emitting source selected from liquid crystal cells, organic EL cells, mini-LED cells, and micro-LED cells. From the viewpoint of excellent light-emitting characteristics, organic EL cells, mini-LED cells, and micro-LED cells are more preferred as the light-emitting source. A mini-LED cell refers to a cell formed by arranging multiple LEDs with a length of approximately 100 μm to 1 mm. A micro-LED cell refers to a cell formed by arranging multiple LEDs with a length of less than 100 μm. The light-emitting source can also be separated by spacers in the stacked body of the present invention. Preferably, the light-emitting source includes the wavelength conversion layer described above. That is, the stacked body of the present invention preferably includes a wavelength conversion layer within the cells divided by the spacers.

[0177] exist Figure 10 The image shows a cross-sectional view of one embodiment of the display device of the present invention, which has a light source and pixels selected from organic EL units, mini LED units, and micro LED units. A light source 9 selected from organic EL units, mini LED units, and micro LED units is provided on a substrate 1 between spacers 3 formed by patterning, and a wavelength conversion layer 4 is further provided thereon.

[0178] Regarding the manufacturing method of the display device of the present invention, an example of a display device having the stacked body and organic EL unit of the present invention will be described. A photosensitive polyimide resin is coated on a glass substrate, and an insulating film with openings is formed using photolithography. After aluminum is sputtered onto the substrate, an aluminum pattern is formed using photolithography, and a back electrode layer formed of aluminum is formed in the openings where there is no insulating film. Next, tris(8-hydroxyquinoline)aluminum (hereinafter abbreviated as Alq3) is formed on the substrate as an electron transport layer by vacuum evaporation, and a white light-emitting layer doped with dicyanomethylenepyran, quinacridone, and 4,4'-bis(2,2-diphenylvinyl)biphenyl is formed as a light-emitting layer. Next, N,N'-diphenyl-N,N'-bis(α-naphthyl)-1,1'-biphenyl-4,4'-diamine is formed as a hole transport layer by vacuum evaporation. Finally, an organic EL unit having a white light-emitting layer is fabricated using ITO as a transparent electrode by sputtering. By using a sealing agent to bond the aforementioned laminated body with a cured film to the organic EL unit obtained in this manner, a display device can be manufactured.

[0179] Next, the information terminal of the present invention will be described.

[0180] The information terminal of the present invention is an information terminal having the display device of the present invention described above, such as an electronic device used as a display, for example, a personal computer, a smartphone, a tablet, a smartwatch, smart glasses, a smart home appliance, etc.

[0181] Example

[0182] The present invention is further illustrated by the following examples and comparative examples, but the invention is not limited to these scopes. It should be noted that substances using abbreviations in the compounds used are hereinafter referred to as names.

[0183] PGMEA: Propylene glycol monomethyl ether acetate

[0184] DAA: Diacetone alcohol

[0185] IPA: Isopropyl alcohol

[0186] MIBK: Methyl isobutyl ketone

[0187] BHT: Butylated hydroxytoluene.

[0188] The solid concentration of the polysiloxane solutions in Synthetic Examples 1-9 was determined by the following method: 1.00 g of the polysiloxane solution was weighed into an aluminum cup and heated at 250°C for 30 minutes using a hot plate to evaporate the liquid components. The weight of the solid components remaining in the aluminum cup after heating was measured, and the solid concentration was determined by the ratio of the weight to the weight before heating.

[0189] Regarding the weight-average molecular weight of the polysiloxane solutions in Synthetic Examples 1 to 11, the weight-average molecular weight converted from polystyrene was determined by the following method.

[0190] Apparatus: GPC measuring apparatus (2695) manufactured by Waters with RI detector.

[0191] Columns: PLgel MIXED-C columns (manufactured by Polymara Boralatories, 300mm) x 2 (connected in series)

[0192] Measurement temperature: 40℃

[0193] Flow rate: 1 mL / min

[0194] Solvent: Tetrahydrofuran (THF) 0.5% by mass solution

[0195] Standard material: polystyrene

[0196] Detection mode: RI.

[0197] The content ratio of each repeating unit in the polysiloxanes of Synthetic Examples 1-9 was determined by the following method: The polysiloxane solution was injected into a 10 mm diameter "Teflon" (registered trademark) NMR sample tube. 29Si-NMR measurements were performed, and the content ratio of each repeating unit was calculated from the ratio of the integral value of Si derived from a specific organosilane to the total integral value of Si derived from the organosilane. The following shows... 29 Si-NMR measurement conditions.

[0198] Apparatus: Nuclear Magnetic Resonance Imaging System (JNM-GX270; manufactured by Nippon Electron Ltd.)

[0199] Measurement method: Gated decoupling method

[0200] Nuclear frequency measured: 53.6693MHz 29 Si core)

[0201] Spectral width: 20000Hz

[0202] Pulse width: 12μs (45° pulse)

[0203] Pulse repetition time: 30.0 seconds

[0204] Solvent: Acetone-d6

[0205] Reference material: Tetramethylsilane

[0206] Measurement temperature: 23℃

[0207] Sample rotation speed: 0.0 Hz.

[0208] Synthesis Example 1: Polysiloxane (PSL-1) Solution

[0209] In a 1000 ml three-necked flask, 71.16 g (0.306 mol) of 3-methacryloyloxypropylmethyldimethoxysilane, 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 were added. While stirring at 40 °C for 30 minutes, an aqueous solution of phosphoric acid (3.30 g dissolved in 92.14 g of water, representing 1.0 wt% of the added monomers) was added. The flask was then immersed in an oil bath at 70 °C and stirred for 60 minutes, after which the oil bath temperature was increased to 115 °C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C. Heating and stirring continued for 2 hours (internal temperature 100–110°C) to obtain a polysiloxane solution. It should be noted that during heating and stirring, a mixed gas of 95% (v / v) nitrogen and 5% (v / v) oxygen was flowed at a rate of 0.05 L / min. A total of 210 g of methanol and water, which were byproducts of the reaction, were distilled off. PGMEA was added to the obtained polysiloxane solution at a solids concentration of 40% (w / w) to obtain a polysiloxane (PSL-1) solution. It should be noted that the weight-average molecular weight of the obtained polysiloxane (PSL-1) was 5,000. Furthermore, the molar ratios of the repeating units derived from 3-methacryloyloxypropylmethyldimethoxysilane, styryltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-1) are 17.5 mol%, 20 mol%, 5 mol%, 47.5 mol%, and 10 mol%, respectively.

[0210] Synthesis Example 2: Polysiloxane (PSL-2) Solution

[0211] In a 1000 ml three-necked flask, 71.16 g (0.306 mol) of 3-methacryloyloxypropylmethyldimethoxysilane, 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 were added. While stirring at 40 °C for 30 minutes, an aqueous solution of phosphoric acid (3.61 g dissolved in 92.14 g of water, representing 1.0% by weight of the added monomers) was added. The flask was then immersed in an oil bath at 70 °C and stirred for 60 minutes, after which the oil bath temperature was increased to 115 °C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C. Heating and stirring continued for 2 hours (internal temperature 100–110°C) to obtain a polysiloxane solution. It should be noted that during heating and stirring, a mixed gas of 95% (v / v) nitrogen and 5% (v / v) oxygen was flowed at a rate of 0.05 L / min. A total of 210 g of methanol and water, which were byproducts of the reaction, were distilled off. PGMEA was added to the obtained polysiloxane solution at a solids concentration of 40% (w / w) to obtain a polysiloxane (PSL-2) solution. It should be noted that the weight-average molecular weight of the obtained polysiloxane (PSL-2) was 5,000. Furthermore, the molar ratios of the repeating units derived from 3-methacryloyloxypropylmethyldimethoxysilane, styryltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-2) are 17.5 mol%, 40 mol%, 5 mol%, 27.5 mol%, and 10 mol%, respectively.

[0212] Synthesis Example 3: Polysiloxane (PSL-3) Solution

[0213] In a 1000 ml three-necked flask, 71.16 g (0.306 mol) of 3-methacryloyloxypropylmethyldimethoxysilane, 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 were added. While stirring at 40 °C for 30 minutes, an aqueous solution of phosphoric acid (3.92 g dissolved in 92.14 g of water, representing 1.0% by weight of the added monomers) was added. The flask was then immersed in an oil bath at 70 °C and stirred for 60 minutes, after which the oil bath temperature was increased to 115 °C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C. Heating and stirring continued for 2 hours (internal temperature 100–110°C) to obtain a polysiloxane solution. It should be noted that during heating and stirring, a mixed gas of 95% (v / v) nitrogen and 5% (v / v) oxygen was flowed at a rate of 0.05 L / min. A total of 210 g of methanol and water, which were byproducts of the reaction, were distilled off. PGMEA was added to the obtained polysiloxane solution at a solids concentration of 40% (w / w) to obtain a polysiloxane (PSL-3) solution. It should be noted that the weight-average molecular weight of the obtained polysiloxane (PSL-3) was 4,000. Furthermore, the molar ratios of the repeating units derived from 3-methacryloyloxypropylmethyldimethoxysilane, styryltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-3) are 17.5 mol%, 60 mol%, 5 mol%, 7.5 mol%, and 10 mol%, respectively.

[0214] Synthesis Example 4: Polysiloxane (PSL-4) Solution

[0215] In a 1000 ml three-necked flask, 71.16 g (0.306 mol) of 3-methacryloyloxypropylmethyldimethoxysilane, 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 were added. While stirring at 40 °C for 30 minutes, an aqueous solution of phosphoric acid (4.00 g dissolved in 92.14 g of water, representing 1.0% by weight of the added monomers) was added. The flask was then immersed in an oil bath at 70 °C and stirred for 60 minutes, after which the oil bath temperature was increased to 115 °C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C. Heating and stirring continued for 2 hours (internal temperature 100–110°C) to obtain a polysiloxane solution. It should be noted that during heating and stirring, a mixed gas of 95% (v / v) nitrogen and 5% (v / v) oxygen was flowed at a rate of 0.05 L / min. A total of 210 g of methanol and water, which were byproducts of the reaction, were distilled off. PGMEA was added to the obtained polysiloxane solution at a solids concentration of 40% (w / w) to obtain a polysiloxane (PSL-4) solution. It should be noted that the weight-average molecular weight of the obtained polysiloxane (PSL-4) was 3,000. Furthermore, the molar ratios of the repeating units derived from 3-methacryloyloxypropylmethyldimethoxysilane, styryltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-3) are 17.5 mol%, 65 mol%, 5 mol%, 2.5 mol%, and 10 mol%, respectively.

[0216] Synthesis Example 5: Polysiloxane (PSL-5) Solution

[0217] In a 1000 ml three-necked flask, 71.16 g (0.306 mol) of 3-methacryloyloxypropylmethyldimethoxysilane, 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 were added. While stirring at 40 °C for 30 minutes, an aqueous solution of phosphoric acid (3.23 g dissolved in 92.14 g of water, representing 1.0% by weight of the added monomers) was added. The flask was then immersed in an oil bath at 70 °C and stirred for 60 minutes, after which the oil bath temperature was increased to 115 °C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C. Heating and stirring continued for 2 hours (internal temperature 100–110°C) to obtain a polysiloxane solution. It should be noted that during heating and stirring, a mixed gas of 95% (v / v) nitrogen and 5% (v / v) oxygen was flowed at a rate of 0.05 L / min. A total of 210 g of methanol and water, which were byproducts of the reaction, were distilled off. PGMEA was added to the obtained polysiloxane solution at a solids concentration of 40% (w / w) to obtain a polysiloxane (PSL-5) solution. It should be noted that the weight-average molecular weight of the obtained polysiloxane (PSL-5) was 5,000. Furthermore, the molar ratios of the repeating units derived from 3-methacryloyloxypropylmethyldimethoxysilane, styryltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-5) are 17.5 mol%, 15 mol%, 5 mol%, 52.5 mol%, and 10 mol%, respectively.

[0218] Synthesis Example 6: Polysiloxane (PSL-6) Solution

[0219] In a 1000 ml three-necked flask, 71.16 g (0.306 mol) of 3-methacryloyloxypropylmethyldimethoxysilane, 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 were added. While stirring at 40 °C for 30 minutes, an aqueous solution of phosphoric acid (3.15 g dissolved in 92.14 g of water, representing 1.0 wt% of the added monomers) was added. The flask was then immersed in an oil bath at 70 °C and stirred for 60 minutes, after which the oil bath temperature was increased to 115 °C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C. Heating and stirring continued for 2 hours (internal temperature 100–110°C) to obtain a polysiloxane solution. It should be noted that during heating and stirring, a mixed gas of 95% (v / v) nitrogen and 5% (v / v) oxygen was flowed at a rate of 0.05 L / min. A total of 210 g of methanol and water, which were byproducts of the reaction, were distilled off. PGMEA was added to the obtained polysiloxane solution at a solids concentration of 40% (w / w) to obtain a polysiloxane (PSL-6) solution. It should be noted that the weight-average molecular weight of the obtained polysiloxane (PSL-6) was 6,000. Furthermore, the molar ratios of the repeating units derived from 3-methacryloyloxypropylmethyldimethoxysilane, styryltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-6) are 17.5 mol%, 10 mol%, 5 mol%, 57.5 mol%, and 10 mol%, respectively.

[0220] Synthesis Example 7: Polysiloxane (PSL-7) Solution

[0221] In a 1000 ml three-necked flask, 71.16 g (0.306 mol) of 3-methacryloyloxypropylmethyldimethoxysilane, 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 were added. While stirring at 40 °C for 30 minutes, an aqueous solution of phosphoric acid (3.07 g dissolved in 92.14 g of water, representing 1.0% by weight of the added monomers) was added. The flask was then immersed in an oil bath at 70 °C and stirred for 60 minutes, after which the oil bath temperature was increased to 115 °C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C. Heating and stirring continued for 2 hours (internal temperature 100–110°C) to obtain a polysiloxane solution. It should be noted that during heating and stirring, a mixed gas of 95% (v / v) nitrogen and 5% (v / v) oxygen was flowed at a rate of 0.05 L / min. A total of 210 g of methanol and water, as byproducts of the reaction, were distilled off. PGMEA was added to the obtained polysiloxane solution at a solids concentration of 40% (w / w) to obtain a polysiloxane (PSL-7) solution. It should be noted that the weight-average molecular weight of the obtained polysiloxane (PSL-7) was 6,500. Furthermore, the molar ratios of the repeating units derived from 3-methacryloyloxypropylmethyldimethoxysilane, styryltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-7) are 17.5 mol%, 5 mol%, 5 mol%, 62.5 mol%, and 10 mol%, respectively.

[0222] Synthesis Example 8: Polysiloxane (PSL-8) Solution

[0223] In a 1000 ml three-necked flask, 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 were added. While stirring at 40 °C for 30 minutes, an aqueous solution of phosphoric acid (3.07 g dissolved in 92.14 g of water, representing 1.0% by weight of the added monomers) was added. The flask was then immersed in an oil bath at 70 °C and stirred for 60 minutes, after which the oil bath temperature was increased to 115 °C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C. Heating and stirring continued for 2 hours (internal temperature 100–110°C) to obtain a polysiloxane solution. It should be noted that during heating and stirring, a mixed gas of 95% (v / v) nitrogen and 5% (v / v) oxygen was flowed at a rate of 0.05 L / min. A total of 196 g of methanol and water, as byproducts of the reaction, were distilled off. PGMEA was added to the obtained polysiloxane solution at a solids concentration of 40% (w / w) to obtain a polysiloxane (PSL-8) solution. It should be noted that the weight-average molecular weight of the obtained polysiloxane (PSL-8) was 2,500. Furthermore, the molar ratios of the repeating units derived from 3-methacryloyloxypropylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-8) are 37.5 mol%, 5 mol%, 47.5 mol%, and 10 mol, respectively.

[0224] Synthesis Example 9: Polysiloxane (PSL-9) Solution

[0225] The synthesis was carried out in the same manner as in Synthesis Example 8, with heating and stirring for 3 hours (internal temperature 100–110°C) after reaching an internal temperature of 100°C, to obtain a polysiloxane solution. It should be noted that during heating and stirring, a mixed gas of 95% (v / v) nitrogen and 5% (v / v) oxygen was flowed at a rate of 0.05 L / min. A total of 200 g of methanol and water, which were byproducts of the reaction, were distilled off. PGMEA was added to the obtained polysiloxane solution at a solids concentration of 40% (w / w) to obtain a polysiloxane (PSL-9) solution. It should be noted that the weight-average molecular weight of the obtained polysiloxane (PSL-9) was 3,600. Furthermore, the molar ratios of the repeating units derived from 3-methacryloyloxypropylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-9) are 37.5 mol%, 5 mol%, 47.5 mol%, and 10 mol, respectively.

[0226] Synthesis Example 10: Polysiloxane (PSL-10) Solution

[0227] The synthesis was carried out in the same manner as in Synthesis Example 8, with heating and stirring for 4 hours (internal temperature 100–110°C) after reaching an internal temperature of 100°C, to obtain a polysiloxane solution. It should be noted that during heating and stirring, a mixed gas of 95% (v / v) nitrogen and 5% (v / v) oxygen was flowed at a rate of 0.05 L / min. A total of 210 g of methanol and water, which were byproducts of the reaction, were distilled off. PGMEA was added to the obtained polysiloxane solution at a solids concentration of 40% (w / w) to obtain a polysiloxane (PSL-10) solution. It should be noted that the weight-average molecular weight of the obtained polysiloxane (PSL-10) was 4,300. Furthermore, the molar ratios of the repeating units derived from 3-methacryloyloxypropylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-10) are 37.5 mol%, 5 mol%, 47.5 mol%, and 10 mol, respectively.

[0228] Synthesis Example 11: Polysiloxane (PSL-11) Solution

[0229] In a 1000 ml three-necked flask, 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 were added. While stirring at 40 °C for 30 minutes, an aqueous solution of phosphoric acid (3.71 g dissolved in 80.33 g of water, representing 1.0% by weight of the added monomers) was added. Then, the flask was immersed in an oil bath at 70°C and stirred for 60 minutes. The oil bath was then heated to 115°C over 30 minutes. One hour after the start of heating, the solution temperature (internal temperature) reached 100°C, and the mixture was heated and stirred for 2 hours (internal temperature 100–110°C) to obtain a polysiloxane solution. It should be noted that during heating and stirring, a mixed gas of 95% (v / v) nitrogen and 5% (v / v) oxygen was flowed at a rate of 0.05 L / min. A total of 183 g of methanol and water, which were byproducts of the reaction, were distilled off. PGMEA was added to the obtained polysiloxane solution at a solids concentration of 40% (w / w) to obtain a polysiloxane (PSL-11) solution. It should be noted that the weight-average molecular weight of the obtained polysiloxane (PSL-11) was 1,500. Furthermore, the molar ratios of the repeating units derived from 3-methacryloyloxypropylmethyldimethoxysilane, diphenylditrimethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, methyltrimethoxysilane, and 3-trimethoxysilylpropylsuccinic anhydride in polysiloxane (PSL-11) are 17.5 mol%, 37.5 mol%, 5 mol%, 30 mol%, and 10 mol%, respectively.

[0230] The composition of synthetic examples 1 to 11 is summarized in Table 1.

[0231] [Table 1-1]

[0232] [Table 1-2]

[0233] Synthesis Example 12: Synthesis of (meth)acrylic acid polymer solution (PAL-1)

[0234] In a 500 mL flask, 3.00 g of 2,2'-azobis(isobutyronitrile) and 50.0 g of PGMEA were added, followed by 30.0 g (0.349 mol) of methacrylic acid, 22.48 g (0.216 mol) of styrene, and 35.0 g (0.149 mol) of tricyclo[5.2.1.02,6]decane-8-ylmethacrylate. The mixture was stirred briefly at room temperature, then purged with nitrogen and heated at 70 °C with stirring 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. The mixture was heated at 90 °C with stirring for 4 hours to obtain a (meth)acrylic acid polymer solution. PGMEA was added to the obtained (meth)acrylic polymer solution at a solid content concentration of 40% by weight to prepare (meth)acrylic polymer solution (PAL-1). The weight-average molecular weight of the (meth)acrylic polymer was 16,000.

[0235] Example 1 Resin Composition (P-1)

[0236] 5.00 g of titanium dioxide pigment (CR-97; manufactured by Ishihara Sangyo Co., Ltd. (hereinafter "CR-97")) as particles, 0.50 g of phosphate polyester ("DISPERBYK" (registered trademark)-111; manufactured by Bickkemijapan Co., Ltd. (hereinafter "DISPERBYK-111")) as dispersant, and 4.50 g of PGMEA as 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 by Synthesis Example 1, 5.00 g of the above-mentioned particle dispersion (MW-1), and acetone as a photopolymerization initiator, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime) (“Ilugacchari” (registered trademark) OXE-02, manufactured by BASF Japan Co., Ltd. (hereinafter “O”) XE-02”))0.150g, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (“Omnirad-819”, manufactured by BASF Japan Co., Ltd. (hereinafter “Omnirad-819”))0.0500g, dipentaerythritol hexaacrylate (“KAYARAD” (registered trademark) DPHA, a photopolymerizable compound manufactured by Shin Nippon Pharmaceutical Co., Ltd. (hereinafter “DPHA”) 1.60g, 0.125g of "Megafack" (registered trademark) RS-57 (20% by weight MIBK diluted solution, manufactured by DIC Co., Ltd. (hereinafter "RS-57")) as a liquid-repellent compound, and 0.125g of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate ("Cerokide" (registered trademark) 2021P, manufactured by Daicel Co., Ltd.) as an adhesion modifier (in the form of... 0.100 g of "Cerok Said 2021P", 0.100 g of "Irganox" (registered trademark) 1010 (manufactured by BASF Japan Co., Ltd., hereinafter "Irganox1010") as a polymerization inhibitor, and 0.100 g of a 10% by weight diluted solution of an acrylic surfactant ("BYK" (registered trademark) 352 (manufactured by Bickchem Japan Co., Ltd., hereinafter "BYK-352")) in PGMEA (equivalent to a concentration of 500 ppm) were dissolved in solvents 1.00 g of PGMEA and 0.500, and stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a resin composition (P-1).

[0237] Example 2 Resin Composition (P-2)

[0238] Instead of polysiloxane (PSL-1) solution, 6.35 g of polysiloxane (PSL-2) solution was added, and the resin composition (P-2) was obtained by operating in the same manner as in Example 1.

[0239] Example 3 Resin Composition (P-3)

[0240] Instead of polysiloxane (PSL-1) solution, 6.35 g of polysiloxane (PSL-3) solution was added, and the resin composition (P-3) was obtained by operating in the same manner as in Example 1.

[0241] Example 4 Resin Composition (P-4)

[0242] Instead of polysiloxane (PSL-1) solution, 6.35 g of polysiloxane (PSL-4) solution was added, and the resin composition (P-4) was obtained by operating in the same manner as in Example 1.

[0243] Example 5 Resin Composition (P-5)

[0244] Instead of polysiloxane (PSL-1) solution, 6.35 g of polysiloxane (PSL-5) solution was added, and the resin composition (P-5) was obtained by operating in the same manner as in Example 1.

[0245] Example 6 Resin Composition (P-6)

[0246] Instead of polysiloxane (PSL-1) solution, 6.35 g of polysiloxane (PSL-6) solution was added, and the resin composition (P-6) was obtained by operating in the same manner as in Example 1.

[0247] Example 7 Resin Composition (P-7)

[0248] Instead of polysiloxane (PSL-1) solution, 6.35 g of polysiloxane (PSL-7) solution was added, and the resin composition (P-7) was obtained by operating in the same manner as in Example 1.

[0249] Example 8 Resin Composition (P-8)

[0250] Instead of polysiloxane (PSL-1) solution, 6.35 g of polysiloxane (PSL-8) solution was added, and the resin composition (P-8) was obtained by operating in the same manner as in Example 1.

[0251] Example 9 Resin Composition (P-9)

[0252] Instead of polysiloxane (PSL-1) solution, 6.35 g of polysiloxane (PSL-9) solution was added, and the resin composition (P-9) was obtained by operating in the same manner as in Example 1.

[0253] Example 10 Resin Composition (P-10)

[0254] Instead of polysiloxane (PSL-1) solution, 6.35 g of polysiloxane (PSL-10) solution was added, and the resin composition (P-10) was obtained by operating in the same manner as in Example 1.

[0255] Example 11 Resin Composition (P-11)

[0256] Instead of polysiloxane (PSL-1) solution, 6.35 g of polysiloxane (PSL-11) solution was added, and the resin composition (P-11) was obtained by operating in the same manner as in Example 1.

[0257] Example 12 Resin Composition (P-12)

[0258] The amount of liquid-repellent compound RS-57 was changed to 0.250 g, and the amount of polysiloxane (PSL-1) solution was changed to 6.29 g. Otherwise, the resin composition (P-12) was obtained by operating in the same manner as in Example 1.

[0259] Example 13 Resin Composition (P-13)

[0260] The amount of liquid-repellent compound RS-57 was changed to 0.500 g, and the amount of polysiloxane (PSL-1) solution was changed to 6.16 g. Otherwise, the resin composition (P-13) was obtained by operating in the same manner as in Example 1.

[0261] Example 14 Resin Composition (P-14)

[0262] Instead of polysiloxane (PSL-1) solution, 6.35 g of polysiloxane (PSL-11) solution was added, and the resin composition (P-14) was obtained by operating in the same manner as in Example 13.

[0263] Example 15 Resin Composition (P-15)

[0264] Instead of the liquid-repellent compound RS-57, 0.125 g of a 20% by weight diluted solution of PGMEA (BYK UV3510, manufactured by BYK-UV3510 Co., Ltd., hereinafter "BYK-UV3510") was added, and the resin composition (P-15) was obtained by operating in the same manner as in Example 1.

[0265] Example 16 Resin Composition (P-16)

[0266] Instead of the liquid-repellent compound RS-57, 0.125 g of a 20% by weight diluted solution of "BYK" (registered trademark) UV3530, manufactured by BYK-UV3530 Co., Ltd. (hereinafter "BYK-UV3530"), was added. Otherwise, the resin composition (P-16) was obtained by operating in the same manner as in Example 1.

[0267] Example 17 Resin Composition (P-17)

[0268] Instead of the liquid-repellent compound RS-57, 0.125 g of a 20% by weight diluted solution of PGMEA (BYK UV3575, manufactured by BYK-UV3575 Co., Ltd., hereinafter "BYK-UV3575") was added, and the resin composition (P-17) was obtained by operating in the same manner as in Example 1.

[0269] Example 18 Resin Composition (P-18)

[0270] 16.1 g of polysiloxane (PSL-1) solution, 0.120 g of OXE-02 (as a photopolymerization initiator), 0.0400 g of Omnirad-819, 1.28 g of DPHA (as a photopolymerizable compound), 0.100 g of RS-57 (as a liquid-repellent compound), 0.0800 g of Cerokide 2021P (as an adhesion modifier), 0.0200 g of Irganox 1010 (as a polymerization inhibitor), and 0.100 g of a 10% by weight diluted solution of the acrylic surfactant BYK-352 in PGMEA (equivalent to a concentration of 500 ppm) were dissolved in solvents containing 1.59 g of PGMEA and 0.600 g of DAA, and the mixture was stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a resin composition (P-18).

[0271] Example 19 Resin Composition (P-19)

[0272] 5.00 g of titanium nitride black pigment as particles, 0.50 g of phosphate polyester DISPERBYK-111 as dispersant, and 4.50 g of PGMEA as 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, 0.120 g of OXE-02 (as a photopolymerization initiator), 0.0400 g of Omnirad-819, 1.28 g of DPHA (as a photopolymerizable compound), 0.100 g of RS-57 (as a liquid-repellent compound), 0.0800 g of Ceroxy Sid 2021P (as an adhesion modifier), 0.0200 g of Irganox 1010 (as a polymerization inhibitor), and 0.100 g of a 10% by weight diluted solution of the acrylic surfactant BYK-352 (equivalent to a concentration of 500 ppm) were dissolved in solvents 1.89 g of PGMEA and 0.600 g of DAA, and the mixture was stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain the resin composition (P-19).

[0273] Example 20 Resin Composition (P-20)

[0274] 5.00 g of titanium dioxide pigment as particles, 0.0188 g of titanium black pigment, 0.50 g of phosphate polyester DISPERBYK-111 as a dispersant, and 4.48 g of PGMEA as a solvent were mixed and dispersed using a mill-type disperser filled with zirconia beads to obtain a particle dispersion (MW-3). Instead of particle dispersion (MW-2), 3.20 g of particle dispersion (MW-3) was added, the amount of polysiloxane (PSL-1) solution added was changed to 7.25 g, and the amount of PGMEA added was changed to 4.00 g. Otherwise, the same procedure as in Example 19 was followed to obtain a resin composition (P-20).

[0275] Example 21 Resin Composition (P-21)

[0276] A resin composition (P-21) was obtained by adding 0.100 g (equivalent to a concentration of 500 ppm) of a 10% wt PGMEA solution of the fluorinated surfactant "Megafaq" (registered trademark) F-477 (manufactured by DIC Co., Ltd. (hereinafter "F-477")) instead of a 10% wt PGMEA solution of the acrylic surfactant BYK-352, and otherwise proceeding in the same manner as in Example 1.

[0277] Example 22 Resin Composition (P-22)

[0278] The amount of polysiloxane (PSL-1) solution added was changed to 6.10 g, the amount of solvent PGMEA added was changed to 1.15 g, and 0.10 g of zirconium tetraacetylacetone (trade name "Orgachix" (registered trademark) ZC-150, manufactured by Matsumetofinkemica Co., Ltd. (hereinafter "ZC-150")) as a metal chelating agent was added. Otherwise, the resin composition (P-22) was obtained by operating in the same manner as in Example 1.

[0279] Example 23 Resin Composition (P-23)

[0280] As a metal chelating agent, 0.10 g of tri(acetylacetone) aluminum (trade name AlmiKiller A(a), manufactured by Kawaken Finkemica Co., Ltd. (hereinafter "AL-A(a)")) was added instead of ZC-150. Otherwise, the resin composition (P-23) was obtained by operating in the same manner as in Example 22.

[0281] Example 24 Resin Composition (P-24)

[0282] As a metal chelating agent, 0.10 of tri(ethylacetoacetic acid) aluminum (ALCH-TR, manufactured by Kawaken Finke Mikael Co., Ltd. (hereinafter "ALCH-TR")) was added instead of ZC-150g. Otherwise, the resin composition (P-24) was obtained by operating in the same manner as in Example 22.

[0283] Example 25 Resin Composition (P-25)

[0284] As a metal chelating agent, 0.10 g of aluminum diisopropoxide of alkyl acetoacetate (trade name AlmiKiller M, manufactured by Kawaken Finkemica Co., Ltd. (hereinafter "AL-M")) was added instead of ZC-150. Otherwise, the resin composition (P-25) was obtained by operating in the same manner as in Example 22.

[0285] Example 26 Resin Composition (P-26)

[0286] As a metal chelating agent, 0.10 g of zinc diacetylacetonate (hereinafter, "Zn(acac)2") was added instead of ZC-150. Otherwise, the resin composition (P-25) was obtained by operating in the same manner as in Example 22.

[0287] Example 27 Resin Composition (P-27)

[0288] 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. Otherwise, the resin composition (P-27) was obtained by operating in the same manner as in Example 23.

[0289] Example 28 Resin Composition (P-28)

[0290] 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. Otherwise, the resin composition (P-28) was obtained by operating in the same manner as in Example 23.

[0291] Example 29 Resin Composition (P-29)

[0292] 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. Otherwise, the resin composition (P-29) was obtained by operating in the same manner as in Example 23.

[0293] Example 30 Resin Composition (P-30)

[0294] 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% by weight diluted solution of the acrylic surfactant BYK-352 PGMEA (equivalent to a concentration of 500 ppm) were dissolved in solvents 4.15 g of PGMEA and 0.700 DAA, and the mixture was stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain the resin composition (P-30).

[0295] Example 31 Resin Composition (P-31)

[0296] 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% by weight diluted solution of the acrylic surfactant BYK-352 in PGMEA (equivalent to a concentration of 500 ppm) were dissolved in solvents containing 4.33 g of PGMEA and 0.700 DAA, and the mixture was stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain the resin composition (P-31).

[0297] Example 32 Resin Composition (P-32)

[0298] 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 20% by weight IPA solution of hollow silica (trade name Sluria 4110, manufactured by Nichiki Catalyst Chemicals Co., Ltd. (hereinafter "Sluria 4110")), and 0.100 g of a 10% by weight diluted solution of PGMEA of acrylic surfactant BYK-352 (equivalent to a concentration of 500 ppm) were dissolved in solvents 7.03 g of PGMEA and 0.700 g of DAA, and the mixture was stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain a resin composition (P-32).

[0299] Example 33 Resin Composition (P-33)

[0300] Instead of polysiloxane (PSL-1) solution, polysiloxane (PSL-7) solution was used, and the resin composition (P-33) was obtained by operating in the same manner as in Example 15.

[0301] Example 34 Resin Composition (P-34)

[0302] Instead of polysiloxane (PSL-1) solution, polysiloxane (PSL-7) solution was used, and the resin composition (P-34) was obtained by operating in the same manner as in Example 16.

[0303] Example 35 Resin Composition (P-35)

[0304] Instead of polysiloxane (PSL-1) solution, polysiloxane (PSL-7) solution was used, and the resin composition (P-35) was obtained by operating in the same manner as in Example 17.

[0305] Example 36 Resin Composition (P-36)

[0306] Instead of polysiloxane (PSL-1) solution, polysiloxane (PSL-3) solution was used, and the resin composition (P-36) was obtained by operating in the same manner as in Example 15.

[0307] Example 37 Resin Composition (P-37)

[0308] Instead of polysiloxane (PSL-1) solution, polysiloxane (PSL-3) solution was used, and the resin composition (P-37) was obtained by operating in the same manner as in Example 16.

[0309] Example 38 Resin Composition (P-38)

[0310] Instead of polysiloxane (PSL-1) solution, polysiloxane (PSL-3) solution was used, and the resin composition (P-38) was obtained by operating in the same manner as in Example 17.

[0311] Comparative Example 1 Resin Composition (P-39)

[0312] Instead of the polysiloxane (PSL-1) solution, 6.35 g of (meth)acrylic polymer solution (PAL-1) was added, and the resin composition (P-39) was obtained by operating in the same manner as in Example 1.

[0313] Comparative Example 2 Resin Composition (P-40)

[0314] Instead of the polysiloxane (PSL-1) solution, 6.35 g of a 40% PGMEA solution of cardo-based polymer V-259ME (trade name, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) was added, and the resin composition (P-40) was obtained by operating in the same manner as in Example 1.

[0315] Comparative Example 3 Resin Composition (P-41)

[0316] Without adding the liquid-repellent compound RS-57, the amount of polysiloxane (PSL-1) solution added was changed to 6.41 g, and the resin composition (P-41) was obtained by operating in the same manner as in Example 1.

[0317] Comparative Example 4 Resin Composition (P-42)

[0318] Instead of the polysiloxane (PSL-1) solution, 6.35 g of (meth)acrylic polymer solution (PAL-1) was added, and the resin composition (P-42) was obtained by operating in the same manner as in Example 13.

[0319] Comparative Example 5 Resin Composition (P-43)

[0320] Instead of the polysiloxane (PSL-1) solution, 6.35 g of cardo-based polymer V-259ME40 wt% PGMEA solution was added, and the resin composition (P-43) was obtained by operating in the same manner as in Example 13.

[0321] Comparative Example 6 Resin Composition (P-44)

[0322] Instead of the liquid-repellent compound RS-57, 0.125 g of "Megafack" (registered trademark) RS-75-A (20% by weight PGMEA diluted solution, manufactured by DIC Co., Ltd.: a fluorinated surfactant with photopolymerizable groups (hereinafter "RS-75-A")) was added, and the resin composition (P-44) was obtained by operating in the same manner as in Example 1.

[0323] Comparative Example 7 Resin Composition (P-45)

[0324] 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. Otherwise, the resin composition (P-45) was obtained by operating in the same manner as in Comparative Example 6.

[0325] Comparative Example 8 Resin Composition (P-46)

[0326] Instead of the polysiloxane (PSL-1) solution, a (meth)acrylic polymer solution (PAL-1) was added, and the resin composition (P-46) was obtained by operating in the same manner as in Example 31.

[0327] Comparative Example 9 Resin Composition (P-47)

[0328] Instead of the polysiloxane (PSL-1) solution, a cardo-based polymer V-259ME40 wt% PGMEA solution was added, and the resin composition (P-47) was obtained by operating in the same manner as in Example 31.

[0329] Comparative Example 10 Resin Composition (P-48)

[0330] 15.06 g of polysiloxane (PSL-1) solution and 0.100 g of a 10% by weight diluted solution of the acrylic surfactant BYK-352 PGMEA (equivalent to a concentration of 500 ppm) were dissolved in solvents containing 4.23 g of PGMEA and 0.700 DAA, and the mixture was stirred. The resulting mixture was filtered through a 5.0 μm filter to obtain the resin composition (P-48).

[0331] The composition of Examples 1-38 and Comparative Examples 1-10 is summarized in Table 2.

[0332] [Table 2-1]

[0333] [Table 2-2]

[0334] [Table 2-3]

[0335] [Table 2-4]

[0336] Modulation Example 1: Color-Converting Luminescent Material Composition (CL-1)

[0337] A mixture of 20 parts by weight of a 0.5% toluene solution of green quantum dot material (Lumidot 640 CdSe / ZnS, average particle size 6.3 nm: manufactured by Artrich Co., Ltd.), 45 parts by weight of DPHA, 5 parts by weight of "Ilugakia" (registered trademark) 907 (manufactured by BASF Japan Co., Ltd.), 166 parts by weight of a 30% PGMEA solution of acrylic resin (SPCR-18 (trade name), manufactured by Showa Denko Co., Ltd.), and 97 parts by weight of toluene was stirred and uniformly dissolved. The resulting mixture was filtered through a 0.45 μm syringe filter to prepare a color-converting luminescent material composition (CL-1).

[0338] Modulation Example 2: Color-converting luminescent material composition (CL-2)

[0339] Instead of green quantum dot material, red quantum dot material (InP / ZnS: manufactured by Aldrich) was used. Otherwise, the same operation as in Modulation Example 1 was used to modulate a color-converting luminescent material composition (CL-2).

[0340] Modulation Example 3: Black Matrix Material Composition (BM-1)

[0341] A slurry was prepared by mixing 150g of carbon black (MA100, manufactured by Mitsubishi Chemical Co., Ltd.), 75g of polymeric dispersant BYK-6919, 100g of P(ACA)Z250, and 675g of PGMEA. A beaker containing the slurry was connected to a Dino mill via a tube, and 0.5mm diameter zirconia beads were used as the dispersing medium. The mixture was dispersed at a circumferential speed of 14m / s for 8 hours to produce a pigment dispersion (MB-1).

[0342] The pigment dispersion (MB-1) 56.54g, P(ACA)Z250 3.14g, DPHA 2.64g, NCI-831 0.330g, BYK-333 0.04g, tert-butylcatechol as a polymerization inhibitor 0.01g and PGMEA 37.30g were mixed to prepare the black matrix material composition (BM-1).

[0343] Modulation Example 4: Color Filter Material (CF-1)

[0344] A slurry was prepared by mixing 90g of CI Pigment Green 59, 60g of CI Pigment Yellow 150, 75g of polymeric dispersant ("BYK" (registered trademark)-6919 (trade name) manufactured by Bickkemy Co., Ltd. (hereinafter "BYK-6919")), 100g of binder resin ("Adek Acrylics" (registered trademark) WR301 (trade name) manufactured by ADEKA Co., Ltd.), and 675g of PGMEA. The beaker containing the slurry was connected to a Dino mill via a tube, and 0.5mm diameter zirconia beads were used as the medium. The dispersion was carried out at a circumferential speed of 14m / s for 8 hours to prepare Pigment Green 59 dispersion (GD-1).

[0345] 56.54g of Pigment Green 59 Dispersion (GD-1) and acrylic resin (“Cyclomar” (registered trademark) P(ACA) Z250 (trade name) Daicel) were added. A color filter material (CF-1) is prepared by mixing 3.14g of Ornex Co., Ltd. (hereinafter "P(ACA)Z250"), 2.64g of DPHA, 0.330g of photopolymerization initiator ("Optoma" (registered trademark) NCI-831 (trade name) (ADEKA Co., Ltd. (hereinafter "NCI-831")), 0.04g of surfactant ("BYK" (registered trademark) -333 (trade name) Bickkeme Co., Ltd. (hereinafter "BYK-333")), 0.01g of BHT as a polymerization inhibitor, and 37.30g of PGMEA as a solvent.

[0346] Examples 39-71, Comparative Examples 11-25

[0347] A 10cm square alkali-free glass substrate (manufactured by AGC Technoglass Co., Ltd., 0.7mm thick; hereinafter the same) or a 6-inch Si wafer was used as the substrate. The resin compositions shown in Tables 3-5 were coated onto the substrate using spin coating. A dried film was then prepared by drying at 90°C for 3 minutes using a hot plate (trade name SCW-636, manufactured by Dai Nippon Screen Manufacturing Co., Ltd.; hereinafter the same). The prepared dried film was then exposed to a parallel light mask using a parallel light mask exposure machine (trade name PLA-501F, manufactured by Kanon Co., Ltd.; hereinafter the same), with an ultra-high pressure mercury lamp (g, h, i rays) as the light source, partially through a photomask at an exposure dose of 300mJ / cm². 2Exposure was performed using (i-ray conversion value). Then, using an automatic developing apparatus (Takizawa Sangyo Co., Ltd. "AD-2000" (trade name); hereinafter the same), spray development was performed for 100 seconds using a 0.045% by weight potassium hydroxide aqueous solution, followed by rinsing with water for 30 seconds. Further, using an oven (trade name IHPS-222, Espec Co., Ltd.; hereinafter the same), heating was performed in air at a temperature of 150°C for 60 minutes, thereby forming a full-coverage film (cured film) with a height of 10 μm and a grid-like spacer pattern (cured film) with a spacing of 10 μm in height, 10 μm in width, and an opening of 40 μm × 140 μm on a glass substrate or Si wafer, thus creating a laminate.

[0348] Examples 72-104, Comparative Examples 26-40

[0349] Using a 10cm square alkali-free glass substrate as the base substrate, the resin compositions shown in Tables 6-8 are coated on it by spin coating. The same operation as in Examples 39-71 and Comparative Examples 11-25 is performed to form a grid-like spacer pattern, thus producing a laminate with a cured film.

[0350] Next, in a portion of the region of the resulting laminate separated by spacers, a color-conversion luminescent material composition (CL-1) was applied using inkjet printing under a nitrogen atmosphere and dried at 100°C for 30 minutes to form a 10 μm thick wavelength conversion layer, thus obtaining... Figure 7 The structure shown is a laminate containing a cured film and a wavelength conversion layer.

[0351] Then, the resulting stack was placed into a sputtering apparatus SH-450 (manufactured by Alback Corporation), using silicon oxide as the sputtering target, and a 0.1 μm thick SiO2 layer as an inorganic protective layer was formed from the top, obtaining... Figure 8 The structure shown is a laminate containing a cured film, a wavelength conversion layer, and an inorganic protective layer.

[0352] Examples 105-122, Comparative Examples 41-50

[0353] A 10cm square alkali-free glass substrate or a 6-inch Si wafer was used as the substrate. The resin composition shown in Tables 9-10 was applied to the substrate using spin coating. The substrate was then dried at 90°C for 3 minutes using a hot plate to create a dried film. The dried film was then exposed using a parallel light mask exposure machine with an ultra-high pressure mercury lamp (g, h, i rays) as the light source, with an exposure dose of 300 mJ / cm². 2Exposure was performed using (i-ray conversion values). Then, using an automatic developing apparatus, development was carried out by spraying with a 0.045 wt% potassium hydroxide aqueous solution for 100 seconds, followed by rinsing with water for 30 seconds. Further, using an oven, the film was heated in air at 90°C for 60 minutes to form a full-coverage film (cured film) with a height of 10 μm on a glass substrate or Si wafer, thereby creating a laminate.

[0354] Example 123

[0355] A 10cm square alkali-free glass substrate or a 6-inch Si wafer was used as the substrate. A resin composition (P-31) was applied to the substrate using spin coating, and the film was dried at 90°C for 3 minutes using a hot plate to create a dried film. The dried film was then exposed using a parallel light mask exposure machine with an ultra-high pressure mercury lamp (g, h, i rays) as the light source, with an exposure dose of 300 mJ / cm². 2 The i-ray conversion value was exposed. Then, without development, the film was heated in an oven at 90°C for 60 minutes to form a full-coverage film (cured film) with a height of 10 μm on the glass substrate or Si wafer, thus creating a stack.

[0356] The configuration and evaluation results of each embodiment and comparative example are shown in Tables 3 to 10.

[0357] [Table 3]

[0358] [Table 4]

[0359] [Table 5]

[0360] [Table 6]

[0361] [Table 7]

[0362] [Table 8]

[0363] [Table 9]

[0364] [Table 10]

[0365] The following shows the evaluation methods for laminated films with cured films in various embodiments and comparative examples.

[0366] <Altitude>

[0367] Regarding the cured film in the laminate obtained through the various embodiments and comparative examples, the film thickness of the spacer portion was measured using a Servocom stylus-type film thickness measuring device, and the difference between the top of the spacer and the surface of the glass substrate was calculated, thereby measuring the height.

[0368] <XPS Analysis>

[0369] Regarding the full-coverage portion of the cured film in the laminate obtained through the various embodiments and comparative examples, the Shiga Prefectural Industrial Technology Center was commissioned to conduct analysis using a PHI5000 Versa Probe2 X-ray photoelectron spectroscopy analyzer. (Manufactured by Fai Co., Ltd.), the presence of fluorine, carbon, oxygen, silicon, and nitrogen atoms was analyzed from the upper surface of the membrane. A case where no peak was detected at 691 eV, below the detection limit of the measuring device, was defined as "no F," and a case where a peak was detected at 691 eV, representing the presence of a peak from fluorine atoms (F1S), was defined as "present F." It should be noted that, as an example, the XPS analysis results of Example 39, which was defined as "no F," are shown below. Figure 12 In the figure, the XPS analysis results of Comparative Example 21, which was determined to have "F", are shown. Figure 13 middle.

[0370] Surface free energy

[0371] Regarding the full-coverage portion of the cured film in the laminates obtained through the various embodiments and comparative examples, the contact angle of the film surface was measured using a microsyringe DM-700 (manufactured by Kyowa Interface Science Co., Ltd.) and a 22G coating needle for a contact angle meter (Teflon, a registered trademark), at 25°C and in atmospheric conditions, according to 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 full-coverage film surface were measured. The surface free energy (mN / m) was calculated from each measured value based on the theoretical formula of Owent and Wendt.

[0372] <FT-IR analysis>

[0373] The full-coverage portion of the cured film in the laminates obtained through the various embodiments and comparative examples was measured using a Fourier transform infrared spectrophotometer, Avatar360 (manufactured by Nicolet Co., Ltd.), by total internal reflection infrared spectroscopy (ATR). The sample surface was measured using a single-reflection horizontal ATR measuring device (OMNISampler) manufactured by Nicolet Co., Ltd., and a diamond ATR crystal as accessories for the total internal reflection measurement. The resolution was set to 4 cm as the measurement conditions. -1 The number of scans was set to 32, and measurements were performed. The resulting spectra were measured in the range of 950–1780 cm⁻¹. -1 After tilt correction, the range of 950–1250 cm⁻¹ derived from siloxane bonds (Si-O) was calculated. -1 The absorption intensity at the peak (E) SiO ) and 1650–1750 cm from carbonyl (C=O) groups -1 The absorption intensity at the peak (E) CO The ratio of (E) SiO / E CO It should be noted that regarding the peak, E... SiO E CO As mentioned above.

[0374] <Inkjet Experiment>

[0375] Spreadability when applying small amounts

[0376] Regarding the spacer wall pattern portion of the cured film in the laminates obtained through the various embodiments and comparative examples, 11 pL of 1,6-hexanediol diacrylate (HDDA) was dropped onto the center portion of the unit separated by the spacer walls using an inkjet coating apparatus (InkjetLabo, manufactured by Classicer Technologie Co., Ltd.). The laminate after the drop was observed from the top surface using an optical microscope (100x magnification), and the "spreadability during small-batch coating" was evaluated according to the following criteria. It should be noted that, as an example, the results of Example 39, which was determined to be "A", are shown below. Figure 3 In the example, the result of Example 48, which was determined to be "B", is shown below. Figure 4-1 The results of Example 49 are shown in the table below. Figure 4-2 The results of Example 50 are shown in the table below. Figure 4-3 In addition, if a partition wall pattern cannot be formed, it is recorded as "-".

[0377] A: The applied 1,6-hexanediol diacrylate is not biased towards the center of the zone or around the first to third sides of a partition wall, but rather exists around the fourth side of the partition wall and is spread out, exhibiting "good spreadability throughout the unit".

[0378] B: The applied 1,6-hexanediol diacrylate is biased towards the center of the zone and around one to three sides of a certain partition wall, resulting in poor overall spreadability within the unit.

[0379] Liquid repellency at the top of the septum during overcoating

[0380] In addition, 84 pL of 1,6-hexanediol diacrylate was similarly added to the center of the other units. The laminate after the addition was observed from the top surface using an optical microscope (100x magnification), and the liquid repellency of the top of the spacer wall during overcoating was evaluated according to the following criteria. It should be noted that, as an example, the results of Example 39, which was determined to be "A", are shown below. Figure 5 In the example, the result of Comparative Example 11, which was judged as "B", is shown below. Figure 6 In addition, if a partition wall pattern cannot be formed, it is recorded as "-".

[0381] A: The coated 1,6-hexanediol diacrylate does not climb to the top of the spacer wall, exhibiting "good top liquid repellency".

[0382] B: The coated 1,6-hexanediol diacrylate climbs to the top of the spacer wall, exhibiting "poor liquid repellency at the top".

[0383] <Reflectivity>

[0384] Regarding the full-coverage portion of the cured film in the laminate obtained through the various embodiments and comparative examples, the reflectance in the wavelength range of 360 nm to 740 nm was measured from the full-coverage film side in SCI mode using a spectrophotometer CM-2600d (manufactured by Conicaminodesk Ltd.). The value at wavelength 550 nm is defined as "reflectance".

[0385] <OD value>

[0386] Regarding the full-coverage portion of the cured film in the laminate obtained through the various embodiments and comparative examples, the transmittance in the wavelength range of 300 nm to 800 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi High Tech Sciences). The "OD value" was calculated by substituting the value of wavelength 450 nm into T in the above formula (1).

[0387] <Crack resistance>

[0388] Regarding the laminates with cured films obtained through the various embodiments and comparative examples, after additional heating in air under the following conditions using an IHPS-222 oven (manufactured by Espec Corporation), the presence or absence of cracks in the full-coverage portion of the cured film was evaluated by visual observation.

[0389] A: No cracks were detected after heating at 230℃ for 30 minutes.

[0390] B: Although no cracks were detected after heating at 180°C for 30 minutes, more than one crack was detected after heating at 230°C for 30 minutes.

[0391] C: More than one crack was confirmed after heating at 180℃ for 30 minutes.

[0392] <Separate coating of wavelength conversion layer>

[0393] Regarding the spacer pattern portion of the cured film in the laminate obtained through the various embodiments and comparative examples, in the central portion of the unit separated by the spacers, the same operation as evaluated in the previous <Inkjet Test> was performed, coating a color-conversion luminescent material composition (CL-1) with a cured thickness of 10 μm to form a wavelength conversion layer. Then, in the same operation, color-conversion luminescent material composition (CL-2) was drop-added to the central portion of adjacent units with a cured thickness of 10 μm up to 11 pL to 84 pL, and the separate coating of the wavelength conversion layer was evaluated according to the following criteria. It should be noted that if a spacer pattern cannot be formed, it is recorded as "-".

[0394] A: When 11 pL of the color-conversion luminescent material composition (CL-2) was added, the spreadability of the entire unit was good, and even after adding 84 pL, it was filled into the unit without gaps. Furthermore, CL-2 did not climb to the top of the spacer wall at all. In the unit where the wavelength conversion layer was formed using the color-conversion luminescent material composition (CL-1), CL-2 did not overflow or mix, and the separate coating of the wavelength conversion layer was good.

[0395] B: When 11 pL of the color-conversion luminescent material composition (CL-2) was added, CL-2 was biased around the 1st to 3rd sides of the spacer wall and its spreadability was poor. However, after adding 84 pL, it was filled into the cell without gaps, and CL-2 did not climb to the top of the spacer wall at all. In the cell where the wavelength conversion layer was formed using the color-conversion luminescent material composition (CL-1), CL-2 did not overflow and mix, and the separate coating of the wavelength conversion layer was better.

[0396] C: When 11 pL of the color-conversion luminescent material composition (CL-2) was added, the overall spreadability within the cell was good, and even after adding 84 pL, it was filled into the cell without gaps. CL-2 partially climbed to the top of the spacer wall, but in cells where a wavelength conversion layer was formed using the color-conversion luminescent material composition (CL-1), CL-2 did not overflow or mix, and the separate coating of the wavelength conversion layer was good.

[0397] D: When 11 pL of the color-conversion luminescent material composition (CL-2) was added, CL-2 was biased around the perimeter of the spacer walls on sides 1 to 3, resulting in poor spreadability. However, after adding 84 pL, it was filled into the cell without gaps. CL-2 partially climbed to the top of the spacer walls. However, in cells where a wavelength conversion layer was formed using the color-conversion luminescent material composition (CL-1), CL-2 did not overflow or mix, and the separate coating of the wavelength conversion layer was better.

[0398] E: When 11 pL of the color conversion luminescent material composition (CL-2) was added, CL-2 was biased around the 1st to 3rd sides of the spacer wall and the coating was not good. Even when 84 pL was added, it was not completely filled in the cell and gaps were generated. The separation coating of the wavelength conversion layer was not good.

[0399] F: When 11 pL of the color-conversion luminescent material composition (CL-2) was added, the overall spreadability within the cell was good, and even after adding 84 pL, it was filled into the cell without gaps. However, CL-2 completely climbed to the top of the spacer wall. In the cell where the wavelength conversion layer was formed using the color-conversion luminescent material composition (CL-1), CL-2 overflowed and mixed, and the separate coating of the wavelength conversion layer was not good.

[0400] <Sealability with the inorganic protective layer>

[0401] The laminates obtained through the various embodiments and comparative examples were placed into a sputtering apparatus SH-450 (manufactured by Alback Corporation). Using silicon oxide as the sputtering target, a SiO2 layer with a thickness of 0.1 μm was formed on the top layer as an inorganic protective layer. The laminate was placed in a constant temperature and humidity bath at a temperature of 85°C and a humidity of 85% for 100 hours. Then, an adhesion test was performed on the full-coverage portion of the cured film with the SiO2 layer in the laminate removed from the constant temperature and humidity bath. The adhesion test involved creating 100 1mm x 1mm squares by drawing 11 parallel vertical and horizontal lines at 1mm intervals on the surface of the SiO2 layer using a cutter to reach the raw substrate. Cellophane tape (width = 18mm, adhesion = 3.7N / 10mm) was then applied to the cut SiO2 layer surface. The tape was then rubbed with an eraser (JIS S6050 compliant) to ensure adhesion. Holding one end of the tape at a right angle to the board, it was instantly peeled off. The number of remaining squares was visually counted. The adhesion of the cured film to the inorganic protective layer was evaluated based on the peeled area of ​​the squares according to the following criteria.

[0402] 5B: Peeling area = 0%

[0403] 4B: Peeling area = greater than 0% and less than 5%.

[0404] 3B: Peeling area = 5% or more but less than 15%.

[0405] 2B: Peeling area = 15% or more but less than 35%.

[0406] 1B: Peeling area = 35% or more but less than 65%.

[0407] 0B: Peeling area = 65% or more.

[0408] The following shows the evaluation methods for the laminates comprising a cured film, a wavelength conversion layer, and an inorganic protective layer in each embodiment and comparative example.

[0409] <Brightness>

[0410] Using a planar light-emitting device equipped with a commercially available LED backlight (peak wavelength 465nm) as the light source, a multilayer structure obtained in Examples 72-104 and Comparative Examples 26-40 was arranged with the pixel portion serving as the light source side. A 30mA current was flowed through the planar light-emitting device to illuminate the LED element, and the luminance (unit: cd / m²) based on the CIE 1931 standard was measured using a spectroradiometer (CS-1000, manufactured by Conicaminodesa). 2 The initial brightness is set as ). The brightness was evaluated by using the initial brightness of Example 85 as a relative value to a standard of 100. It should be noted that if a spacer pattern cannot be formed, it is recorded as "-".

[0411] <Mixed Colors>

[0412] Blue organic EL cells with the same width at the same location as the wavelength conversion layer partially formed within the lattice-shaped spacers were fabricated. A blocking agent was used to bond the laminates obtained in Examples 72-104 and Comparative Examples 26-40 to the blue organic EL cells, resulting in… Figure 11 The display device shown is configured to only enable... Figure 11 The blue organic EL unit 10, located directly below the wavelength conversion layer formed by the color-converting luminescent material composition (CL-1), is illuminated. In this state, the absorbance intensity A (540nm) at a wavelength of 540nm was measured using a microspectrophotometer LVmicro-V (manufactured by Lambda Visual Co., Ltd.) for adjacent unit portions where the wavelength conversion layer is not formed. The smaller the value of absorbance intensity A (540nm), the less likely color mixing will occur. Color mixing was determined using the following criteria. It should be noted that if a spacer pattern cannot be formed, it is recorded as "-".

[0413] A: A(540nm) < 0.01

[0414] B: 0.01 ≤ A(540nm) ≤ 0.5

[0415] C: 0.5 < A (540nm).

[0416] <Refractive Index>

[0417] Using a 6-inch Si wafer as the substrate, the refractive index of the laminates obtained through Examples 120-123 and Comparative Examples 48-50 was measured by irradiating light with a wavelength of 633 nm from a direction perpendicular to the cured film surface using a prism coupler (PC-2000 (manufactured by Metricon Corporation)) at atmospheric pressure and 20°C. The refractive index was rounded to the third decimal place. It should be noted that if the refractive index cannot be measured due to strong reflection or light blocking, it is recorded as "-".

[0418] <Stain resistance>

[0419] Using an alkali-free glass substrate as the base substrate, for the laminates obtained through Examples 120-123 and Comparative Examples 48-50, straight lines with a distance of 1 cm were drawn on the surface of the cured film using a black oil-based pen ("Mackie Kikushin" (Zebura Co., Ltd.)). The film was placed in a room at 25°C for 1 minute. Then, a standard weight (International Bureau of Metrology F2 grade, Murakami Weighing Instruments Co., Ltd.) weighing 500g was wrapped in a cleaning cloth ("Tracey MK" (Tore Co., Ltd.)) and placed on the cured film. The weight was wiped off by reciprocating 30 times at a speed of 1 time per second. The condition of the straight lines after wiping was visually checked, and the stain resistance was determined according to the following criteria.

[0420] A: The line disappeared after erasing the work.

[0421] B: After erasing, the line color is lighter than before erasing, but some residue remains.

[0422] C: After the erasure operation, the line remained unchanged compared to before the erasure operation.

[0423] <Chemical Resistance (Low-Temperature Curing Properties)>

[0424] Using an alkali-free glass substrate as the base material, chemical resistance tests were conducted on the laminates obtained through Examples 120-123 and Comparative Examples 48-50 by immersion in PGMEA at 25°C for 5 minutes. The film thickness before and after the test was measured, and the chemical resistance was evaluated using the film thickness change rate ({|film thickness after test - film thickness before test| / film thickness before test} × 100) according to the following criteria.

[0425] A: The film thickness change rate is less than 1%.

[0426] B: Film thickness change rate is greater than 1% and less than 5%.

[0427] C: Film thickness change rate is above 5%.

[0428] Explanation of symbols

[0429] 1 substrate

[0430] 2 Cured film

[0431] H is the height of the partition wall.

[0432] L is the width of the partition wall.

[0433] θ is the cone angle of the partition wall.

[0434] 3. Spacer

[0435] HDDA 1,6-hexanediol diacrylate

[0436] 4 Wavelength conversion layer

[0437] 4(CL-1) Wavelength conversion layer formed from color-converting luminescent material composition (CL-1)

[0438] 5 Inorganic protective layer

[0439] 6 Color Filter Layers

[0440] 7 Black Matrix

[0441] 8. Color Filter Section

[0442] 9. Light sources selected from organic EL units, mini LED units, and micro LED units.

[0443] 10 Blue Organic EL Units.

Claims

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

2. The laminated body according to claim 1, characterized in that, The surface free energy of the cured film is above 10 mN / m and below 25 mN / m.

3. The laminate according to claim 1 or 2, characterized in that, The cured film, in FT-IR (ATR) analysis, showed that the Si-O bonds originating from siloxane bonds (Si-O) were located in the 950–1250 cm⁻¹ range of the crystalline structure. -1 The absorption intensity E at the peak SiO With 1650–1750 cm⁻¹ derived from carbonyl groups, i.e., C=O groups -1 The absorption intensity E at the peak CO The ratio is E SiO / E CO The following relation (I) must be satisfied. 1.2≤E SiO / E CO ≤20 (I).

4. The laminate according to claim 1 or 2, characterized in that, The cured film is a spacer wall obtained by pattern formation.

5. The laminated body according to claim 4, characterized in that, The reflectivity of each 10 μm thick film of the spacer wall at a wavelength of 550 nm is above 20% and below 85%.

6. The laminate according to claim 4, characterized in that, The OD value of each 10 μm film thickness of the spacer wall at a wavelength of 450 nm is greater than 1.5 and less than 3.

0.

7. The laminate according to claim 1 or 2, characterized in that, The cured film is a cured film obtained by curing a resin composition containing (A) polysiloxane, (B) photopolymerization initiator, (C) photopolymerizable compound and (D) liquid-repellent compound.

8. The laminate according to claim 7, characterized in that, The (A) polysiloxane contains at least a styrene group.

9. The laminate according to claim 8, characterized in that, The (A) polysiloxane contains 10 to 60 moles of repeating units with styrene groups in all repeating units.

10. The laminate according to claim 7, characterized in that, The liquid-repellent compound (D) is an organosilicon surfactant.

11. The laminate according to claim 7, characterized in that, The resin composition contains 0.05% to 2.00% by weight of the liquid-repellent compound (D) in its total solid components.

12. The laminate according to claim 7, characterized in that, The resin composition does not contain compounds containing fluorine atoms.

13. The laminate according to claim 7, characterized in that, The resin composition also contains (E) a metal chelating agent.

14. The laminate according to claim 13, characterized in that, The metal chelating agent (E) is an aluminum chelate.

15. A resin composition, characterized in that, It contains (A) polysiloxane and (D) liquid-repellent compound.

16. The resin composition according to claim 15, characterized in that, The (A) polysiloxane contains at least a styrene group.

17. The resin composition according to claim 16, characterized in that, The (A) polysiloxane contains 10 to 60 moles of repeating units with styrene groups in all repeating units.

18. The resin composition according to claim 15 or 16, characterized in that, The liquid-repellent compound (D) is an organosilicon surfactant.

19. The laminate according to claim 4, characterized in that, A wavelength conversion layer is provided within the unit divided by the spacer wall.

20. A display device having a stack as described in claim 1 or 2, and a light source selected from liquid crystal cells, organic EL cells, mini LED cells, and micro LED cells.

21. An information terminal having the display device of claim 20.

Images