Low refractive index film comprising hollow silica and method for producing same

Abstract

An objective of the present invention is to provide a thin film having a lower refractive index compared to conventional thin films. Said objective is achieved by a low refractive index film comprising hollow silica. Said objective is also achieved by a method for producing a low refractive index film, the method comprising the following steps: a step for mixing the hollow silica, a polymer, and an additive to obtain a mixed solution; a step for applying the mixed solution onto a substrate and curing by heating and / or light irradiation to obtain a cured film; and a step for subjecting the cured film to a washing treatment.

Description

Low refractive index film made of hollow silica and method for manufacturing the same

[0001] This invention relates to a novel low refractive index film. More specifically, it relates to a low refractive index film made of hollow silica and a method for producing the same.

[0002] In recent years, the use of technologies such as AR (Augmented Reality), VR (Virtual Reality), and MR (Mixed Reality), also known as XR (Cross Reality), has been advancing. For these technologies, specialized headsets, goggles, and other devices have been developed for combining them with video.

[0003] In this device, materials with different refractive indices are used in combination to deliver the image (light) output from the output device to the user's eyes, and there is a need to develop materials with high refractive indices and low refractive indices. Among materials with such properties, hollow silica is known as a thin-film material that can achieve a particularly low refractive index.

[0004] As a composition that can realize a low refractive index film containing hollow silica, for example, a curable composition containing a curable component such as a siloxane resin and particles such as hollow silica has been proposed (see Patent Document 1).

[0005] Furthermore, a film has been proposed in which a low refractive index layer is provided on a transparent substrate, and hollow silica particles are contained in the low refractive index layer (see Patent Document 2). The low refractive index film is a cured film of a composition containing hollow silica particles, acrylic resin, fluororesin, and a leveling agent.

[0006] Japanese Patent Publication No. 2014-25012 Japanese Patent Publication No. 2022-150906

[0007] However, while such thin films can achieve a low refractive index of, for example, around 1.28, they cannot achieve thin films with an even lower refractive index (for example, 1.25 or less) (hereinafter simply referred to as "low refractive index films").

[0008] Therefore, the present invention aims to provide a thin film with a lower refractive index compared to conventional thin films.

[0009] As a result of diligent research, the inventors have discovered that it may be possible to reduce the refractive index of a thin film containing hollow silica by using a dispersion or mixture containing hollow silica. Furthermore, surprisingly, they have discovered that such a thin film can achieve a refractive index equivalent to or lower than that of the hollow silica itself used as a material. Further research has led to the completion of the present invention.

[0010] In other words, the present invention and its various embodiments are as follows [1] to

[19] . However, the present invention is not limited to the following. [1] A low refractive index film made of hollow silica. [2] The low refractive index film according to [1], wherein the hollow silica is surface-modified with a silane coupling agent. [3] The low refractive index film according to [2], wherein the silane coupling agent has a crosslinkable double bond. [4] The low refractive index film according to [3], wherein at least a portion of the crosslinkable double bond forms a crosslink. [5] The low refractive index film according to any one of [2] to [4], wherein the silane coupling agent has an acrylic group. [6] The low refractive index film according to any one of [1] to [5], wherein the hollow silica is surface-modified with a group represented by the following formula 1. [Chemical Formula 1] (In the formula, R represents a hydrogen atom or a methyl group, and * represents a bond.) [7] A low refractive index film according to any one of [1] to [6], wherein the refractive index is 1.24 or less. [8] A low refractive index film according to any one of [1] to [7], wherein the hollow silica has an average particle size of 30 nm to 90 nm. [9] A low refractive index film according to any one of [1] to [8], having a film thickness of 40 nm to 10000 nm.

[10] A method for producing a low refractive index film according to any one of [1] to [9], comprising the following steps: a step of mixing the hollow silica, polymer, and additive to obtain a mixed solution; a step of applying the mixed solution onto a substrate and obtaining a cured film by heating and / or light irradiation; and a step of subjecting the cured film to a cleaning treatment.

[11] The method for producing a low refractive index film according to

[10] , wherein the cleaning treatment is PEGMEA cleaning, dry cleaning, or alkaline development treatment.

[12] The method for producing the polymer according to

[10] or

[11] , wherein the polymer has a weight-average molecular weight of 1,000 or more and 15,000 or less.

[13] The method for producing the polymer according to any one of

[10] to

[12] , wherein the polymer is the following triazine ring-containing polymer: comprising a repeating unit structure represented by the following formula (1), having at least one triazine ring end, and at least a portion of this triazine ring end being sealed with an amino group having a crosslinking group [Chemical Formula 2] (In the formula, R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group, Q represents a divalent group having 3 to 30 carbon atoms and a ring structure, and * represents a bond).

[14] The manufacturing method according to

[13] , wherein Q in formula (1) is represented by the following formula (A), (B), or (C): [Chemical Formula 3] [C4] [C5] (In the formula, * represents a bond).

[15] The amino group having the crosslinking group is -NH-R １０２ , or the manufacturing method described in

[13] or

[14] , which is represented by the following formula (1-4): [Chemical Formula 6] (In the formula, R １０２ (where represents a crosslinking group, and * represents a bonding site).

[16] The R １０２is a hydroxyalkyl group, a (meth)acryloyloxyalkyl group, or a group represented by the following formula (1-5), the production method described in

[15] : [Chemical formula 7] (In the formula, １ A represents an alkylene group having 1 to 10 carbon atoms, and A ２ represents a single bond or the following formula (1-6) [Chemical formula 8] represents a group represented by, and A ３ represents an (a + 1)-valent aliphatic hydrocarbon group which may be substituted with a hydroxy group, and A ４ represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bond).

[17] The R １０２ is a group selected from a hydroxymethyl group, a 2-hydroxyethyl group, a (meth)acryloyloxymethyl group, a (meth)acryloyloxyethyl group, and groups represented by the following formulas (1-5-1) to (1-5-4), the production method described in

[15] : [Chemical formula 9] (In the formula, * represents a bond).

[18] The method for producing a low refractive index film according to any one of [1] to [9], including the following steps: A step of dispersing the hollow silica in a solvent to obtain a dispersion liquid, a step of applying the dispersion liquid onto a substrate, and a step of firing the dispersion liquid to volatilize the solvent.

[19] A mixed liquid for forming the low refractive index film according to [1] to [9], containing at least hollow silica and a polymer.

[0011] According to the present invention, a novel low refractive index film made of hollow silica can be provided. Such a low refractive index film has an effect of having a refractive index lower than that of a conventional thin film. Further, according to the present invention, a method for producing the low refractive index film can be provided.

[0012] FIG. 1 shows the １ measurement result of the 1H-NMR spectrum of compound P-1. FIG. 2 shows the １ measurement result of the 1H-NMR spectrum of compound P-3. FIG. 3 shows the １ ​​Figure 5 shows the measurement results of the H-NMR spectrum. Figure 6 shows the micrograph of the cured film of Example 2-1 after solvent exposure. Figure 7 shows the micrograph of the cured film of Example 2-2 after solvent exposure. Figure 8 shows the micrograph of the cured film of Example 2-4 after solvent exposure. Figure 9 shows the micrograph of the cured film of Example 2-5 after solvent exposure. Figure 10 shows the micrograph of the cured film of Example 2-6 after solvent exposure. Figure 11 shows the micrograph of the cured film of Example 2-7 after solvent exposure. Figure 12 shows the micrograph of the cured film of Example 2-8 after solvent exposure. Figure 13 shows the micrograph of the cured film of Example 2-9 after solvent exposure. Figure 14 shows the results of compound P-6. １ These are the results of the 1H-NMR spectrum measurement. Figure 15 is a micrograph of the cured film of Example 2-10 after solvent exposure. Figure 16 is a micrograph of the cured film of Example 2-11 after solvent exposure. Figure 17 is a micrograph of the cured film of Example 2-12 after solvent exposure. Figure 18 is a micrograph of the cured film of Example 2-13 after solvent exposure.

[0013] The present invention relates to a low refractive index film made of hollow silica.

[0014] <Hollow Silica> In this specification, hollow silica refers to silica particles having an outer shell mainly composed of silica and having a space inside the outer shell.

[0015] Hollow silica is obtained by forming an outer shell mainly composed of silica on the surface of a core-like portion called a template in a dispersion medium, and then removing the core-like portion.

[0016] The hollow silica obtained as described above is obtained as a hollow silica sol dispersed in a dispersion medium. Here, the average particle size of the hollow silica particles determined by dynamic light scattering (DLS) is 20 nm to 150 nm. Alternatively, the average particle size of the hollow silica particles may be measured by transmission electron microscopy (TEM).

[0017] Furthermore, the thickness of the outer shell of the hollow silica particles may be 3.0 nm to 15.0 nm, 4.0 nm to 12.0 nm, or 5.0 nm to 10.0 nm. The thickness of the outer shell of the hollow silica particles can be measured by transmission electron microscopy.

[0018] The refractive index of hollow silica is generally between 1.25 and 1.45.

[0019] However, the low refractive index film of the present invention achieves a refractive index even lower than that of the hollow silica. In the low refractive index film of the present invention, the hollow silica particles are bonded to each other on a portion of their surfaces by physical adsorption, or if modifying groups are present on the surface of the hollow silica particles, the hollow silica particles are bonded to each other via the modifying groups, and it is believed that the film contains voids surrounded by multiple hollow silica particles. Therefore, it is possible to form a thin film using only hollow silica, and it is believed that the refractive index of the entire thin film decreases due to the voids (refractive index of 1.00) contained in the thin film.

[0020] The low refractive index film of the present invention consists solely of hollow silica and contains no resin components, thus being less affected by external factors such as temperature, humidity, and ultraviolet light, as well as by changes in properties due to elution into solvents. In other words, it is a low refractive index film with excellent reliability, solvent resistance, and weather resistance.

[0021] In this invention, "reliability" and "weather resistance" are evaluated by the rate of change in refractive index, film thickness, haze value, and YI value before and after storing the target cured film for a certain period of time (e.g., more than 200 hours) under a predetermined environment. The smaller the rate of change, the better the reliability or weather resistance. The rate of change is calculated using the following formula: Rate of change (%) = (Physical properties after test - Physical properties before test) ÷ (Physical properties before test) × 100

[0022] Furthermore, "solvent resistance" is evaluated by exposing the cured film in question to a solvent, then removing the solvent, and measuring the percentage change in the film thickness before and after solvent exposure as the residual film rate. A higher residual film rate indicates higher solvent resistance. The residual film rate is calculated using the following formula: Residual film rate (%) = (Film thickness after solvent exposure) ÷ (Film thickness before solvent exposure) × 100

[0023] In one embodiment of the present invention, the hollow silica may have its surface modified with a silane coupling agent.

[0024] <Silane Coupling Agent> The silane coupling agent in the present invention is not particularly limited as long as it contains a silicon atom to which one or more alkoxy groups and predetermined functional groups are bonded in one molecule, and is capable of undergoing a crosslinking reaction on its own or in combination with the triazine ring-containing polymer described later to form a crosslinked structure.

[0025] Examples of silane coupling agents include treatment with epoxy-based silane coupling agents, styrene-based silane coupling agents, amino-based silane coupling agents, isocyanate-based silane coupling agents, isocyanurate-based silane coupling agents, mercapto-based silane coupling agents, vinyl-based silane coupling agents, acrylic-based silane coupling agents, methacrylic-based silane coupling agents, ureido-based silane coupling agents, phenyl-based silane coupling agents, and fluorinated alkyl-based silane coupling agents.

[0026] Among these silane coupling agents, epoxy-based silane coupling agents, amino-based silane coupling agents, vinyl-based silane coupling agents, acrylic-based silane coupling agents, methacrylic-based silane coupling agents, or acid anhydride-based silane coupling agents are preferred.

[0027] Epoxy silane coupling agents are compounds containing silicon atoms bonded to a group having one or more alkoxy groups and one or more epoxy groups in a single molecule.

[0028] The amino-based silane coupling agent is a compound containing a silicon atom to which one or more alkoxy groups and amino groups are bonded in a single molecule, and the amino group may be -NH2, -NHR'', or -N(R'')2 (where R'' represents an organic group). Examples of amino-based silane coupling agents include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane.

[0029] Vinyl silane coupling agents are compounds containing silicon atoms bonded to a group having one or more alkoxy groups and one or more vinyl groups in a single molecule.

[0030] Acrylic silane coupling agents are compounds containing silicon atoms bonded to a group having one or more alkoxy groups and one or more acrylic groups in a single molecule.

[0031] A methacrylic silane coupling agent is a compound containing a silicon atom bonded to a group having one or more alkoxy groups and one or more methacrylic groups in a single molecule.

[0032] Acid anhydride-based silane coupling agents are compounds containing silicon atoms bonded to a group having one or more alkoxy groups and one or more acid anhydride groups in a single molecule.

[0033] More specifically, silane coupling agents having the following structure can be cited.

[0034] When the surface of hollow silica is modified with these silane coupling agents, the hollow silica particles can bond to each other via the modifying groups. Therefore, even after the polymers and other components described later have been removed, a thin film can be formed using only hollow silica.

[0035] In one embodiment of the present invention, the silane coupling agent may have crosslinkable double bonds. When the surface of hollow silica is modified with a silane coupling agent having crosslinkable double bonds, at least a portion of the crosslinkable double bonds forms crosslinks, allowing the hollow silica particles to bond to each other, thus enabling the formation of a thin film using only hollow silica.

[0036] In this embodiment, it is preferable that at least a portion of the crosslinkable double bond forms a crosslink.

[0037] The silane coupling agent may be hydrophilic or hydrophobic. The silane coupling agent can be appropriately selected depending on the dispersion medium in order to stably disperse the hollow silica.

[0038] In one embodiment of the present invention, the silane coupling agent may have acrylic groups. When the surface of hollow silica is modified with a silane coupling agent having acrylic groups, at least a portion of the acrylic groups can form crosslinks, thereby bonding the hollow silica particles together, and thus a thin film can be formed using only hollow silica.

[0039] In one embodiment of the present invention, it is preferable that the hollow silica is modified on its surface with a group represented by the following formula 1. (In the formula, R represents a hydrogen atom or a methyl group, and * represents a bond.)

[0040] When the surface of hollow silica is modified with a group represented by formula 1, the hollow silica particles can bond to each other via the modifying group. Therefore, even after polymers and other materials described later have been removed, a thin film can be formed using only hollow silica.

[0041] Hollow silica may contain aluminum from the viewpoint of dispersion in polymers and solvents. In this case, aluminum-containing hollow silica refers to silica particles on which aluminum atoms exist as aluminosilicate on the surface of the silica particles.

[0042] The low refractive index film of the present invention consists of the hollow silica described above and may contain voids surrounded by multiple hollow silica particles. Therefore, it is possible to achieve a refractive index lower than that of the hollow silica itself that forms the low refractive index film. The proportion of voids contained in the low refractive index film can be evaluated by the porosity, which can be measured by methods such as the Archimedes method, the mercury porosity method, or the gravimetric porosity method.

[0043] Therefore, in one embodiment of the present invention, the refractive index of the low refractive index film may be 1.24 or less. Preferably, the refractive index may be 1.22 or less, more preferably 1.20 or less, and even more preferably 1.19 or less.

[0044] In one embodiment of the present invention, the hollow silica may have an average particle diameter of 30 nm to 90 nm. Here, the "average particle diameter" of the hollow silica in the present invention refers to the value measured by TEM observation.

[0045] The larger the hollow silica particles, the larger the voids surrounded by multiple hollow silica particles formed in the low refractive index film. Therefore, the larger the average particle size of the hollow silica, the lower the refractive index can be. On the other hand, the thickness of a low refractive index film made of hollow silica depends on the size and deposition of the hollow silica particles constituting the film. The smaller the average particle size of the hollow silica, the thinner the low refractive index film can be obtained.

[0046] The average particle size of the hollow silica is preferably 35 nm to 80 nm, and more preferably 40 nm to 70 nm.

[0047] In one embodiment of the present invention, the low refractive index film can have a film thickness of 40 nm to 10,000 nm. Since the low refractive index film of the present invention can be appropriately fabricated within the above range, low refractive index films of various film thicknesses can be provided depending on the application of the low refractive index film.

[0048] The film thickness of the low refractive index film can be adjusted by the rotation speed of the spin coater or the concentration of solids in the mixture, as described later in the method for manufacturing the low refractive index film. For example, the film thickness of the low refractive index film can be increased by reducing the rotation speed of the spin coater or increasing the concentration of solids in the mixture.

[0049] The present invention provides a method for manufacturing the low refractive index film described above. The method for manufacturing the low refractive index film of the present invention includes the following steps: mixing hollow silica, a polymer, and an additive to obtain a mixed solution; applying the mixed solution onto a substrate and obtaining a cured film by heating and / or light irradiation; and subjecting the cured film to a cleaning treatment.

[0050] According to the manufacturing method of the present invention, a low refractive index film made of hollow silica can be obtained by mixing hollow silica with a polymer and an additive to obtain a mixed solution for forming a low refractive index film, forming a cured film with the mixed solution, and then washing the cured film.

[0051] In the process of mixing hollow silica, a polymer, and an additive to obtain a mixture, a mixture for forming a low refractive index film is provided. The hollow silica can be the one described above. By mixing the hollow silica with the polymer and additive described later, a mixture with high dispersibility of hollow silica can be obtained.

[0052] From the viewpoint of the dispersibility of hollow silica, the amount of hollow silica in the mixture may be between 200 phr and 1200 phr.

[0053] The method for mixing hollow silica, polymer, and additives is not particularly limited as long as the hollow silica is sufficiently dispersed in the mixture. In the present invention, the polymer described later has high dispersibility of hollow silica, and it is possible to sufficiently disperse the hollow silica in the mixture by known methods.

[0054] In the process of applying the mixed solution onto a substrate and obtaining a cured film by heating and / or light irradiation, a cured film is formed.

[0055] For applying the mixed solution, known methods such as spin coating, dip coating, flow coating, inkjet coating, jet dispenser coating, spray coating, bar coating, gravure coating, slit coating, roll coating, transfer printing, brush coating, blade coating, and air knife coating can be used.

[0056] Examples of substrates to which the mixture is applied include plastics, glass, and ceramics. Alternatively, substrates with silicon, indium tin oxide (ITO), indium zinc oxide (IZO), or silicon nitride film-formed on their surface, which are used in electronic devices, may also be used.

[0057] The heating and / or light irradiation conditions are not particularly limited as long as a cured film can be formed, and can be appropriately adjusted depending on the type and amount of additives contained in the mixture.

[0058] For example, the heating temperature may be between 50°C and 400°C, and the heating time may be between 1 minute and 10 hours. For example, the heating method may be a hot plate or an oven, and heating may be carried out in an appropriate atmosphere such as air, an inert gas such as nitrogen, or a vacuum.

[0059] For example, the light irradiation conditions could be 10 mJ / cm². ２ ~1000mJ / cm ２ One example is UV irradiation with the specified exposure dose.

[0060] In this way, a cured film containing hollow silica in the polymer can be obtained.

[0061] A low refractive index film can be obtained by subjecting the cured film to a cleaning process. Specifically, in this process, polymer components can be removed from the cured film, so a film made of hollow silica can be obtained, and voids surrounded by hollow silica particles are created in proportion to the removed polymer components. As a result, the refractive index of the low refractive index film obtained by the manufacturing method of the present invention can be made smaller than the refractive index of the hollow silica itself that constitutes the low refractive index film.

[0062] The cleaning process is not particularly limited as long as it can remove polymer components, and examples include cleaning with organic solvents, dry cleaning, and alkaline development with aqueous developer.

[0063] Cleaning with organic solvents can be performed using, for example, PGME (propylene glycol monomethyl ether), PGMEA (propylene glycol monomethyl ether acetate), a mixed solvent of PGME and PGMEA, NMP (N-methyl-2-pyrrolidone), γ-butyrolactone, or DMSO (dimethyl sulfoxide). Cleaning with organic solvents may also be performed, for example, by immersing the substrate on which the cured film has been formed in the organic solvent for a certain period of time. The immersion time will vary depending on the thickness of the formed cured film, the type of polymer on which the cured film was formed, or the type or concentration of the organic solvent, but may be, for example, 1 minute to 1 hour.

[0064] For dry cleaning, UV-O ３ Washing, or O ２ Etching is one example. Dry cleaning may be performed, for example, using an etching apparatus, under conditions of a flow rate of 50 sccm, a pressure of 5.0 Pa, and a frequency of 100 W for 2 to 30 minutes.

[0065] Examples of alkaline developing treatments using aqueous developers include washing with aqueous solutions of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, or tetramethylammonium.

[0066] In one embodiment of the present invention, the washing process may be PEGMEA washing, dry washing, or alkaline developing.

[0067] The polymer used in the mixture for forming a low refractive index film only needs to be able to sufficiently disperse hollow silica and be removable from the cured film by washing. In one embodiment of the present invention, the polymer may have a weight-average molecular weight of 1,000 to 15,000.

[0068] The weight-average molecular weight of the polymer is preferably 1,000 to 13,000, more preferably 1,000 to 11,000, even more preferably 1,000 to 9,000, even more preferably 1,000 to 7,000, and even more preferably 1,000 to 5,000. In this invention, "weight-average molecular weight" refers to the average molecular weight obtained on a standard polystyrene basis by gel permeation chromatography (hereinafter referred to as "GPC") analysis.

[0069] Examples of such polymers include acrylic polymers, cycloolefin polymers, and triazine ring-containing polymers, which will be discussed later.

[0070] <Triadine Ring-Containing Polymers> Triazine ring-containing polymers have hydroxyl groups directly bonded to aromatic rings. The aromatic ring in the hydroxyl group directly bonded to the aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle. Examples of aromatic hydrocarbon rings include benzene rings and naphthalene rings. The hydroxyl group directly bonded to the aromatic ring may be one or two or more.

[0071] Examples of triazine ring-containing polymers include the triazine ring-containing polymer described in International Publication No. 2019 / 093203 and the triazine ring-containing polymer described in International Publication No. 2022 / 225014. All of these publications are incorporated herein to the same extent as if they were explicitly stated.

[0072] The triazine ring-containing polymer may be a linear polymer or a branched polymer.

[0073] In one embodiment of the present invention, the polymer may be the following triazine ring-containing polymer. The triazine ring-containing polymer contains a repeating unit structure represented by the following formula (1). (In the formula, R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group; Q represents a divalent group having 3 to 30 carbon atoms and a ring structure; and * represents a bond.)

[0074] The triazine ring-containing polymer may contain one type of repeating unit structure represented by formula (1), or it may contain two or more types.

[0075] Triazine ring-containing polymers are, for example, so-called hyperbranched polymers. Hyperbranched polymers are highly branched polymers that have an irregular branching structure. Irregularity here means that the branching structure is more irregular than that of dendrimers, which are highly branched polymers that have a regular branching structure.

[0076] For example, a hyperbranched polymer containing a triazine ring includes a structure (structure A) that is larger than the repeating unit structure represented by formula (1), in which each of the three bonds of the repeating unit structure represented by formula (1) is bonded to the repeating unit structure represented by formula (1). In a hyperbranched polymer containing a triazine ring, structure A is distributed throughout the entire triazine ring containing polymer except for the ends.

[0077] In a hyperbranched polymer containing a triazine ring, the repeating unit structure may consist solely of a repeating unit structure represented by formula (1).

[0078] <Q> Q in formula (1) is not particularly limited as long as it is a divalent group having 3 to 30 carbon atoms and having a ring structure. The ring structure may be an aromatic ring structure or an alicyclic structure.

[0079] The above Q preferably represents at least one selected from the group shown by formulas (2) to (13). * represents a combination.

[0080] The above R １ ~R ９２Each of these independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, a C1-C10 alkyl group, a C1-C10 halogenated alkyl group, or a C1-C10 alkoxy group. ９３ and R ９４ W represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. １ and W ２ These are independent of each other, single bonds, CR ９５ R ９６ (R ９５ and R ９６ Each of these independently represents a hydrogen atom, a C1-C10 alkyl group (which may together form a ring), or a C1-C10 halogenated alkyl group. ２ , or NR ９７ (R ９７ (This represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.)

[0081] Also, X １ and X ２ These independently represent a single bond, an alkylene group having 1 to 10 carbon atoms, or a group represented by formula (14). The structures of these alkyl groups, alkyl halides, alkoxy groups, and alkylene groups are not particularly limited and may be linear, branched, cyclic, or any combination of two or more of these.

[0082] * represents a combination.

[0083] The above R ９８ ~R １０１ Each of these independently represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, a C1-C10 alkyl group, a C1-C10 halogenated alkyl group, or a C1-C10 alkoxy group. １ and Y ２ These independently represent a single bond or an alkylene group having 1 to 10 carbon atoms. These halogen atoms, alkyl groups, alkyl halides, and alkoxy groups include R. １ ~R ９２Examples include halogen atoms, alkyl groups, alkyl halides, and alkoxy groups, similar to those in R. ９８ ~R １０１ The structures of the alkyl and alkoxy groups in are not particularly limited and may be linear, branched, cyclic, or any combination of two or more of these. １ and Y ２ The structure of the alkylene group in is not particularly limited and may be linear, branched, cyclic, or a combination of two or more of these.

[0084] Among these, R １ ~R ９２ and R ９８ ~R １０１ Preferred members include hydrogen atoms, halogen atoms, sulfo groups, C1-C5 alkyl groups, C1-C5 halogenated alkyl groups, or C1-C5 alkoxy groups. １ ~R ９２ and R ９８ ~R １０１ Of these, hydrogen atoms are more preferable.

[0085] In particular, Q is preferably at least one of those represented by formulas (2), (5) to (13), and more preferably at least one of those represented by formulas (2), (5), (7), (8), (11) to (13). Specific examples of the divalent group represented by the above formulas (2) to (13) include, but are not limited to, those shown in the following formulas.

[0086] "Ph" represents a phenyl group. * represents a bond.

[0087] (In the formula, A independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, a C1-C10 alkyl group, or a C1-C10 halogenated alkyl group. p independently represents an integer from 0 to 4, q independently represents an integer from 0 to 3, r independently represents an integer from 0 to 2, s independently represents an integer from 0 to 5, t independently represents an integer from 1 to 6, and u independently represents an integer from 1 to 4. However, the sum of p, q, r, and s in each group is 1 or greater. "Ph" represents a phenyl group. * represents a bond.)

[0088] Furthermore, Q in equation (1) may be, for example, at least one selected from the group shown in equations (102) to (115). (In the formula, * represents a bond.)

[0089] In equations (102) to (115), the above R １ and R ２ This represents alkylene groups having 1 to 5 carbon atoms, which may have a branched structure independently of each other.

[0090] In one embodiment of the present invention, Q in formula (1) may be a structure represented by the following formulas (A), (B), or (C). (In the formula, * represents a bond).

[0091] <Amino Groups Having Crosslinking Groups> Furthermore, the triazine ring-containing polymer has at least one triazine ring end, and at least a portion of this triazine ring end is encapsulated with an amino group having a crosslinking group. The triazine ring-containing polymer has at least one triazine ring end, but the triazine ring at this end may be bonded to the same triazine ring end via an amino group having a crosslinking group. Also, if there are multiple triazine ring ends, each may be bonded to a different triazine ring end.

[0092] The number of crosslinking groups in an amino group having crosslinking groups is not particularly limited and can be any number, but considering solvent resistance, 1 to 4 groups are preferred, 1 to 2 groups are more preferred, and 1 group is even more preferred. If an amino group having crosslinking groups has multiple crosslinking groups, the multiple crosslinking groups may have the same structure or may have different structures.

[0093] An amino group having a crosslinking group can be represented, for example, by the following formula (X). (In the formula, Z represents a group having a bridging group. * represents a bond.)

[0094] In formula (X), Z may be the crosslinking group itself. Preferably, the crosslinking group is bonded to the amino group by an arylene group.

[0095] In one embodiment of the present invention, the amino group having a crosslinking group is -NH-R １０２ , or it can be expressed by the following formula (1-4). (In formula (1-4), R １０２ (where * represents a crosslinking group, and * represents a bonding site.)

[0096] Furthermore, the amino group having a crosslinking group is preferably represented by the following formula (16). (In the formula, R １０２ (where * represents a crosslinking group, and * represents a bonding site.)

[0097] Examples of the aforementioned crosslinking groups include hydroxyl-containing groups, vinyl-containing groups, epoxy-containing groups, oxetane-containing groups, carboxyl-containing groups, sulfo-containing groups, thiol-containing groups, and (meth)acryloyl-containing groups.

[0098] Examples of (meth)acryloyl-containing groups include (meth)acryloyl groups, (meth)acryloyloxyalkyl groups, and groups represented by the following formula (i), but (meth)acryloyloxyalkyl groups having an alkylene group with 1 to 10 carbon atoms and groups represented by the following formula (i) are preferred, and groups represented by the following formula (i) are more preferred. (In the formula, A １ This represents an alkylene group with 1 to 10 carbon atoms, A ２ is a single bond or the following formula (j) It represents a base represented by A ３ represents an (a+1) valent aliphatic hydrocarbon group which may be substituted with a hydroxyl group, A ４ (where represents a hydrogen atom or a methyl group, 'a' represents 1 or 2, and * represents a bond.)

[0099] Examples of alkylene groups included in (meth)acryloyloxyalkyl groups having an alkylene group (alkanediyl group) with 1 to 10 carbon atoms include methylene, ethylene, trimethylene, propane-1,2-diyl, tetramethylene, butane-1,3-diyl, butane-1,2-diyl, 2-methylpropane-1,3-diyl, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and decamethylene groups. Considering the improvement of heat resistance and resistance to high temperature and high humidity, among these, those having an alkylene group with 1 to 5 carbon atoms are preferred, those having an alkylene group with 1 to 3 carbon atoms are preferred, and those having an alkylene group with 1 or 2 carbon atoms are more preferred.

[0100] In equation (i), A １ The alkylene group has 1 to 10 carbon atoms, but an alkylene group with 1 to 5 carbon atoms is preferred, and a methylene group, ethylene group, or propylene group is more preferred. Examples of alkylene groups with 1 to 10 carbon atoms include those similar to the alkylene groups included in the (meth)acryloyloxyalkyl groups described above.

[0101] A ２ This represents a single bond or a group represented by formula (j), but the group represented by formula (j) is preferred.

[0102] A ３ This is an aliphatic hydrocarbon group with an (a+1) value that may be substituted with a hydroxyl group, and specific examples include alkylene groups having 1 to 5 carbon atoms and the following formulas (k-1) to (k-3). (In the formula, * represents a bond.) Examples of groups represented by are, preferably alkylene groups having 1 to 5 carbon atoms, more preferably alkylene groups having 1 to 3 carbon atoms, and even more preferably methylene groups and ethylene groups. A ３ As for the alkylene group, A １Among the alkylene groups exemplified above, alkylene groups having 1 to 5 carbon atoms can be cited.

[0103] 'a' represents either 1 or 2, but 1 is preferred.

[0104] A preferred embodiment of the base represented by formula (i) is the one represented by the following formula (i-1). (In the formula, A １ This represents an alkylene group with 1 to 10 carbon atoms, A ３ represents an (a+1) valent aliphatic hydrocarbon group which may be substituted with a hydroxyl group, A ４ (where represents a hydrogen atom or a methyl group, 'a' represents 1 or 2, and * represents a bond.)

[0105] More preferred embodiments of the base represented by formula (i) include those represented by the following formulas (i-2) to (i-5). (In the formula, * represents a bond.)

[0106] Specific examples of amino groups having a crosslinking group include, but are not limited to, those shown in the following formula.

[0107] (In the formula, * represents a bond.)

[0108] An amino group having a (meth)acryloyloxyalkyl group can be introduced by using the corresponding (meth)acryloyloxyalkylamino compound, or by introducing an amino group having a hydroxyalkyl group into a triazine ring-containing polymer, and then reacting the hydroxyl group contained in the hydroxyalkyl group with (meth)acrylate halide or (meth)acrylate glycidyl.

[0109] An amino group having the group represented by formula (i) can be introduced by using an amino compound having the desired crosslinking group, or by introducing an amino group having a hydroxyalkyl group into a triazine ring-containing polymer, and then reacting the hydroxyl group contained in the hydroxyalkyl group with an isocyanate group represented by the following formula (i') using an (meth)acrylic acid ester compound. (In the formula, A ３represents an (a+1) valent aliphatic hydrocarbon group which may be substituted with a hydroxyl group, A ４ (where represents a hydrogen atom or a methyl group, 'a' represents 1 or 2, and * represents a bond.)

[0110] In one embodiment of the present invention, the crosslinking group R in formula (1-4) １０２ This is a hydroxyalkyl group, a (meth)acryloyloxyalkyl group, or a group represented by the following formula (1-5). (In the formula, A １ This represents an alkylene group with 1 to 10 carbon atoms, A ２ This is a single bond or the following formula (1-6) It represents a base represented by A ３ represents an (a+1) valent aliphatic hydrocarbon group which may be substituted with a hydroxyl group, A ４ (where represents a hydrogen atom or a methyl group, 'a' represents 1 or 2, and * represents a bond.)

[0111] In one embodiment of the present invention, the R １０２ The group is selected from a hydroxymethyl group, a 2-hydroxyethyl group, a (meth)acryloyloxymethyl group, a (meth)acryloyloxyethyl group, and a group represented by the following formulas (1-5-1) to (1-5-4). (In the formula, * represents a bond.)

[0112] Crosslinking group R １０２ However, the above structure improves the heat resistance of the triazine ring-containing polymer and the solvent resistance (crack resistance) of the resulting film, thus allowing these properties to be imparted to the final nanoimprint material.

[0113] The triazine ring-containing polymer (hyperbranched polymer) of the present invention can be produced, for example, according to the method disclosed in International Publication No. 2010 / 128661.

[0114] The content of the triazine ring-containing polymer is not particularly limited, but is preferably 1% to 50% by mass, and more preferably 5% to 30% by mass.

[0115] Examples of additives used in the mixture for forming a low refractive index film include crosslinking agents and photoradical initiators.

[0116] <Crosslinking Agent> The crosslinking agent that can be used in the present invention is not particularly limited as long as it is a compound that can undergo a crosslinking reaction on its own or in combination with the polymers described above to form a crosslinked structure. Examples of such compounds include polyfunctional (meth)acrylate compounds, melamine compounds having crosslinking substituents such as methylol groups and methoxymethyl groups (e.g., phenoplast compounds, aminoplast compounds, etc.), substituted urea compounds, compounds containing crosslinking substituents such as epoxy groups or oxetane groups (e.g., polyfunctional epoxy compounds, polyfunctional oxetane compounds, etc.), compounds containing blocked isocyanate groups, compounds having acid anhydride groups, and compounds having (meth)acrylic groups. From the viewpoint of heat resistance and storage stability, compounds containing epoxy groups, blocked isocyanate groups, and (meth)acrylic groups are preferred, and polyfunctional (meth)acrylate compounds are particularly preferred because the curing reaction can proceed rapidly. In this specification, "polyfunctional (meth)acrylate compound" refers to a polyfunctional acrylate compound, a polyfunctional methacrylate compound, or a mixture of a polyfunctional acrylate compound and a polyfunctional methacrylate compound.

[0117] The polyfunctional (meth)acrylate compounds are not particularly limited as long as they have two or more (meth)acrylic groups in one molecule. Specific examples include ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated glycerin triacrylate, ethoxylated glycerin trimethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated dipentaerythritol hexaacrylate, polyglycerin monoethylene oxide polyacrylate, polyglycerin polyethylene glycol polyacrylate, and dipentaerythritol hexaacrylate. Examples include dipentaerythritol hexamethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tricyclodecanedimethanol diacrylate, tricyclodecanedimethanol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, and polybasic acid-modified acrylic oligomers.

[0118] The polyfunctional epoxy compound is not particularly limited as long as it has two or more epoxy groups in one molecule. Specific examples include tris(2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, pentaerythritol polyglycidyl ether, and the like.

[0119] Compounds containing an acid anhydride group are not particularly limited as long as they are carboxylic acid anhydrides obtained by dehydrating and condensing two molecules of carboxylic acid. Specific examples include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, maleic anhydride, succinic anhydride, octyl succinic anhydride, dodecenyl succinic anhydride, etc., which have one acid anhydride group in their molecule; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene Examples include succinic acid dianhydride, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid dianhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, which have two acid anhydride groups in their molecule.

[0120] Compounds containing blocked isocyanate groups are not particularly limited as long as they have two or more blocked isocyanate groups in one molecule, in which the isocyanate group (-NCO) is blocked by an appropriate protecting group, and when exposed to high temperatures during thermal curing, the protecting group (blocking portion) thermally dissociates and detaches, and the resulting isocyanate group undergoes a crosslinking reaction with the crosslinking group (e.g., hydroxyl group) of the triazine ring-containing polymer included in the present invention. For example, compounds having two or more groups represented by the following formula in one molecule (these groups may be the same or different) are included. (In the formula, R ｂ (This represents the organic group in the block.)

[0121] Such compounds can be obtained, for example, by reacting a compound having two or more isocyanate groups in one molecule with a suitable blocking agent. Examples of compounds having two or more isocyanate groups in one molecule include polyisocyanates of isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylenebis(4-cyclohexyl isocyanate), and trimethylhexamethylene diisocyanate, as well as their dimers and trimers, and reaction products of these with diols, triols, diamines, or triamines. Examples of blocking agents include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N,N-dimethylaminoethanol, 2-ethoxyethanol, and cyclohexanol; phenols such as phenol, o-nitrophenol, p-chlorophenol, and o-, m-, or p-cresol; lactams such as ε-caprolactam; oximes such as acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime; pyrazoles such as pyrazole, 3,5-dimethylpyrazole, and 3-methylpyrazole; and thiols such as dodecanethiol and benzenethiol.

[0122] The aminoplast compound is not particularly limited as long as it has two or more methoxymethylene groups in one molecule. The polyfunctional oxetane compound is not particularly limited as long as it has two or more oxetanyl groups in one molecule.

[0123] Phenoplast compounds have two or more hydroxymethylene groups in a single molecule and, when exposed to high temperatures during thermosetting, undergo a crosslinking reaction via dehydration condensation with phenolic hydroxyl groups in the polymer. Examples of phenoplast compounds include 2,6-dihydroxymethyl-4-methylphenol, 2,4-dihydroxymethyl-6-methylphenol, bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, bis(3-formyl-4-hydroxyphenyl)methane, bis(4-hydroxy-2,5-dimethylphenyl)formylmethane, and α,α-bis(4-hydroxy-2,5-dimethylphenyl)-4-formyltoluene.

[0124] The crosslinking agents described above may be used alone or in combination of two or more. The crosslinking agent content is preferably 1 to 200 parts by mass per 100 parts by mass of polymer, but considering solvent resistance, the lower limit is preferably 2 parts by mass, more preferably 5 parts by mass, and further considering control of refractive index and residue in unexposed areas, the upper limit is preferably 150 parts by mass, more preferably 120 parts by mass, and even more preferably 110 parts by mass.

[0125] <Photoradical polymerization initiator> The mixture may contain a photoradical polymerization initiator. The photoradical polymerization initiator can be appropriately selected from known ones, for example, acetophenones, benzophenones, Michler's benzoylbenzoate, amyloxime esters, oxime esters, tetramethylthiuram monosulfide, and thioxanthones. Photocleavage-type photoradical polymerization initiators are particularly preferred. Photocleavage-type photoradical polymerization initiators are described in "Latest UV Curing Technology" (page 159, publisher: Kazuhiro Takasuki, publisher: Technical Information Association Co., Ltd., published in 1991). When using a photoradical polymerization initiator, it is preferable to use it in the range of 0.1 to 200 parts by mass, and more preferably in the range of 1 to 150 parts by mass, per 100 parts by mass of crosslinking agent.

[0126] <Other Additives> In addition to the above components, other additives may include, for example, leveling agents, surfactants, silane coupling agents, polymerization inhibitors, antioxidants, rust inhibitors, mold release agents, plasticizers, defoaming agents, thickeners, dispersants, antistatic agents, anti-settling agents, pigments, dyes, UV absorbers, and light stabilizers. Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate.

[0127] These surfactants may be used individually or in combination of two or more. The amount of surfactant used is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 1 part by mass, and even more preferably 0.01 to 0.5 parts by mass, per 100 parts by mass of polymer.

[0128] When forming a low refractive index film, the mixture is not limited to the hollow silica, polymer, and additives described above. For example, a dispersion of hollow silica in a solvent may be used.

[0129] In one aspect of the present invention, a method for producing a low refractive index film is provided, comprising the following steps: dispersing hollow silica in a solvent to obtain a dispersion; coating the dispersion onto a substrate; and calcining the dispersion to volatilize the solvent.

[0130] Examples of solvents for dispersing hollow silica include PGMEA, PGME, or methyl ethyl ketone (MEK). From the viewpoint of dispersibility and volatility of hollow silica, PGMEA or PGME may be preferred, and PGMEA may be more preferred.

[0131] In the process of applying the dispersion onto a substrate, the method of applying the dispersion and the substrate to which the dispersion is applied may be the same as those used for applying the mixed solution.

[0132] In the process of calcining the dispersion to volatilize the solvent, the calcination conditions are not particularly limited as long as the solvent can be volatilized. The calcination conditions vary depending on the solvent, but for example, the calcination temperature may be 50°C to 400°C, and the calcination time may be 1 minute to 10 hours. As for the calcination method, for example, a hot plate, oven, or electric furnace may be used, and the calcination may be carried out in an appropriate atmosphere such as air, an inert gas such as nitrogen, or a vacuum.

[0133] According to the method of the present invention, a relatively thin film can be easily formed using a polymer-containing mixture, compared to the method used to form a low refractive index film.

[0134] The film thickness of the low refractive index film produced by this method may be, for example, 40 nm to 5000 nm, 50 nm to 1000 nm, 60 nm to 500 nm, or 70 nm to 100 nm.

[0135] Furthermore, the present invention provides a mixture for forming a low refractive index film. The mixture may contain at least hollow silica and a polymer.

[0136] The hollow silica and polymer contained in the mixture of the present invention are as described above. In the mixture of the present invention, hollow silica is dispersed in the polymer, and when a cured film is formed, the refractive index of the cured film can be further reduced.

[0137] The proportions of polymer and hollow silica in the mixture are not particularly limited as long as the hollow silica is sufficiently dispersed, and the amount of hollow silica in the mixture may be between 200 phr and 1200 phr.

[0138] The mixture may further contain additives. These additives may include the aforementioned crosslinking agents, photoradical polymerization initiators, and the like.

[0139] The low refractive index film of the present invention and its manufacturing method have been described above. The low refractive index film of the present invention can be suitably used in the fields of electronic devices and optical materials, such as liquid crystal displays, organic electroluminescent (EL) displays, touch panels, optical semiconductor (LED) elements, solid-state image sensors, organic thin-film solar cells, dye-sensitized solar cells, organic thin-film transistors (TFTs), lenses, prism cameras, binoculars, microscopes, semiconductor exposure equipment, etc.

[0140] The present invention will be described more specifically below with reference to synthesis examples and embodiments, but the present invention is not limited to the following embodiments.

[0141] The measuring devices used in the examples are as follows: １ [H-NMR] Instrument: Bruker NMR System AVANCE III HD 500 (500MHz) Measurement solvent: Deuterated dimethyl sulfoxide (DMSO-d ６) Reference material: Tetramethylsilane (TMS) (δ 0.0 ppm) [GPC] Instrument: HLC-8200 GPC manufactured by Tosoh Corporation Column: Tosoh TSKgel α-3000 + Tosoh TSKgel α-4000 Column temperature: 40℃ Solvent: Dimethylformamide (DMF) Detector: UV (271 nm) Detection line: Standard polystyrene [Ellipsometer] Instrument: Multi-incidence angle spectroscopic ellipsometer VASE manufactured by J.A. Woolam Japan [Spectrophotometer] Instrument: Konica Minolta CM-3700A [Turbidimeter] Instrument: Nippon Denshoku Industries Ltd. HAZE METER NDH 5000 [Optical microscope] Instrument: Evident Co., Ltd. Erecting microscope system BX53M [Etching] Instrument: Samco Co., Ltd., etching equipment RIE-10NR [UV cleaning] Equipment: Technovision Co., Ltd., UV ozone cleaning equipment UV-208 [Reliability testing] Equipment: ESPEC Corporation, small environmental tester SH-221 [Weathering resistance testing] Equipment: Sanyo Trading Co., Ltd., xenon weathering resistance tester Xe-1-B

[0142] [1] Synthesis of triazine ring-containing polymers [Synthesis Example 1-1] Synthesis of polymer compound [5] In a 3000 mL four-necked flask, 2,2-bis(3-amino-4-hydroxyphenyl)propane [2] (56.0 g, 0.217 mol, manufactured by Wakayama Seika Kogyo Co., Ltd.) and 3-methoxy-N,N-dimethylpropanamide (600.0 g, KJCMPA-100, manufactured by KJ Chemicals Co., Ltd.) were added, and after purging with nitrogen, the mixture was stirred to dissolve 2,2-bis(3-amino-4-hydroxyphenyl)propane [2] in KJCMPA-100. The mixture was then cooled to -5°C using an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (50.0 g, 0.271 mol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added while ensuring that the internal temperature did not exceed 5°C. Finally, the mixture was washed with KJCMPA-100 (50.0 g). After stirring for 30 minutes, 4-aminophenethyl alcohol [3] (19.2 g, 0.108 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 4-(trifluoromethoxy)aniline [4] (44.6 g, 0.325 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and KJCMPA-100 (150.0 g) were dissolved by stirring and added dropwise, then washed with KJCMPA-100 (50.0 g). The mixture was then heated and stirred at 85°C for 3 hours. Next, N,N-diethylethanolamine (108.3 g, manufactured by Kanto Chemical Co., Ltd.) was added dropwise, and the mixture was heated and stirred at 85°C for 30 minutes, after which stirring was stopped. Tetrahydrofuran (THF) (250 g, manufactured by Junsei Chemical Co., Ltd.), ammonium acetate (500.0 g), and deionized water (500.0 g) were added to the reaction solution and stirred for 30 minutes. After stopping the stirring, the solution was transferred to a separatory funnel and separated into an organic layer and an aqueous layer, and the organic layer was recovered. Ammonium acetate (500.0 g) and deionized water (500.0 g) were added again to the recovered organic layer and the mixture was stirred for 30 minutes. After stopping the stirring, the solution was transferred to a separatory funnel and separated into an organic layer and an aqueous layer, and the organic layer was recovered again. The recovered organic layer was added dropwise to methanol (800.0 g) and deionized water (1200.0 g) and reprecipitation was performed. The obtained precipitate was filtered off and dried in a vacuum dryer at 80°C for 8 hours to obtain 156.7 g of the target polymer compound [5] (hereinafter referred to as compound P-1).

[0143] [Synthesis Example 1-2] Synthesis of polymer compound [6] 20.00 g of compound P-1[5] obtained in Synthesis Example 1-1 and 68.6 g of PGMEA were added to a 100 mL four-necked flask, and after purging with nitrogen, the mixture was stirred to dissolve. The solution was then heated to an internal temperature of 70°C, and 0.0060 g of 2,2'-ethylidenebis(4,6-di-tert-amylphenol) monoacrylate (SUMILIZER GS, manufactured by Sumitomo Chemical Co., Ltd.) and 6.01 g of 2-isocyanatoethyl acrylate (AOI-VM, manufactured by Showa Denko K.K.) were added dropwise. The mixture was stirred at an internal temperature of 70°C for 3 hours to obtain a 26.8 wt% PGMEA solution (hereinafter referred to as P-1-1 solution).

[0144] The weight-average molecular weight Mw of compound P-1, measured in polystyrene equivalent by GPC, was 2,012, and the polydispersity Mw / Mn was 2.3. １ The measurement results of the H-NMR spectrum are shown in Figure 1.

[0145] [Synthesis Example 1-3] Synthesis of polymer compound [7] The target polymer compound [7] was obtained in the same manner as in Synthesis Example 1-2 of Japanese Patent Application No. 2023-113883 (hereinafter referred to as compound P-2).

[0146] [Synthesis Example 1-4] Synthesis of polymer compound [8] A 29.2 wt% PGMEA solution of the target polymer compound [8] was obtained in the same manner as in Synthesis Example 1-3 of Japanese Patent Application No. 2023-113883 (hereinafter referred to as P-2 solution).

[0147] [Synthesis Example 1-5] Synthesis of polymer compound [9] In a 3000 mL four-necked flask, 2,2-bis(3-amino-4-hydroxyphenyl)propane [2] (56.0 g, 0.217 mol, manufactured by Wakayama Seika Kogyo Co., Ltd.) and 3-methoxy-N,N-dimethylpropanamide (676.0 g, KJCMPA-100, manufactured by KJ Chemicals Co., Ltd.) were added, and after purging with nitrogen, the mixture was stirred to dissolve 2,2-bis(3-amino-4-hydroxyphenyl)propane [2] in KJCMPA-100. The mixture was then cooled to -5°C using an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (50.0 g, 0.271 mol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added while ensuring that the internal temperature did not exceed 5°C. Finally, the mixture was washed with KJCMPA-100 (50.0 g). After stirring for 30 minutes, 4-(trifluoromethoxy)aniline [4] (44.6 g, 0.325 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and KJCMPA-100 (186.4 g) were dissolved by stirring and added dropwise, then washed with KJCMPA-100 (45.1 g). The mixture was then heated and stirred at 85°C for 3 hours. Next, N,N-diethylethanolamine (108.3 g, manufactured by Kanto Chemical Co., Ltd.) was added dropwise, and the mixture was heated and stirred at 85°C for 30 minutes, after which stirring was stopped. Tetrahydrofuran (THF) (135 g, manufactured by Junsei Chemical Co., Ltd.), ammonium acetate (540.0 g), and deionized water (540.0 g) were added to the reaction solution and stirred for 30 minutes. After stirring was stopped, the solution was transferred to a separatory funnel and separated into an organic layer and an aqueous layer, and the organic layer was recovered. THF (60.0 g) was added again to the recovered organic layer, separating it into an organic layer and an aqueous layer, and the organic layer was recovered. The recovered organic layer was added dropwise to methanol (2404 g) and deionized water (1200.0 g) and reprecipitation was performed. The resulting precipitate was filtered off and dried in a vacuum dryer at 80°C for 8 hours to obtain 148.2 g of the target polymer compound [9] (hereinafter referred to as compound P-3).

[0148] The weight-average molecular weight Mw of compound P-3, measured in polystyrene equivalent by GPC, was 1952, and the polydispersity Mw / Mn was 1.8. １ The measurement results of the H-NMR spectrum are shown in Figure 2.

[0149] [Synthesis Example 1-6] Synthesis of polymer compounds

[11] In a 3000 mL four-necked flask, 2,2-bis[4-(4-aminophenoxy)phenyl]propane

[10] (89.0 g, 0.217 mol, manufactured by Wakayama Seika Kogyo Co., Ltd.) and 3-methoxy-N,N-dimethylpropanamide (750.8 g, KJCMPA-100, manufactured by KJ Chemicals Co., Ltd.) were added, and after purging with nitrogen, the mixture was stirred to dissolve 2,2-bis[4-(4-aminophenoxy)phenyl]propane

[10] in KJCMPA-100. The mixture was then cooled to -5°C using an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine[1] (50.0 g, 0.271 mol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added while ensuring that the internal temperature did not exceed 5°C. Finally, the mixture was washed with KJCMPA-100 (41.7 g). After stirring for 30 minutes, 4-(trifluoromethoxy)aniline [4] (76.8 g, 0.434 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and KJCMPA-100 (41.7 g) were dissolved by stirring and added dropwise. The mixture was then heated and stirred at 85°C for 3 hours. Next, N,N-diethylethanolamine (108.3 g, manufactured by Kanto Chemical Co., Ltd.) was added dropwise, and the mixture was heated and stirred at 85°C for 30 minutes, after which stirring was stopped. Tetrahydrofuran (THF) (135 g, manufactured by Junsei Chemical Co., Ltd.), ammonium acetate (520.0 g), and deionized water (520.0 g) were added to the reaction solution and stirred for 30 minutes. After stirring was stopped, the solution was transferred to a separatory funnel and separated into an organic layer and an aqueous layer, and the organic layer was recovered. THF (70.0 g) was added again to the recovered organic layer, and the mixture was separated into an organic layer and an aqueous layer, and the organic layer was recovered. The recovered organic layer was added dropwise to methanol (2317.0 g) and deionized water (1158.0 g) and reprecipitation was performed. The resulting precipitate was further washed with deionized water (3475.0 g) and dried in a vacuum dryer at 80°C for 8 hours to obtain 188.1 g of the target polymer compound

[11] (hereinafter referred to as compound P-4).

[0150] The weight-average molecular weight Mw of compound P-4, measured in polystyrene equivalent by GPC, was 4854, and the polydispersity Mw / Mn was 2.5. １ The measurement results of the H-NMR spectrum are shown in Figure 3. [Synthesis Example 1-7] Synthesis of polymer compound

[12] In a 3000 mL four-necked flask, 2,2-bis[4-(4-aminophenoxy)phenyl]propane

[10] (80.1 g, 0.195 mol, manufactured by Wakayama Seika Kogyo Co., Ltd.) and 3-methoxy-N,N-dimethylpropanamide (520.0 g, KJCMPA-100, manufactured by KJ Chemicals Co., Ltd.) were added, and after purging with nitrogen, the mixture was stirred to dissolve 2,2-bis[4-(4-aminophenoxy)phenyl]propane

[10] in KJCMPA-100. The mixture was then cooled to -5°C using an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine[1] (40.0 g, 0.271 mol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added while ensuring that the internal temperature did not exceed 5°C. Finally, the mixture was washed with KJCMPA-100 (40.0 g). After stirring for 30 minutes, 4-aminophenethyl alcohol [3] (23.8 g, 0.174 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 4-(trifluoromethoxy)aniline [4] (15.4 g, 0.0870 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and KJCMPA-100 (100.0 g) were dissolved by stirring and added dropwise. Then, the mixture was washed with KJCMPA-100 (20.0 g) and heated and stirred at 85°C for 3 hours. Next, N,N-diethylethanolamine (52.0 g, manufactured by Kanto Chemical Co., Ltd.) was added dropwise, and the mixture was heated and stirred at 85°C for 30 minutes, after which stirring was stopped. Tetrahydrofuran (THF) (360 g, manufactured by Junsei Chemical Co., Ltd.), ammonium acetate (400.0 g), and deionized water (400.0 g) were added to the reaction solution and stirred for 30 minutes. After stopping the stirring, the solution was transferred to a separatory funnel and separated into an organic layer and an aqueous layer, and the organic layer was recovered. The recovered organic layer was added dropwise to methanol (800.0 g) and deionized water (1200.0 g) and reprecipitation was performed. The resulting precipitate was further washed with deionized water (2560.0 g) and dried in a vacuum dryer at 80°C for 8 hours to obtain 120.0 g of the target polymer compound

[12] (hereinafter referred to as compound P-5).

[0151] The weight-average molecular weight Mw of compound P-5, measured in polystyrene equivalent by GPC, was 17636, and the polydispersity Mw / Mn was 6.4. １ The measurement results of the H-NMR spectrum are shown in Figure 4.

[0152] [Synthesis Example 1-8] Synthesis of polymer compounds

[14] In a 3000 mL four-necked flask, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[13] (33.0 g, 0.087 mol, manufactured by JFE Chemical Corporation) and 3-methoxy-N,N-dimethylpropanamide (300.0 g, KJCMPA-100, manufactured by KJ Chemicals Co., Ltd.) were added, and after purging with nitrogen, the mixture was stirred to dissolve 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[13] in KJCMPA-100. The mixture was then cooled to -5°C using an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (20.0 g, 0.108 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added while ensuring that the internal temperature did not exceed 5°C. Finally, the mixture was washed with KJCMPA-100 (20.0 g). After stirring for 30 minutes, 4-aminophenethyl alcohol [3] (17.9 g, 0.130 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 4-(trifluoromethoxy)aniline [4] (7.7 g, 0.043 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and KJCMPA-100 (60.0 g) were dissolved by stirring and added dropwise, then washed with KJCMPA-100 (20.0 g). The mixture was then heated and stirred at 85°C for 3 hours. Next, N,N-diethylethanolamine (43.3 g, manufactured by Kanto Chemical Co., Ltd.) was added dropwise, and the mixture was heated and stirred at 85°C for 30 minutes, after which stirring was stopped. Tetrahydrofuran (THF) (180 g, manufactured by Junsei Chemical Co., Ltd.), ammonium acetate (250.0 g), and deionized water (250.0 g) were added to the reaction solution and stirred for 30 minutes. After stopping the stirring, the solution was transferred to a separatory funnel and separated into an organic layer and an aqueous layer, and the organic layer was recovered. Ammonium acetate (500.0 g) and deionized water (500.0 g) were added again to the recovered organic layer and the mixture was stirred for 30 minutes. After stopping the stirring, the solution was transferred to a separatory funnel and separated into an organic layer and an aqueous layer, and the organic layer was recovered again. The recovered organic layer was added dropwise to methanol (440.0 g) and deionized water (660.0 g) and reprecipitation was performed. The obtained precipitate was filtered off and dried in a vacuum dryer at 80°C for 8 hours to obtain 68.7 g of the target polymer compound

[14] (hereinafter referred to as compound P-6).

[0153] The weight average molecular weight Mw of Compound P-6 measured by GPC in terms of polystyrene was 1,953, and the polydispersity Mw / Mn was 2.5. For Compound P-6 １ The measurement results of the 1H-NMR spectrum are shown in Fig. 14.

[0154] [2] Production of hollow silica particles and dispersion [Production Example 2-1]: Production of surface-modified hollow silica particles (D1) (1) Preparation of an aluminum-containing hollow silica aqueous dispersion sol (a) As a starting material, a commercially available hollow silica aqueous sol (2,500.0 g, manufactured by Ningbo Dilato, HKT-A20-40D) was placed in a container, stirred, and a diluted sodium aluminate solution (42.5 g, an aqueous solution with a concentration of 1.0% by mass in terms of Al ２ O ３ was added dropwise over 1 minute and stirred for 60 minutes. 2,537.6 g of the above mixture was placed in a 3 L-SUS autoclave container, heat-treated at 150 °C for 5 hours, and cooled to room temperature. Further, 8% sulfuric acid (6.1 g) was added with stirring and stirred for 1 hour, and then passed through a column-packed cation exchange resin (H-type Amberlite IR-120B) at a space velocity (SV) of 5 / hour to obtain an aqueous sol A with 18.9% by mass of SiO ２ and a pH of 2.4. The aqueous sol A was heat-treated at 80 °C for 10 hours, cooled to room temperature, and then passed through a column-packed cation exchange resin (H-type Amberlite IR-120B) at a space velocity (SV) of 5 / hour to obtain an aqueous dispersion sol (a) of aluminum-containing hollow silica particles. Its physical properties were 17.0% by mass of SiO ２ , a pH of 2.3, an average particle diameter of 54 nm by the DLS method, a specific surface area (C) of 116 m ２ / g by the BET method, an aluminum amount (A) of 1,500 ppm bound to the particle surface, an aluminum amount (B) of 2,500 ppm present in the whole particle, (A / B ratio) of 0.60, an average particle diameter of 43 nm by TEM observation, a TEM-converted specific surface area (D) of 63 m ２ / g, a specific surface area ratio (C / D ratio) of 1.8, a particle refractive index of 1.27, and a shell thickness of 6.0 nm.

[0155] (2) Preparation of methanol dispersion sol (a1) of aluminum-containing hollow silica particles 690.4 g of aqueous dispersion sol (a) of aluminum-containing hollow silica particles was placed in a 2 L round-bottom flask, and 68.1 g of methanol was added. The mixture was then evaporated using a rotary evaporator under reduced pressure of 580 Torr and heated to 120°C, to obtain methanol dispersion sol (a1) of aluminum-containing hollow silica particles. Its properties were pH 3.5, average particle size 72 nm by DLS method, and SiO ２ As such, 23.5% by mass, moisture content 0.4% by mass, viscosity 1.3 mPa·sec, hollow silica particles SiO ２ The surface charge amount, converted to 1g, was 52 μeq / g. Methanol was added to this, and SiO ２ When adjusted to 20.5% by mass, the physical properties were pH 3.6, moisture content 0.3% by mass, and viscosity 1.2 mPa·sec.

[0156] (3) Preparation of methanol dispersion sol (a2) of silane-treated aluminum-containing hollow silica particles 151.2 g (SiO2) ２ 20.5% by mass was placed in a 500 mL round-bottom flask, 45.9 g of methanol and 1.55 g of water were added and stirred, and then 1.35 g of 3-(acryloyloxy)propyltrimethoxysilane (AcPS, manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-5103) was added and refluxed at 72°C for 5 hours while stirring. After that, it was cooled to room temperature to prepare methanol dispersion sol (a2) of silane-treated aluminum-containing hollow silica particles. Its physical properties were pH 3.7, average particle size 72 nm by DLS method, SiO ２ As such, 15.6% by mass, moisture content 1.0% by mass, viscosity 1.1 mPa·sec, SiO2 of hollow silica particles ２ The surface charge, converted to a per-gram amount, was 56 μeq / g.

[0157] (4) Preparation of PGME dispersion sol (a3) ​​of silane-treated aluminum-containing hollow silica particles 101.8 g of methanol dispersion sol (a2) and 85.4 g of PGME were added to a 500 mL round-bottom flask, and the methanol was completely removed using an evaporator to obtain a 16.8% by mass PGME dispersion sol (a3).

[0158] [Production Example 2-2]: Production of Unmodified Hollow Silica Particles (D2) (5) Preparation of Aluminum-Containing Hollow Silica Aqueous Dispersion Sol (b) As a starting material, a commercially available hollow silica aqueous sol (1573.2 g, manufactured by Ningbo Dilato, HKT-A20-45D B1 Lot 230928, SiO ２ at 20.2% by mass) was placed in a container, stirred, and a diluted sodium aluminate solution (27.0 g, Al ２ O ３ in an aqueous solution with a concentration of 1.0% by mass in terms of conversion) was added dropwise over 1 minute. After stirring for 60 minutes, pure water (514.5 g) was added and stirred for 30 minutes. 2060.3 g of the above mixture was placed in a 3 L-SUS autoclave container, heat-treated at 150°C for 5 hours, and cooled to room temperature. Further, 8% sulfuric acid (3.7 g) was added under stirring, and stirred for 1 hour. The solution was passed through a column-packed cation exchange resin (H-type Amberlite IR-120B) at a space velocity (SV) of 5 / hour to obtain an aqueous sol B with a pH of 4.2. The aqueous sol B was heat-treated at 80°C for 10 hours, cooled to room temperature, and then passed through a column-packed cation exchange resin (H-type Amberlite IR-120B) at a space velocity (SV) of 5 / hour to obtain an aqueous dispersion sol (b) of aluminum-containing hollow silica particles. Its physical properties were 13.7% by mass as SiO ２ , pH 3.0, average particle diameter of 62 nm by the DLS method, specific surface area of 109 m ２ / g, average particle diameter of 45 nm by TEM observation, and outer shell thickness of 7 nm.

[0159] (6) Preparation of PGME Dispersion Sol (b1) of Aluminum-Containing Hollow Silica Particles 926.7 g of the aqueous dispersion sol (b) of aluminum-containing hollow silica particles was placed in a 2 L eggplant flask, and 146.0 g of PGME was further added. The pressure was reduced to 580 Torr using a rotary evaporator, and PGME substitution was carried out while heating at 120°C to obtain a PGME dispersion sol (b1) of 15.1% by mass of aluminum-containing hollow silica particles.

[0160] [Manufacturing Example 2-3]: Manufacturing of surface-modified hollow silica particles (D3) (7) Preparation of aluminum-containing hollow silica aqueous dispersion sol (c) Commercial hollow silica aqueous sol (Ningbo Dilato, HKT-D20-225-2 Lot 220506, SiO2) as starting material ２ Place 1856.4 g (20.2% by mass) into a container, stir, and dilute sodium aluminate (Al ２ O ３ 31.9 g of an aqueous solution (converted to 1.0 mass% concentration) was added dropwise over 1 minute, stirred for 60 minutes, then 611.7 g of pure water was added and stirred for 30 minutes. 2443.7 g of the above mixture was placed in a 3 L stainless steel autoclave container and heated at 150°C for 5 hours, then cooled to room temperature. Furthermore, 4.2 g of 8% sulfuric acid was added under stirring, stirred for 1 hour, and then passed through a cation exchange resin (H-type Amberlite IR-120B) packed into a column at a space velocity (SV) of 5 / hour to obtain an aqueous sol with a pH of 2.8. Aqueous sol A was heated at 80°C for 10 hours, cooled to room temperature, and then passed through a cation exchange resin (H-type Amberlite IR-120B) packed into a column at a space velocity (SV) of 5 / hour to obtain an aqueous dispersion sol (c) of aluminum-containing hollow silica particles. Its physical properties are SiO ２ Assuming a composition of 14.3% by mass, pH 2.5, average particle size of 87 nm by DLS method, and specific surface area of ​​106 m² by BET method. ２ The particle size was 79 nm and the outer shell thickness was 7 nm, as observed by TEM, at a density of / g.

[0161] (8) Preparation of methanol dispersion sol (c1) of aluminum-containing hollow silica particles 1077.6 g of aqueous dispersion sol (c) of aluminum-containing hollow silica particles was placed in a 2 L round-bottom flask, and 108.0 g of methanol was added. The mixture was then evaporated with methanol under reduced pressure of 580 Torr and heated to 120°C using a rotary evaporator to obtain methanol dispersion sol (c1) of aluminum-containing hollow silica particles. Its properties were pH 3.2, average particle size 110 nm by DLS method, and SiO ２ As such, 20.6% by mass, moisture content 0.6% by mass, viscosity 1.5 mPa·sec, SiO2 of hollow silica particles ２ The surface charge per gram is 35 μeq / g-SiO２ It was 120.8 g (SiO₂) of methanol dispersion sol of aluminum-containing hollow silica particles (c1). ２ 20.6% by mass was placed in a 300 mL round-bottom flask, 37.8 g of methanol and 0.9 g of water were added and stirred, and then 1.0 g of 3-(acrylooxy)propyltrimethoxysilane (AcPS, manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-5103) was added and reflux treatment was carried out at 72°C for 5 hours while stirring to obtain an AcPS-treated methanol dispersion sol (c1) of aluminum-containing hollow silica particles. Its physical properties were pH 3.4, average particle size 110 nm by DLS method, SiO ２ As such, 15.9% by mass, moisture 1.2% by mass, hollow silica particles SiO ２ The surface charge amount per gram is 27 μeq / g-SiO ２ That was the case.

[0162] (9) Preparation of aluminum-containing hollow silica aqueous dispersion sol (c2) 1070.9 g of aluminum-containing hollow silica particle aqueous dispersion sol (c1) was mixed with 360.0 g of pure water and concentrated using a UF membrane with a molecular weight cutoff of 200,000. Its physical properties were as follows: SiO ２ Assuming a concentration of 21.8% by mass, pH 2.5, average particle size of 96 nm by DLS method, and specific surface area of ​​106 m² by BET method. ２ The particle size was 79 nm and the outer shell thickness was 7 nm, as observed by TEM, at a density of / g.

[0163] (10) Preparation of methanol dispersion sol (c3) of aluminum-containing hollow silica particles 616.9 g of aqueous dispersion sol (c2) of aluminum-containing hollow silica particles was placed in a 2 L round-bottom flask, and 248.8 g of methanol was added. Using a rotary evaporator, the pressure was reduced to 580 Torr and the mixture was heated to 120°C, and methanol substitution was performed to obtain methanol dispersion sol (c3) of aluminum-containing hollow silica particles. Its properties were pH 3.3, average particle size 114 nm by DLS method, SiO ２ As such, 20.7% by mass, moisture content 0.7% by mass, viscosity 2.3 mPa·sec, SiO2 of hollow silica particles ２ The surface charge amount per gram is 31 μeq / g-SiO ２It was 565.0 g (SiO₂) of methanol dispersion sol (c3) of aluminum-containing hollow silica particles. ２ 20.7% by mass was placed in a 1 L round-bottom flask, 180.9 g of methanol and 3.4 g of water were added and stirred, and then 4.5 g of 3-(acrylooxy)propyltrimethoxysilane (AcPS, manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-5103) was added and reflux treatment was carried out at 72°C for 5 hours while stirring to obtain an AcPS-treated methanol dispersion sol (c3) of aluminum-containing hollow silica particles. Its physical properties were pH 3.5, average particle size 123 nm by DLS method, SiO ２ As such, 15.2% by mass, moisture 0.9% by mass, hollow silica particles SiO ２ Surface charge per gram: 28 μeq / g-SiO ２ That was the case.

[0164] (11) Preparation of PGME dispersion sol (c4) of aluminum-containing hollow silica particles 46.3 g of methanol dispersion sol (c3) and 38.2 g of PGME were added to a 500 mL round-bottom flask, and the methanol was completely removed using an evaporator to obtain a 20.1% by mass PGME dispersion sol (c4).

[0165] [Production Example 2-4]: Production of surface-modified hollow silica particles (D4) (12) Synthesis of cation exchange treated MeOH-dispersed hollow silica sol (d) 2000 g of HKT-A20-40D (manufactured by Ningbo Dilato, trade name) was placed in a 3 L poly container and stirred at a rotation speed of 650 rpm with a mechanical stirrer equipped with a glass stirring blade. Under this stirring, Al ２ O ３35.0 g of an aqueous sodium aluminate solution diluted to a concentration of 1.0% by mass was added dropwise over 1 minute, and the mixture was stirred at the same rotational speed for 30 minutes. 716 g of pure water was then added, and the mixture was stirred for an additional 10 minutes to obtain the mixture. Next, 2443 g of this mixture was placed in a 3 L stainless steel autoclave container and heated at 150°C for 5 hours under stirring at 80 rpm, and then cooled to below 50°C. 1000 g of the resulting aqueous dispersion silica sol of aluminum atom-containing hollow silica particles was placed in a 2 L round-bottom flask. Using a rotary evaporator, the pressure was reduced to 580 Torr, and the solvent (dispersion medium), water, was replaced with methanol (MeOH) while heated to 120°C. Methanol was then added to adjust the concentration, and a 20% by mass MeOH-dispersed silica sol (pH 6.1) of aluminum atom-containing hollow silica particles was obtained. 500 g of the obtained MeOH-dispersed silica sol was passed through a 100 mL glass column packed with 50 mL of cation exchange resin at a space velocity (sv) of 7 / hour to obtain cation exchange-treated MeOH-dispersed hollow silica sol (d).

[0166] (13) Synthesis of PGME-dispersed hollow silica sol (d-1) 200 g of the obtained cation exchange treated MeOH-dispersed silica sol was placed in a 500 mL round-bottom flask, and MeOH was removed by distillation while adding PGME in a rotary evaporator under a pressure of 450 Torr to 100 Torr and a bath temperature of 80 to 90°C to obtain PGME-dispersed hollow silica sol (d-1) with a silica particle concentration of 20% by mass.

[0167] [Manufacturing Example 2-5]: Manufacturing of surface-modified hollow silica particles (D5) (14) Synthesis of MeOH-dispersed hollow silica sol (e) 1856 g of HKT-A20-70D (manufactured by Ningbo Dilato, trade name) is placed in a 3 L poly container, Al ２ O ３32.2 g of sodium aluminate, diluted to a concentration of 1.0% by mass, was added dropwise over 1 minute, followed by the addition of 643.6 g of pure water. The mixture was then stirred for 30 minutes at a rotational speed of 600 rpm using a mechanical stirrer equipped with a glass stirring blade. Next, 2442 g of this mixture was placed in a stainless steel autoclave container and subjected to heat treatment at 150°C for 5 hours, followed by cooling to room temperature. To 1700 g of the obtained heat-treated aqueous silica sol, 1.51 g of 8.2% aqueous sulfuric acid solution was added dropwise, and the mixture was stirred at a stirring speed of 800 rpm for 1 hour at room temperature to obtain a sulfuric acid-added heat-treated aqueous silica sol. Next, the solution was passed through a cation exchange resin (product name H-type Amberlite IR-120B) packed into a column at a space velocity (SV) of 5 / hour to obtain an aqueous dispersion sol of aluminum-containing hollow silica particles. The physical properties of the obtained aqueous dispersion sol were measured, and the result showed that SiO ２ The composition is 14.3% by mass, pH 2.5, with an average primary particle diameter of 71 nm as observed by TEM, and a specific surface area of ​​102 m² as measured by the BET method. ２ The result was / g. Subsequently, the eggplant-shaped flask containing the obtained aqueous dispersion sol was placed in a rotary evaporator, and distillation was performed while supplying MeOH under reduced pressure of 580 Torr at a bath temperature of 120°C, thereby replacing the dispersion medium with MeOH to obtain the target sol. The obtained MeOH-dispersed hollow silica sol (e) with methanol as the dispersion medium had a pH of 3.1, a silica concentration of 20.3% by mass, and a water content of 1.2% by mass. Furthermore, there was no precipitate, indicating good dispersibility.

[0168] (15) Synthesis of PGMEA-dispersed hollow silica sol (e-1) 50 g of the MeOH-dispersed silica sol of the obtained aluminum atom-containing hollow silica particles was placed in a 100 mL poly container, 50 mL of cation exchange resin (manufactured by Dow Chemical, product name: Amberlite IR-120B) was added, and the mixture was held for 60 minutes while stirring at 100 times per minute with a mix rotor (manufactured by AS ONE Corporation, product name: MIX-ROTAR MR-5) to obtain MeOH-dispersed silica sol of hollow silica particles. Next, 25 g of the MeOH-dispersed silica sol of the obtained hollow silica particles was placed in a 50 mL round-bottom flask. While stirring with a magnetic stirrer, 3.8 g of PGMEA, 0.16 g of a 10% by mass MeOH solution of 4-methoxyphenol (MEHQ) diluted with MeOH, and 0.20 g of methacryloxypropylmethyldimethoxysilane (MPMDMS) were added, and the mixture was heated to 60°C and held for 3 hours. Then, 0.29 g of hexamethyldisiloxane (TMSO) was added, and the mixture was heated to 60°C and held for 3 hours. After that, diisopropanolamine (DiPA) was added to adjust the pH to 8.0-10.0, and the mixture was heated to 60°C and held for 1 hour to obtain the MeOH-dispersed silica sol of surface-modified hollow silica particles. The resulting eggplant-shaped flask containing the silica sol was placed in a rotary evaporator, and distillation was performed under reduced pressure of 550 Torr to 350 Torr at a bath temperature of 80°C while supplying PGMEA. By replacing the dispersion medium from MeOH to PGMEA, a hollow silica sol (e-1) with hollow silica particles dispersed in PGMEA was obtained.

[0169] [3] Preparation of composition and production of cured film [Example 1-1] To the P-1-1 solution (0.143 g) obtained in Synthesis Example 1-2 and the PGME dispersion sol (a3) ​​(1.28 g) obtained in Production Example 2-1, 0.0387 g of CEL-2021P (manufactured by Daicel Corporation), 0.00130 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.00130 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.0022 g of EFS-521 (manufactured by DIC Corporation) as a 20% by mass PGMEA solution as a surfactant, and 12.2 g of PGME and 1.37 g of PGMEA as additional diluting monomers were added and it was confirmed that the mixture was dissolved visually to prepare the solution (hereinafter referred to as SP-1 solution). This SP-1 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 1300 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２ The exposure was measured under nitrogen. After UV irradiation, etching was performed for 2 minutes using a Samco RIE-10NR etching system under the conditions of a flow rate of 50 sccm, a pressure of 5.0 Pa, and a frequency of 100 W. ２ The desired cured film (hereinafter referred to as SP-1 film) was obtained by etching with gas.

[0170] [Example 1-2] The SP-1 solution prepared in Example 1-1 was spin-coated onto a 50 mm x 50 mm x 0.7 t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 1300 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２ The exposure dose was measured under nitrogen. After UV irradiation, the sample was treated with a UV-208 UV ozone cleaning device manufactured by Technovision Co., Ltd. for 20 minutes. ３ The desired cured film (hereinafter referred to as SP-2 film) was obtained by cleaning.

[0171] [Example 1-3] The SP-1 solution prepared in Example 1-1 was spin-coated onto a 50 mm x 50 mm x 0.7 t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 1300 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２ The exposure was measured under nitrogen. After UV irradiation, 1 mL of PGMEA was applied to the film using a spin coater, and the film was washed at 50 rpm for 60 seconds and then at 1000 rpm for 30 seconds. Finally, the film was baked on a 100°C hot plate for 30 minutes to obtain the desired cured film (hereinafter referred to as SP-3 film).

[0172] [Example 1-4] The SP-1 solution prepared in Example 1-1 was spin-coated onto a 50 mm x 50 mm x 0.7 t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 1300 rpm for 30 seconds, and pre-dried on a 100°C hot plate for 10 minutes. After drying, etching was performed for 2 minutes using a Samco RIE-10NR etching apparatus under the conditions of a flow rate of 50 sccm, a pressure of 5.0 Pa, and a frequency of 100 W. ２ The desired cured film (hereinafter referred to as SP-4 film) was obtained by etching with gas.

[0173] [Example 1-5] To the P-1-1 solution (0.646 g) obtained in Synthesis Example 1-2 and the PGME dispersion sol (a3) ​​(5.15 g) obtained in Production Example 2-1, 0.00520 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.00520 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.00860 g of EFS-521 (manufactured by DIC Corporation), a 20% by mass PGMEEA solution, as a surfactant, and 1.07 g of PGME and 0.115 g of PGMEEA as additional diluting monomers were added, and the solution was prepared by visual confirmation that it was dissolved (hereinafter referred to as SP-2 solution). This SP-2 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 1100 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２The exposure was measured under nitrogen. After UV irradiation, 1 mL of PGMEA was applied to the film using a spin coater, and the film was washed at 50 rpm for 60 seconds and then at 1000 rpm for 30 seconds. Finally, it was baked on a 100°C hot plate for 30 minutes to obtain the desired cured film (hereinafter referred to as SP-5 film).

[0174] [Example 1-6] To the PGME dispersion sol (a3) ​​(1.19 g) obtained in Production Example 2-1, 0.0020 g of EFS-521 (manufactured by DIC Corporation), a 20% by mass PGMEA solution, was added as a surfactant, and 7.83 g of PGME and 0.978 g of PGMEA were added as additional diluent monomers. Visual confirmation of dissolution was made to prepare the solution (hereinafter referred to as SP-3 solution). This SP-3 solution was spin-coated onto a 50 mm × 50 mm × 0.7 t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 2280 rpm for 30 seconds, and then baked on a hot plate at 100°C for 30 minutes to obtain the desired cured film (hereinafter referred to as SP-6 film).

[0175] [Example 1-7] To the PGME dispersion sol (a3) ​​(1.79 g) obtained in Production Example 2-1, 0.00180 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.00180 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.00300 g of EFS-521 (manufactured by DIC Corporation), a 20% by mass PGMEA solution, as a surfactant, and 11.7 g of PGME and 1.47 g of PGMEA as additional diluting monomers were added, and the solution was prepared by visual confirmation that the substances were dissolved (hereinafter referred to as SP-4 solution). This SP-4 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 2280 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２ By irradiating the material under nitrogen, the desired cured film (hereinafter referred to as SP-7 film) was obtained.

[0176] [Example 1-8] Compound P-1 (0.151 g) obtained in Synthesis Example 1-1 and PGME dispersion sol (a3) ​​(4.48 g) obtained in Production Example 2-1 were mixed with 0.136 g of CEL-2021P (manufactured by Daicel Corporation), 0.00450 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.00450 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.00750 g of EFS-521 (manufactured by DIC Corporation) as a 20% by mass PGMEA solution as a surfactant, and 1.55 g of PGME and 0.2224 g of PGMEA as additional diluting monomers. The mixture was visually dissolved to prepare the solution (hereinafter referred to as SP-5 solution). This SP-5 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 760 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２ The exposure was measured under nitrogen. After UV irradiation, 1 mL of PGMEA was applied to the film using a spin coater, and the film was washed at 50 rpm for 60 seconds and then at 1000 rpm for 30 seconds. Finally, the film was baked on a 100°C hot plate for 30 minutes to obtain the desired cured film (hereinafter referred to as SP-8 film).

[0177] [Example 1-9] Compound P-2 (0.516 g) obtained in Synthesis Example 1-4 and PGME dispersion sol (a3) ​​(4.48 g) obtained in Production Example 2-1 were mixed with 0.136 g of CEL-2021P (manufactured by Daicel Corporation), 0.00450 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.00450 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.00750 g of EFS-521 (manufactured by DIC Corporation) as a 20% by mass PGMEA solution as a surfactant, and 1.62 g of PGME and 0.2224 g of PGMEA as additional diluting monomers. The mixture was visually dissolved to prepare the solution (hereinafter referred to as SP-6 solution). This SP-6 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 760 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２ The exposure was measured under nitrogen. After UV irradiation, 1 mL of PGMEA was applied to the film using a spin coater, and the film was washed at 50 rpm for 60 seconds and then at 1000 rpm for 30 seconds. Finally, the film was baked on a 100°C hot plate for 30 minutes to obtain the desired cured film (hereinafter referred to as SP-9 film).

[0178] [Example 1-10] Compound P-3 (0.173 g) obtained in Synthesis Example 1-5 and PGME dispersion sol (a3) ​​(5.15 g) obtained in Production Example 2-1 were mixed with 0.00520 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.00520 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.00860 g of EFS-521 (manufactured by DIC Corporation) as a 20% by mass PGMEEA solution as a surfactant, and 1.07 g of PGME and 0.588 g of PGMEEA as additional diluting monomers. The mixture was visually dissolved to prepare the solution (hereinafter referred to as SP-7 solution). This SP-7 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 760 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２ The exposure was measured under nitrogen. After UV irradiation, 1 mL of PGMEA was applied to the film using a spin coater, and the film was washed at 50 rpm for 60 seconds and then at 1000 rpm for 30 seconds. Finally, the film was baked on a 100°C hot plate for 30 minutes to obtain the desired cured film (hereinafter referred to as SP-10 film).

[0179] [Example 1-11] Compound P-3 (0.247 g) obtained in Synthesis Example 1-5 and PGME dispersion sol (c4) (5.15 g) obtained in Production Example 2-3 were mixed with 0.00740 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.00740 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.0124 g of EFS-521 (manufactured by DIC Corporation) as a 20% by mass PGMEEA solution as a surfactant, and 2.72 g of PGME and 0.840 g of PGMEEA as additional diluting monomers. The mixture was visually dissolved to prepare the solution (hereinafter referred to as SP-8 solution). This SP-8 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 800 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２The exposure was measured under nitrogen. After UV irradiation, 1 mL of PGMEA was applied to the film using a spin coater, and the film was washed at 50 rpm for 60 seconds and then at 1000 rpm for 30 seconds. Finally, the film was baked on a 100°C hot plate for 30 minutes to obtain the desired cured film (hereinafter referred to as SP-11 film).

[0180] [Example 1-12] The SP-1 solution obtained in Example 1-1 was spin-coated onto a 50 mm × 50 mm × 0.7 t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 1300 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２ The exposure was measured under nitrogen. After UV irradiation, etching was performed for 2 minutes using a Samco RIE-10NR etching system under the conditions of a flow rate of 50 sccm, a pressure of 5.0 Pa, and a frequency of 100 W. ２ After etching with gas, the desired cured film (hereinafter referred to as SP-12 film) was obtained by firing it on a 100°C hot plate for 30 minutes.

[0181] [Example 1-13] Compound P-4 (0.149 g) obtained in Synthesis Example 1-6 and PGME dispersion sol (a3) ​​(7.98 g) obtained in Production Example 2-1 were mixed with 0.00450 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.00450 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.0074 g of EFS-521 (manufactured by DIC Corporation) as a 20% by mass PGMEA solution as a surfactant, and 1.02 g of PGME and 0.844 g of PGMEA as additional diluting monomers. The mixture was visually dissolved to prepare the solution (hereinafter referred to as SP-9 solution). This SP-9 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 860 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２ The exposure was measured under nitrogen. After UV irradiation, etching was performed for 15 minutes using a Samco RIE-10NR etching system under the conditions of a flow rate of 50 sccm, a pressure of 5.0 Pa, and a frequency of 100 W.２ The desired cured film (hereinafter referred to as SP-13 film) was obtained by etching with gas.

[0182] [Example 1-14] To the PGME dispersion sol (b1) (1.04 g) obtained in Production Example 2-2, 0.000900 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.000900 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.00160 g of EFS-521 (manufactured by DIC Corporation), a 20% by mass PGMEA solution, as a surfactant, and 6.17 g of PGME and 0.783 g of PGMEA as additional diluting monomers were added, and the solution was prepared by visual confirmation that the substances were dissolved (hereinafter referred to as SP-10 solution). The SP-10 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 1290 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２ The desired cured film (hereinafter referred to as SP-14 film) was obtained by irradiating the film under nitrogen and baking it on a 100°C hot plate for 30 minutes.

[0183] [Example 1-15] Compound P-4 (0.0264 g) obtained in Synthesis Example 1-6 and PGME dispersion sol (b1) (0.875 g) obtained in Production Example 2-2 were mixed with 0.00080 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.00080 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.0013 g of EFS-521 (manufactured by DIC Corporation) as a 20% by mass PGMEA solution as a surfactant, and 6.31 g of PGME and 0.783 g of PGMEA as additional diluting monomers. The mixture was visually dissolved to prepare the solution (hereinafter referred to as SP-11 solution). The SP-11 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 1290 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２The exposure was measured under nitrogen. After UV irradiation, 1 mL of PGMEA was applied to the film using a spin coater, and the film was washed at 50 rpm for 60 seconds and then at 1000 rpm for 30 seconds. Finally, the film was baked on a 100°C hot plate for 30 minutes to obtain the desired cured film (hereinafter referred to as SP-15 film).

[0184] [Example 1-16] Compound P-6 (0.033 g) obtained in Synthesis Example 1-8 and PGME dispersion sol (a3) ​​(0.99 g) obtained in Production Example 2-1 were mixed with 0.0010 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.0010 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.0016 g of EFS-521 (manufactured by DIC Corporation) as a 20% by mass PGMEEA solution as a surfactant, and 8.00 g of PGME and 0.98 g of PGMEEA as additional diluting monomers. The mixture was visually dissolved to prepare the solution (hereinafter referred to as SP-12 solution). The SP-12 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 1290 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２ The exposure was measured under nitrogen. After UV irradiation, 1 mL of PGMEA was applied to the film using a spin coater, and the film was washed at 50 rpm for 60 seconds and then at 1000 rpm for 30 seconds. Finally, it was baked on a 100°C hot plate for 30 minutes to obtain the desired cured film (hereinafter referred to as SP-16 film).

[0185] [Example 1-17] EHPE-3150 (manufactured by Daicel Corporation) (0.033 g) and the PGME dispersion sol (a3) ​​(0.99 g) obtained in Production Example 2-1 were mixed with 0.0010 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.0010 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.0016 g of EFS-521 (manufactured by DIC Corporation) as a 20% by mass PGMEA solution as a surfactant, and 8.00 g of PGME and 0.98 g of PGMEA as additional diluting monomers. The mixture was visually dissolved to prepare the solution (hereinafter referred to as SP-13 solution). The SP-13 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 1290 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２ The exposure was measured under nitrogen. After UV irradiation, 1 mL of PGMEA was applied to the film using a spin coater, and the film was washed at 50 rpm for 60 seconds and then at 1000 rpm for 30 seconds. The film was then baked on a 100°C hot plate for 30 minutes to obtain the desired cured film (hereinafter referred to as SP-17 film).

[0186] [Example 1-18] VP-8000 (manufactured by Nippon Soda Co., Ltd.) (0.033 g) and the PGME dispersion sol (a3) ​​(0.99 g) obtained in Production Example 2-1 were mixed with 0.0010 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.0010 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.0016 g of EFS-521 (manufactured by DIC Corporation) as a 20% by mass PGMEEA solution as a surfactant, and 8.00 g of PGME and 0.98 g of PGMEEA as additional diluting monomers. The mixture was visually dissolved to prepare the solution (hereinafter referred to as SP-14 solution). The SP-14 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 1290 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２The exposure was measured under nitrogen. After UV irradiation, 1 mL of PGMEA was applied to the film using a spin coater, and the film was washed at 50 rpm for 60 seconds and then at 1000 rpm for 30 seconds. Finally, it was baked on a 100°C hot plate for 30 minutes to obtain the desired cured film (hereinafter referred to as SP-18 film).

[0187] [Example 1-19] Compound P-2 (0.430 g) obtained in Synthesis Example 1-4 and PGME dispersion sol (d-1) (9.97 g) obtained in Production Example 2-4 were mixed with 0.387 g of CEL-2021P (manufactured by Daicel Corporation), 0.0129 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.0129 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.0215 g of EFS-521 (manufactured by DIC Corporation) as a 20% by mass PGMEA solution as a surfactant, and 2.98 g of PGME and 1.18 g of PGMEA as additional diluting monomers. The mixture was visually dissolved to prepare the solution (hereinafter referred to as SP-15 solution). The SSP-15 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 1270 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２ The exposure was measured under nitrogen. After UV irradiation, 1 mL of PGMEA was applied to the film using a spin coater, and the film was washed at 50 rpm for 60 seconds and then at 1000 rpm for 30 seconds. Finally, the film was baked on a 100°C hot plate for 30 minutes to obtain the desired cured product (hereinafter referred to as SSP-19 film).

[0188] [Example 1-20] Compound P-2 (0.297 g) obtained in Synthesis Example 1-4 and PGMEA dispersion sol (e-1) (10.2 g) obtained in Production Example 2-5 were mixed with 0.00890 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.00890 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.0149 g of EFS-521 (manufactured by DIC Corporation) as a 20% by mass PGMEA solution as a surfactant, and 0.960 g of PGME and 0.500 g of PGMEA as additional diluting monomers. The mixture was then visually confirmed to be dissolved, and a solution was prepared (hereinafter referred to as SP-16 solution). The SP-16 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 1190 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２ The exposure was measured under nitrogen. After UV irradiation, 1 mL of PGMEA was applied to the film using a spin coater, and the film was washed at 50 rpm for 60 seconds and then at 1000 rpm for 30 seconds. Finally, the film was baked on a 100°C hot plate for 30 minutes to obtain the desired cured product (hereinafter referred to as SP-20 film).

[0189] [Comparative Example 1-1] To the P-1-1 solution (1.421 g) obtained in Synthesis Example 1-2, 0.343 g of CEL-2021P (manufactured by Daicel Corporation), 0.0114 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.0114 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.0190 g of EFS-521 (manufactured by DIC Corporation) as a 20% by mass PGMEA solution as a surfactant, and 2.98 g of PGME and 0.219 g of PGMEA as additional diluting monomers were added, and the solution was prepared by visual confirmation that it was dissolved (hereinafter referred to as SP-21 solution). The SP-21 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 760 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２The exposure was measured under nitrogen. After UV irradiation, 1 mL of PGMEA was applied to the film using a spin coater, and the film was washed at 50 rpm for 60 seconds and then at 1000 rpm for 30 seconds. However, the film dissolved and a cured film could not be obtained.

[0190] [Comparative Example 1-2] Compound P-5 (0.215 g) obtained in Synthesis Example 1-7 and PGME dispersion sol (a3) ​​(6.41 g) obtained in Production Example 2-1 were mixed with 0.194 g of CEL-2021P (manufactured by Daicel Corporation), 0.00650 g of NCI-730 (manufactured by ADEKA Corporation) as a UV radical generator, 0.00650 g of X-12-1333A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, 0.0108 g of EFS-521 (manufactured by DIC Corporation) as a 20% by mass PGMEA solution as a surfactant, and 2.32 g of PGME and 0.841 g of PGMEA as additional diluting monomers. The mixture was visually dissolved to prepare the solution (hereinafter referred to as SP-22 solution). The SP-22 solution was spin-coated onto a 50mm x 50mm x 0.7t alkali-free glass substrate using a spin coater at 200 rpm for 5 seconds and then at 760 rpm for 30 seconds. After pre-drying on a 100°C hot plate for 10 minutes, it was irradiated with a UV-LED at a wavelength of 365 nm at a rate of 500 mJ / cm². ２ The exposure was measured under nitrogen. After UV irradiation, 1 mL of PGMEA was applied to the film using a spin coater, and the film was washed at 50 rpm for 60 seconds and then at 1000 rpm for 30 seconds. The film haze was measured at a high level of 19.8%, indicating whitening, and a highly transparent film could not be obtained.

[0191] Table 1 summarizes the film formation process for the cured films obtained in the above examples.

[0192] [4] Confirmation of physical properties of the cured film For the SP-1 to SP-15 films obtained above, the refractive index and film thickness were measured at a measurement wavelength of 589 nm. The results are shown in Table 2-1. For the SP-16 to SP-18 films obtained above, the refractive index and film thickness were measured at a measurement wavelength of 589 nm. The results are shown in Table 2-2. For the SP-19 to SP-20 films obtained above, the refractive index and film thickness were measured at a measurement wavelength of 589 nm. The results are shown in Table 2-3.

[0193] These results indicate that all films have a refractive index of 1.24 or less.

[0194] [5] Reliability Test of Cured Films The SP-1 to SP-10 films (excluding SP-9 film), SP-19 film, and SP-20 film obtained above were stored in a constant temperature chamber at 65°C and 90% humidity for 500 hours, and a reliability test was conducted. The film properties were measured before and after storage. The properties were the refractive index, film thickness, transmittance (average value from 400nm to 800nm), haze value, and YI value at a measurement wavelength of 589nm, and the results are shown in Tables 3 to 7. For refractive index, film thickness, and transmittance, the percentage change before and after the reliability test was calculated, and the percentage change was calculated using the following formula: Percentage change (%) = (Property value after reliability test - Property value before reliability test) ÷ (Property value before reliability test) × 100

[0195] These results indicate that all films showed small changes before and after reliability testing, demonstrating their excellent reliability.

[0196] [6] Solvent Resistance Test of Cured Film [Example 2-1] After obtaining a cured film (SP-1 film) in the same manner as in Example 1-1, it was set in a spin coater and 1 mL of propolene glycol monomethyl ether (PGME) was applied. Next, the cured film was exposed to the solvent by rotating at 50 rpm for 60 seconds to prevent the liquid from splashing from the substrate. After that, the solvent was removed from the substrate by rotating at 1000 rpm for 30 seconds. Finally, the film was dried at 100°C for 10 seconds using a hot plate, and then the refractive index and film thickness were measured, the residual film percentage was calculated, and the film surface was observed using an optical microscope. The residual film percentage was calculated using the following formula: Residual film percentage (%) = (Film thickness after solvent exposure) ÷ (Film thickness before solvent exposure) × 100

[0197] [Example 2-2] The cured film was prepared and solvent resistance tested in the same manner as in Example 2-1, except that the solvent to be applied was changed to propylene glycol monomethyl ether acetate (PGMEA).

[0198] [Example 2-3] Solvent resistance tests were conducted in the same manner as in Example 2-1, except that the film used was changed to the SP-4 film.

[0199] [Example 2-4] Solvent resistance tests were conducted in the same manner as in Example 2-2, except that the film used was changed to the SP-4 film.

[0200] [Example 2-5] Solvent resistance tests were conducted in the same manner as in Example 2-1, except that the film used was changed to the SP-6 film.

[0201] [Example 2-6] Solvent resistance tests were conducted in the same manner as in Example 2-1, except that the film used was changed to the SP-14 film.

[0202] [Example 2-7] Solvent resistance tests were conducted in the same manner as in Example 2-2, except that the film used was changed to the SP-14 film.

[0203] [Example 2-8] Solvent resistance tests were conducted in the same manner as in Example 2-1, except that the film used was changed to the SP-15 film.

[0204] [Example 2-9] Solvent resistance tests were conducted in the same manner as in Example 2-2, except that the film used was changed to the SP-15 film.

[0205] [Example 2-10] Solvent resistance testing was performed in the same manner as in Example 2-1, except that the film used was changed to the SP-19 film.

[0206] [Example 2-11] The solvent resistance test was performed in the same manner as in Example 2-2, except that the film used was changed to the SP-19 film.

[0207] [Example 2-12] The solvent resistance test was performed in the same manner as in Example 2-1, except that the film used was changed to the SP-20 film.

[0208] [Example 2-13] The solvent resistance test was performed in the same manner as in Example 2-2, except that the film used was changed to the SP-20 film.

[0209] Table 8 shows the results of film thickness measurement and residual film percentage for Examples 2-1 to 2-9 and Examples 2-10 to 2-13. Figures 5 to 13 show micrographs of the cured films of Examples 2-1 to 2-9 after solvent exposure. Figures 15 to 18 show micrographs of the cured films of Examples 2-10 to 2-13 after solvent exposure.

[0210] From the results shown in the table and figures above, it can be seen that the cured films of the present invention, SP-1, SP-4, SP-6, SP-14, and SP-15, maintained high solvent resistance, as no film loss or cracks were observed. Furthermore, it can be seen that the SP-19 and SP-20 films also maintained high solvent resistance, as no film loss or cracks were observed.

[0211] [7] Weathering Test of Cured Film A UV-cut filter (HOYA, L38) was placed on the SP-12 film obtained in Example 1-12, and a weathering test was conducted for 300 hours at 60°C and 0.8W @ 340nm. The film properties before and after the test were measured. The properties were the refractive index, film thickness, transmittance (average value from 400nm to 800nm), haze value, and YI value at a measurement wavelength of 589nm. The results are shown in Table 9. For refractive index, film thickness, and transmittance, the percentage change before and after the test was calculated using the following formula: Percentage change (%) = (Property value after weathering test - Property value before weathering test) ÷ (Property value before weathering test) × 100

[0212] As can be seen from Table 9, the rate of change before and after the weathering test is small, indicating that the film has excellent weather resistance.

[0213] According to the present invention, it is possible to provide an imprint material composition that can form a cured film having a high refractive index. Therefore, the present invention will greatly contribute to the development of manufacturing and related industries that require high-performance electronic devices and optical materials.

Claims

1. A low refractive index film made of hollow silica.

2. The low refractive index film according to claim 1, wherein the hollow silica is surface-modified with a silane coupling agent.

3. The low refractive index film according to claim 2, wherein the silane coupling agent has a crosslinkable double bond.

4. The low refractive index film according to claim 3, wherein at least a portion of the crosslinkable double bonds forms a crosslink.

5. The low refractive index film according to claim 2, wherein the silane coupling agent has an acrylic group.

6. The low refractive index film according to claim 1, wherein the hollow silica is modified on the surface with a group represented by the following formula 1. (In the formula, R represents a hydrogen atom or a methyl group, and * represents a bond.) 7. The low refractive index film according to claim 1, wherein the refractive index is 1.24 or less.

8. The low refractive index film according to claim 1, wherein the hollow silica has an average particle diameter of 30 nm or more and 90 nm or less.

9. The low refractive index film according to claim 1, having a film thickness of 40 nm or more and 10,000 nm or less.

10. A method for producing a low refractive index film according to claim 1, comprising the following steps: mixing the hollow silica, polymer, and additive to obtain a mixed solution; applying the mixed solution onto a substrate and obtaining a cured film by heating and / or light irradiation; and subjecting the cured film to a cleaning treatment.

11. The manufacturing method according to claim 10, wherein the washing treatment is PEGMEA washing, dry washing, or alkaline developing treatment.

12. The manufacturing method according to claim 10, wherein the polymer has a weight-average molecular weight of 1,000 or more and 15,000 or less.

13. The method for producing the polymer according to claim 12, wherein the polymer is a triazine ring-containing polymer as follows: comprising a repeating unit structure represented by the following formula (1), having at least one triazine ring end, and at least a portion of this triazine ring end being encapsulated with an amino group having a crosslinking group. (In the formula, R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an aralkyl group; Q represents a divalent group having 3 to 30 carbon atoms and a ring structure; and * represents a bond.) 14. The manufacturing method according to claim 13, wherein Q in formula (1) is represented by the following formulas (A), (B), or (C): (In the formula, * represents a bond).

15. The amino group having the crosslinking group is -NH-R １０２ , or the manufacturing method according to claim 13, represented by the following formula (1-4): (In the formula, R １０２ (where represents a crosslinking group, and * represents a bond).

16. The aforementioned R １０２ The manufacturing method according to claim 15, wherein the group is a hydroxyalkyl group, a (meth)acryloyloxyalkyl group, or a group represented by the following formula (1-5): (In the formula, A １ This represents an alkylene group with 1 to 10 carbon atoms, A ２ This is a single bond or the following formula (1-6) It represents a base represented by A ３ This represents an (a+1) valent aliphatic hydrocarbon group which may be substituted with a hydroxyl group, and A ４ (where represents a hydrogen atom or a methyl group, 'a' represents 1 or 2, and * represents a bond).

17. The aforementioned R １０２ The manufacturing method according to claim 15, wherein the group is selected from a hydroxymethyl group, a 2-hydroxyethyl group, a (meth)acryloyloxymethyl group, a (meth)acryloyloxyethyl group, and a group represented by the following formulas (1-5-1) to (1-5-4): (In the formula, * represents a bond).

18. A method for producing a low refractive index film according to claim 1, comprising the following steps: dispersing the hollow silica in a solvent to obtain a dispersion; coating the dispersion onto a substrate; and calcining the dispersion to volatilize the solvent.

19. A mixture for forming a low refractive index film according to claim 1, comprising at least hollow silica and a polymer.

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