Composition, cured film, structure, optical filter, solid-state image sensor, image display device, and method for manufacturing a cured film

Abstract

The present invention provides: a composition which contains particles each having a silanol group, at least one generator that is selected from the group consisting of an acid generator and a base generator, and a solvent, wherein the content of the particles each having a silanol group in the total solid content of the composition is 43% by mass or more; a cured film, a structure, an optical filer, a solid-state imaging element and an image display device, each of which uses the above-described composition; and a method for producing a cured film which uses the above-described composition.

Description

[Technical Field]

[0001] This invention relates to a composition containing particles. Furthermore, this invention relates to a cured film, a structure, an optical filter, a solid-state image sensor, an image display device, and a method for manufacturing a cured film. [Background technology]

[0002] Optical functional layers, such as low refractive index films, are applied to the surface of transparent substrates, for example, to prevent the reflection of incident light. Their applications are wide-ranging, and they are used in products in various fields, including display devices, optical instruments, building materials, observation equipment, and window glass. A wide variety of materials, both organic and inorganic, are used and are being developed for these applications. In particular, the development of materials for optical instruments has been progressing in recent years.

[0003] For example, optical functional layers applied to precision optical instruments such as image sensors require fine and precise processing and formability. Therefore, conventional vapor phase methods such as vacuum deposition and sputtering, which are suitable for microfabrication, have been employed. As for materials, single-layer films made of materials such as MgF2 and cryolite have been put into practical use. The application of metal oxides such as SiO2, TiO2, and ZrO2 is also being attempted.

[0004] On the other hand, vapor phase methods such as vacuum deposition and sputtering can result in high manufacturing costs due to the expensive processing equipment. In response to this, recent research has explored the use of compositions containing inorganic particles such as silica particles to manufacture optical functional layers, such as low refractive index films.

[0005] Patent Document 1 describes the production of an anti-reflective coating and the like using a composition containing hollow silica particles. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2014-034488 [Overview of the project] [Problems that the invention aims to solve]

[0007] In recent years, attempts have been made to form cured films on materials with low heat resistance. For example, recent display devices are increasingly using organic electroluminescence (EL). Organic semiconductor elements such as organic electroluminescent display elements are materials with low heat resistance, so when forming a cured film on such materials, it is desirable to form the cured film using a low-temperature process, for example, below 150°C, to suppress thermal damage to the support.

[0008] However, when a cured film is formed using a low-temperature process, the degree of curing of the film may be insufficient, and there was room for improvement in the moisture resistance of the cured film. Furthermore, according to the inventors' research, it was found that even with the composition described in Patent Document 1, there is room for further improvement in the moisture resistance of the resulting cured film.

[0009] Therefore, an object of the present invention is to provide a composition that can form a cured film with excellent moisture resistance. Furthermore, the present invention is to provide a cured film, a structure, an optical filter, a solid-state image sensor, an image display device, and a method for manufacturing a cured film. [Means for solving the problem]

[0010] The present invention provides the following: <1> Particles having a silanol group, At least one generating agent selected from the group consisting of acid generating agents and base generating agents, A composition comprising a solvent, A composition wherein the content of particles having the silanol group in the total solid content of the composition is 43% by mass or more. <2> The total content of particles having the silanol group and the generating agent in the total solid content of the above composition is 45 to 99% by mass. <1> The composition described above. <3> The particles having the silanol group described above are silica particles. <1> or <2> The composition described above. <4> The above-mentioned silica particles include at least one selected from the group consisting of silica particles in which a plurality of spherical silica particles are linked together in a bead-like manner, silica particles in which a plurality of spherical silica particles are linked together in a planar manner, and silica particles with a hollow structure. <3> The composition described above. <5> The above generating agent is an acid generating agent. The above acid generator includes a photoacid generator. <1> ~ <4> A composition as described in any one of the following. <6> The content of the photoacid generator in the total solid content of the above composition is 1 to 10% by mass. <5> The composition described above. <7> The above photoacid generator comprises at least one selected from the group consisting of oximesulfonate compounds and triazine compounds. <5> or <6> The composition described above. <8> The above generating agent is a base generating agent. The above base generator includes a photobase generator. <1> ~ <4> A composition as described in any one of the following. <9> The content of the photobase generator in the total solid content of the above composition is 1 to 10% by mass. <8> The composition described above. <10> The above photobase generator comprises at least one selected from the group consisting of carbamate compounds and acyloxime compounds. <8> or <9> The composition described above. <11> Furthermore, it contains silanol compounds with a molecular weight of 1000 or less. <1> ~ <10> A composition as described in any one of the following. <12> Furthermore, containing surfactants, <1> ~ <11> A composition as described in any one of the following. <13> Furthermore, the compound includes a compound having an alkoxysilyl group. <1> ~ <12> A composition as described in any one of the following. <14> The resin content in the total solids of the above composition is 30% by mass or less. <1> ~ <13> A composition as described in any one of the following. <15> A composition for forming a component adjacent to a pixel in an optical filter having multiple pixels. <1> ~ <14> A composition as described in any one of the following. <16> A composition for forming partitions, <1> ~ <15> A composition as described in any one of the following. <17> When the above composition is coated onto a silicon wafer and heated at 100°C for 5 minutes to form a film with a thickness of 0.4 μm, the refractive index of the above film at a wavelength of 633 nm is 1.4 or less. <1> ~ <16> A composition as described in any one of the following. <18> <1> ~ <17> A cured film obtained from any one of the compositions described in the following. <19> Support and Provided on the above support <1> ~ <17> A partition obtained from any one of the compositions described in, A structure having pixels provided in a region partitioned by the above-mentioned partition wall. <20> <18> An optical filter having the cured film described above. <21> <18> A solid-state image sensor having the cured film described above. <22> <18> An image display device having the cured film described above. <23> <1> ~ <17> A step of applying one of the compositions described in any one of the above onto a support to form a composition layer, The process includes curing the above composition layer, A method for producing a cured film, wherein the above composition layer is cured at a temperature of 150°C or lower throughout the entire process, The step of curing the above composition layer includes a step of generating an acid or a base from an acid generator or a base generator contained in the composition layer by irradiating the composition layer with light or heating it. A method for manufacturing a cured film. [Effects of the Invention]

[0011] According to the present invention, a composition capable of forming a cured film with excellent moisture resistance can be provided. Furthermore, the present invention can provide a cured film, a structure, an optical filter, a solid-state image sensor, an image display device, and a method for manufacturing a cured film. [Brief explanation of the drawing]

[0012] [Figure 1] This is a schematic, enlarged view showing silica particles in which multiple spherical silica particles are linked together in a bead-like structure. [Figure 2] This is a side cross-sectional view showing one embodiment of the structure of the present invention. [Figure 3] This is a plan view of the support structure as seen from directly above. [Modes for carrying out the invention]

[0013] The details of the present invention will be described in detail below. In this specification, "~" is used to mean that the numbers before and after it include the lower and upper limits, respectively. In this specification, when groups (atomic groups) are not specified as substituted or unsubstituted, the notation includes both groups (atomic groups) with and without substituents. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" refers to both acrylate and methacrylate, or either of them; "(meth)acrylic" refers to both acrylic and methacrylic, or either of them; and "(meth)acryloyl" refers to both acryloyl and methacryloyl, or either of them. In this specification, the weight-average molecular weight and number-average molecular weight are polystyrene-equivalent values ​​measured by GPC (gel permeation chromatography). In this specification, total solids refers to the total mass of the components of the composition excluding the solvent. In this specification, the term "process" includes not only independent processes but also any process that cannot be clearly distinguished from other processes, as long as its intended function is achieved.

[0014] <Composition> The composition of the present invention, Particles having a silanol group, At least one generating agent selected from the group consisting of acid generating agents and base generating agents, A composition comprising a solvent, The above composition is characterized in that the content of particles having the silanol group in the total solid content is 43% by mass or more.

[0015] According to the composition of the present invention, a cured film with excellent moisture resistance can be formed. In particular, even when the cured film is formed at a low temperature of 150°C or lower (preferably 120°C or lower), a cured film with excellent moisture resistance can be formed.

[0016] Although the detailed reasons for obtaining such effects are unknown, it is presumed that they are due to the following: Since the composition of the present invention contains at least one generating agent selected from the group consisting of acid generating agents and base generating agents, it is presumed that when energy such as light or heat is applied when forming a cured film using the composition of the present invention, an acid or base is generated from the generating agent, and this generated acid or base can promote the dehydration condensation reaction of particles having silanol groups. Furthermore, since the composition of the present invention contains 43% by mass or more of the above-mentioned particles having silanol groups in the total solid content of the composition, it is presumed that the proportion of silanol groups in the composition is high, and the dehydration condensation reaction of particles having silanol groups proceeds more easily. For these reasons, it is presumed that the composition of the present invention was able to form a cured film with excellent moisture resistance.

[0017] The viscosity of the composition of the present invention at 25°C is preferably 3.6 mPa·s or less, more preferably 3.4 mPa·s or less, and even more preferably 3.2 mPa·s or less. The lower limit is preferably 1.0 mPa·s or more, more preferably 1.4 mPa·s or more, and even more preferably 1.8 mPa·s or more.

[0018] The solid content concentration of the composition of the present invention is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 8% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 10% by mass or less.

[0019] The surface tension of the composition of the present invention at 25°C is preferably 27.0 mN / m or less, more preferably 26.0 mN / m or less, even more preferably 25.5 mN / m or less, and even more preferably 25.0 mN / m or less. The lower limit is preferably 20.0 mN / m or more, more preferably 21.0 mN / m or more, and even more preferably 22.0 mN / m or more.

[0020] When the composition of the present invention is applied to a glass substrate and heated at 100°C for 5 minutes to form a film with a thickness of 0.4 μm, the contact angle of the aforementioned film with respect to water at 25°C is preferably 20° or more, more preferably 25° or more, and even more preferably 30° or more, from the viewpoint of the stability of the composition. The upper limit is preferably 70° or less, more preferably 65° or less, and even more preferably 60° or less, from the viewpoint of the coatability of the composition. The above contact angles were measured using a contact angle meter (Kyowa Interface Science Co., Ltd., DM-701).

[0021] When the composition of the present invention is applied to a silicon wafer and heated at 100°C for 5 minutes to form a film with a thickness of 0.4 μm, the refractive index of the aforementioned film at a wavelength of 633 nm is preferably 1.45 or less, more preferably 1.4 or less, even more preferably 1.35 or less, even more preferably 1.3 or less, and even more preferably 1.27 or less. There is no particular lower limit, but it can be 1.15 or more. The above refractive index is the value measured using an ellipsometer (manufactured by JA Woolam, VUV-vase [product name]). The measurement temperature is 25°C.

[0022] The composition of the present invention can be used in optical functional layers in image display devices and solid-state image sensors. Examples of optical functional layers include anti-reflective layers, low refractive index layers, and waveguides.

[0023] Furthermore, the composition of the present invention can also be used as a composition for forming members adjacent to pixels in an optical filter having a plurality of pixels. Examples of such members include partitions for separating pixels of an optical filter. That is, the composition of the present invention can be preferably used as a composition for forming partitions. Examples of pixels partitioned by partitions include colored pixels, transparent pixels, pixels of the near-infrared transmission filter layer, and pixels of the near-infrared cut filter layer. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. Furthermore, the above-mentioned component may be used by placing it on the light incident side or the light emission side of the optical filter. In this specification, the term "adjacent to a pixel" is not limited to cases where the component and the pixel are in contact, but also includes cases where another layer is interposed between the component and the pixel.

[0024] Furthermore, the composition of the present invention may be used to form a cured film on the microlenses of a solid-state image sensor or an image display device having microlenses.

[0025] The following describes each component used in the composition of the present invention.

[0026] <<Particles containing silanol groups>> The composition of the present invention contains particles having a silanol group (hereinafter also referred to as specific particles).

[0027] The specific particles are preferably those that are poorly soluble in water.

[0028] Silica particles can be cited as one form of specific particles.

[0029] Furthermore, other forms of specific particles include surface-treated particles obtained by surface-treating inorganic particles or resin particles with a silanol compound. Methods for surface treatment with silanol compounds include the sol-gel method and silane coupling treatment. In the case of surface-treated particles, the total mass of the inorganic particles or resin particles being treated with the silanol compound, and the silanol compound adhering to the surface of the treated material, constitutes the mass of the particles containing silanol groups. Examples of the inorganic particles mentioned above include titanium oxide particles, strontium titanate particles, barium titanate particles, zinc oxide particles, magnesium oxide particles, zirconium oxide particles, aluminum oxide particles, barium sulfate particles, aluminum hydroxide particles, calcium silicate particles, aluminum silicate particles, and zinc sulfide particles. Examples of resin particles include (meth)acrylic resin particles, epoxy resin particles, polycarbonate resin particles, polyether resin particles, polyimide resin particles, polyamide resin particles, polyolefin resin particles, cyclic olefin resin particles, polyester resin particles, styrene resin particles, fluororesin particles, and siloxane resin particles. Examples of silanol compounds used for surface treatment include monosilanol compounds such as trimethylsilanol, triethylsilanol, phenyldimethylsilanol, diphenylmethylsilanol, triphenylsilanol, and dihydroxydiphenylsilane (diphenyldisilanol). The content of the silanol compound in the surface-treated particles is preferably 0.1 to 30% by mass. The lower limit is preferably 1% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 20% by mass or less, and more preferably 15% by mass or less.

[0030] The specific particles are preferably silica particles because they have excellent moisture resistance and readily form a hardened film with a low refractive index.

[0031] Examples of silica particles include silica particles in which multiple spherical silica particles are linked together in a bead-like structure, silica particles in which multiple spherical silica particles are linked together in a planar structure, silica particles with a hollow structure, and solid silica particles. The silica particles are preferably at least one selected from the group consisting of silica particles in the shape of multiple spherical silica connected in a bead-like manner, silica particles in the shape of multiple spherical silica connected in a planar manner, and silica particles with a hollow structure, for the reasons that they have better moisture resistance and are more likely to form a cured film with a lower refractive index. Hereinafter, silica particles in which multiple spherical silica particles are linked together in a bead-like structure, and silica particles in which multiple spherical silica particles are linked together in a planar structure, will both be referred to as bead-like silica. Note that silica particles in which multiple spherical silica particles are linked together in a bead-like structure may also have a shape in which multiple spherical silica particles are linked together in a planar structure. Furthermore, hollow silica particles are silica particles that have cavities inside. Hereafter, hollow silica particles will also be referred to as hollow silica. Furthermore, solid silica particles refer to silica particles that do not have internal cavities.

[0032] Furthermore, it is preferable that the silica particles are treated with a hydrophobic agent that reacts with some of the silanol groups on the surface of the silica particles. As the hydrophobic agent, a compound is used that has a structure that reacts with the silanol groups on the surface of the silica particles (preferably a structure that undergoes a coupling reaction with the silanol groups on the surface of the silica particles) and improves the hydrophobicity of the silica particles. The hydrophobic agent is preferably an organic compound. Specific examples of hydrophobic agents include organic silane compounds, organic titanium compounds, organic zirconium compounds, and organic aluminum compounds, with organic silane compounds being more preferable because they can suppress an increase in refractive index. When the surface of silica particles is treated with a surface treatment agent such as a hydrophobic agent, the total mass of the silica particles and the surface treatment agent attached to the silica particles is considered to be the mass of the particles having silanol groups.

[0033] In this specification, "spherical" in "spherical silica" means that it is sufficient if it is substantially spherical, and it may be deformed as long as it does not produce the effects of the present invention. For example, it includes shapes with irregularities on the surface and flattened shapes with a long axis in a predetermined direction. Furthermore, "multiple spherical silicas linked together in a bead-like manner" means a structure in which multiple spherical silicas are connected to each other in a linear and / or branched manner. For example, as shown in Figure 1, a structure in which multiple spherical silicas 1 are connected to each other by a joint 2 with a smaller outer diameter is included. Furthermore, in the present invention, the structure "multiple spherical silicas linked together in a bead-like manner" includes not only structures that are connected in a ring shape, but also structures that are in a chain shape with ends. Furthermore, "multiple spherical silicas linked in a planar manner" means a structure in which multiple spherical silicas are connected to each other on substantially the same plane. Furthermore, "substantially the same plane" means not only that they are on the same plane, but that they may be offset vertically from the same plane. For example, they may be offset vertically within a range of 50% or less of the particle diameter of the spherical silicas.

[0034] For bead-shaped silica, it is preferable that the ratio D1 / D2 between the average particle diameter D1 measured by dynamic light scattering and the average particle diameter D2 obtained by the following formula (1) is 3 or greater. There is no particular upper limit to D1 / D2, but it is preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less. By setting D1 / D2 within this range, good optical properties can be achieved. The value of D1 / D2 in bead-shaped silica is also an indicator of the degree of connectivity of the spherical silica. D2 = 2720 / S ... (1) In the formula, D2 is the average particle diameter of beaded silica, in units of nm, and S is the specific surface area of ​​beaded silica measured by the nitrogen adsorption method, in units of m 2 It is / g.

[0035] The average particle diameter D2 of the bead-shaped silica can be considered as an average particle diameter that approximates the diameter of the primary particles of the spherical silica. The average particle diameter D2 is preferably 1 nm or more, more preferably 3 nm or more, even more preferably 5 nm or more, and particularly preferably 7 nm or more. As an upper limit, it is preferably 100 nm or less, more preferably 80 nm or less, even more preferably 70 nm or less, even more preferably 60 nm or less, and particularly preferably 50 nm or less.

[0036] The average particle diameter D2 can be substituted with the equivalent diameter (D0) of the spherical portion in the projection image measured by a transmission electron microscope (TEM). Unless otherwise specified, the average particle diameter based on the equivalent diameter is evaluated using the number average of 50 or more particles.

[0037] The average particle diameter D1 of the bead-like silica can be considered as the number-average particle diameter of secondary particles formed by the aggregation of multiple spherical silica particles. Therefore, the relationship D1 > D2 usually holds. The average particle diameter D1 is preferably 5 nm or more, more preferably 7 nm or more, and particularly preferably 10 nm or more. As an upper limit, it is preferably 100 nm or less, more preferably 70 nm or less, even more preferably 50 nm or less, and particularly preferably 45 nm or less.

[0038] Unless otherwise specified, the measurement of the average particle size D1 of bead-shaped silica is performed using a dynamic light scattering particle size distribution analyzer (Microtrac UPA-EX150, manufactured by Nikkiso Co., Ltd.). The procedure is as follows: A 20 ml sample vial is filled with a dispersion of bead-shaped silica and diluted with propylene glycol monomethyl ether to a solid content concentration of 0.2% by mass. The diluted sample solution is irradiated with 40 kHz ultrasound for 1 minute and used for testing immediately thereafter. Data is acquired 10 times using a 2 ml quartz cell at a temperature of 25°C, and the resulting "number mean" is taken as the average particle size. For other detailed conditions, refer to JIS Z 8828:2013 "Particle size analysis - Dynamic light scattering method" as needed. Five samples are prepared for each level, and their average value is adopted.

[0039] The bead-like silica preferably consists of multiple spherical silica particles with an average particle diameter of 1 to 80 nm linked together via a connecting material. The upper limit of the average particle diameter of the spherical silica is preferably 70 nm or less, more preferably 60 nm or less, and even more preferably 50 nm or less. The lower limit of the average particle diameter of the spherical silica is preferably 3 nm or more, more preferably 5 nm or more, and even more preferably 7 nm or more. In this invention, the value of the average particle diameter of the spherical silica is determined from the equivalent diameter of the circle in the projection image of the spherical portion measured by a transmission electron microscope (TEM).

[0040] In bead-like silica, a metal oxide-containing silica can be used as a linking material to connect the spherical silica particles. Examples of metal oxides include oxides of metals selected from Ca, Mg, Sr, Ba, Zn, Sn, Pb, Ni, Co, Fe, Al, In, Y, and Ti. Examples of metal oxide-containing silica include reaction products and mixtures of these metal oxides with silica (SiO2). For details on linking materials, refer to the description in International Publication No. 2000 / 015552, which is incorporated herein by reference.

[0041] In bead-like silica, the number of linked spherical silica atoms is preferably 3 or more, more preferably 5 or more. The upper limit is preferably 1000 or less, more preferably 800 or less, and even more preferably 500 or less. The number of linked spherical silica atoms can be measured by TEM.

[0042] Commercially available particulate liquids containing bead-like silica include the Snowtex series and Organo Silica Sol series (methanol dispersion, isopropyl alcohol dispersion, ethylene glycol dispersion, methyl ethyl ketone dispersion, etc., product numbers IPA-ST-UP, MEK-ST-UP, etc.) manufactured by Nissan Chemical Industries, Ltd. Alternatively, silica sols described in, for example, Japanese Patent Publication No. 4328935 can be used as particulate liquids containing bead-like silica.

[0043] The average particle size of hollow silica is preferably 10 to 500 nm. The lower limit is preferably 15 nm or more, more preferably 20 nm or more, and even more preferably 25 nm or more. The upper limit is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less. The average particle size of hollow silica is the value measured by dynamic light scattering. A commercially available particulate liquid containing hollow silica is JGC Catalysts & Chemicals Ltd.'s Thru-Ria 4110, among others.

[0044] The average particle size of the solid silica particles is preferably 5 to 500 nm. The lower limit is preferably 10 nm or more. The upper limit is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less. The average particle size of the solid silica particles is the value measured by dynamic light scattering. A commercially available particle liquid containing solid silica particles is MIBK-ST manufactured by Nissan Chemical Industries, Ltd.

[0045] The content of specific particles in the total solid content of the composition is 43% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 95% by mass or less. Furthermore, the content of specific particles in the composition is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 7% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0046] When silica particles are used as the specific particles, the content of the specific particles in the total solid content of the composition is preferably 43% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 95% by mass or less. Furthermore, the silica particle content in the composition is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 7% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. If the silica particle content is within the above range, a cured film with a low refractive index, high anti-reflective effect, and excellent moisture resistance is easily obtained.

[0047] Furthermore, for reasons such as the ease of obtaining a cured film with a low refractive index, high anti-reflective effect, and excellent moisture resistance, the silica particle content in the total amount of particles in the composition is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more. It is preferable that the particles in the composition consist substantially only of silica particles. When the particles in the composition consist substantially only of silica particles, this means that the silica particle content in the total amount of particles is 99% by mass or more, more preferably 99.9% by mass or more, and even more preferably entirely of silica particles.

[0048] <<Generating agent>> The composition of the present invention comprises at least one generating agent selected from the group consisting of acid generating agents and base generating agents. Preferably, the generating agent is substantially acid generating agent only, or substantially base generating agent only, and is preferably substantially base generating agent only from the viewpoint of suppressing damage to films and suppressing corrosion of metal components, etc. In this specification, when the generating agent is substantially composed of an acid generating agent, it means that the content of the acid generating agent in the total mass of the generating agent is 99% by mass or more, preferably 99.9% by mass or more, and more preferably 100% by mass (consisting solely of an acid generating agent). Furthermore, when the generating agent is substantially composed of a base generating agent, it means that the content of the base generating agent in the total mass of the generating agent is 99% by mass or more, preferably 99.9% by mass or more, and more preferably 100% by mass (consisting solely of a base generating agent).

[0049] (Acid generator) Examples of acid generators include thermal acid generators and photoacid generators. It is preferable that the acid generator contains a photoacid generator. Alternatively, the acid generator may consist of both a photoacid generator and a thermal acid generator. When using both, the mass ratio of the thermal acid generator to the photoacid generator is preferably 100 to 2000 parts by mass of the photoacid generator per 100 parts by mass of the thermal acid generator. The lower limit is preferably 150 parts by mass or more, and more preferably 200 parts by mass or more. The upper limit is preferably 1500 parts by mass or less, and more preferably 1000 parts by mass or less. In particular, it is especially preferable that the acid generator consists substantially only of a photoacid generator, as this allows for lower process temperatures and the formation of a film with excellent moisture resistance. In this specification, when the acid generator is substantially composed of a photoacid generator, it means that the content of the photoacid generator in the total mass of the acid generator is 99% by mass or more, preferably 99.9% by mass or more, and more preferably 100% by mass (consisting solely of the photoacid generator). In this specification, "acid generator" refers to a compound that generates acid when energy such as heat or light is applied. Furthermore, "thermal acid generator" refers to a compound that generates acid through thermal decomposition. Finally, "photoacid generator" refers to a compound that generates acid through light irradiation.

[0050] The acid generator may be an ionic acid generator or a nonionic acid generator, but a nonionic acid generator is preferred. When a nonionic acid generator is used as the acid generator, malfunctions caused by ionic impurities in solid-state image sensors and image display devices can be reduced when the composition of the present invention is used in these devices.

[0051] The acid generator is preferably a compound that generates an acid with a pKa of 4 or less, more preferably a compound that generates an acid with a pKa of 3 or less, and even more preferably a compound that generates an acid with a pKa of 2 or less. This embodiment makes it easier to form a cured film with better moisture resistance. In this specification, pKa basically refers to the pKa in water at 25°C. If it cannot be measured in water, it refers to the pKa measured after changing to a solvent suitable for measurement. Specifically, the pKa listed in chemical handbooks, etc. can be used as a reference. As for the acid with a pKa of 3 or less, it is preferably a sulfonic acid or a phosphonic acid, and more preferably a sulfonic acid.

[0052] The molecular weight of the acid generator is preferably 200 to 1000. The lower limit is preferably 230 or higher, and the upper limit is preferably 800 or lower. If the molecular weight of the acid generator is within the above range, the acid generator can be easily volatilized during baking or other processes in the production of the cured film, and the residue of the acid generator or its decomposition products in the film can be suppressed.

[0053] -Hot acid generator- The acid generation temperature of the thermal acid generator is preferably 80°C to 130°C, and more preferably 90°C to 110°C.

[0054] The thermal acid generator is preferably a compound that generates low nucleophilic acids such as sulfonic acids, carboxylic acids, and disulfonylimides upon heating. Acids with a pKa of 4 or less are preferred, those with a pKa of 3 or less are more preferred, and those with a pKa of 2 or less are even more preferred. For example, sulfonic acids, alkylcarboxylic acids, arylcarboxylic acids, and disulfonylimides substituted with electron-withdrawing groups are preferred. Examples of electron-withdrawing groups include halogen atoms such as fluorine atoms, haloalkyl groups such as trifluoromethyl groups, nitro groups, and cyano groups.

[0055] Examples of thermal acid generators include diazomethane compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, phosphate ester compounds, sulfonimide compounds, sulfonbenzotriazole compounds, and sulfonium salts, with sulfonic acid ester compounds and sulfonimide compounds being preferred.

[0056] Furthermore, it is preferable that the thermal acid generator is a sulfonic acid ester compound that does not substantially generate acid upon irradiation with active light or radiation, but generates acid upon heat. The fact that it does not substantially generate acid upon irradiation with active light or radiation can be determined by measuring the infrared absorption (IR) spectrum and nuclear magnetic resonance (NMR) spectrum of the compound before and after exposure, by checking that there is no change in the spectrum. The molecular weight of the above sulfonic acid ester compound is preferably 230 to 1,000, and more preferably 230 to 800.

[0057] Examples of sulfonic acid ester compounds include tetraethylene glycol bis(p-toluenesulfonate), butyl p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenyldimethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenylbenzylmethylsulfonium trifluoromethanesulfonate, 4-(methoxycarbonyloxy)phenyldimethylsulfonium trifluoromethanesulfonate, and benzyl-4-(methoxycarbonyloxy)phenylmethylsulfonium trifluoromethanesulfonate.

[0058] Examples of sulfonimide compounds include N-(trifluoromethylsulfonyloxy)succinimide (trade name "SI-105", Midori Chemical Co., Ltd.), N-(camphasulfonyloxy)succinimide (trade name "SI-106", Midori Chemical Co., Ltd.), N-(4-methylphenylsulfonyloxy)succinimide (trade name "SI-101", Midori Chemical Co., Ltd.), N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, and N-(trifluoromethyls (Phthalimide) Phthalimide, N-(Camphasulfonyloxy) Phthalimide, N-(2-Trifluoromethylphenylsulfonyloxy) Phthalimide, N-(2-Fluorophenylsulfonyloxy) Phthalimide, N-(Trifluoromethylsulfonyloxy) Diphenylmaleimide (Trade name "PI-105", Midori Chemical Co., Ltd.), N-(Camphasulfonyloxy) Diphenylmaleimide, 4-Methylphenylsulfonyloxy) Diphenylmaleimide, N-(2-Trifluoromethylphenylsulfonyloxy) Diphenyl Lumaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(phenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxilimide (trade name "NDI-100", Midori Chemical Co., Ltd.), N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxilimide (trade name "NDI-101", Midori Chemical Co., Ltd.), N-(trifluoromethanesulfonyl Oxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxilimide (trade name "NDI-105", Midori Chemical Co., Ltd.), N-(nonafluorobutanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxilimide (trade name "NDI-109", Midori Chemical Co., Ltd.), N-(camphasulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxilimide (trade name "NDI-106", Midori Chemical Co., Ltd.), N-(camphasulfonyloxy)-7-oxabicyclo[2.2.1]Hepto-5-ene-2,3-dicarboxilimide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]Hepto-5-ene-2,3-dicarboxilimide, N-(4-methylphenylsulfonyloxy)-bicyclo[2.2.1]Hepto-5-ene-2,3-dicarboxilimide, N-(4-methylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]Hepto-5-ene-2,3-dicarboxilimide, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]Hepto-5-ene-2,3-dicarboxilimide, N-(4-fluorophenylsulfonyloxy)-bicyclo[2 .2.1]Hepto-5-ene-2,3-dicarboxilimide, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]Hepto-5-ene-2,3-dicarboxilimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]Heptane-5,6-oxy-2,3-dicarboxilimide, N-(camphasulfonyloxy)bicyclo[2.2.1]Heptane-5,6-oxy-2,3-dicarboxilimide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]Heptane-5,6-oxy-2,3-dicarboxilimide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]Heptane-5,6-oxy-2,3-dicarboxilimide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1] Heptane-5,6-oxy-2,3-dicarboxilimide, N-(trifluoromethylsulfonyloxy)naphthyldicarboxilimide (product name "NAI-105", Midori Chemical Co., Ltd.), N-(camphasulfonyloxy)naphthyldicarboxilimide (product name "NAI-106", Midori Chemical Co., Ltd.), N-(4-methylphenylsulfonyloxy)naphthyldicarboxilimide (product name "NAI-101", Midori Chemical Co., Ltd.), N-(phenylsulfonyloxy)naphthyldicarboxilimide (product name "NAI-100", Midori Chemical Co., Ltd.), N-(2-trifluoromethylphenylsulfonyloxy)naphthyldicarboxilimide, N-(4-fluorophenylsulfonyloxy)naphthyldicarboxilimide, N-(pentafluoroethylsulfonyloxy)naphthyldicarboxilimide, N- Examples include (heptafluoropropylsulfonyloxy)naphthyldicarboxylimide, N-(nonafluorobutylsulfonyloxy)naphthyldicarboxylimide (trade name "NAI-109", Midori Chemical Co., Ltd.), N-(ethylsulfonyloxy)naphthyldicarboxylimide, N-(propylsulfonyloxy)naphthyldicarboxylimide, N-(butylsulfonyloxy)naphthyldicarboxylimide (trade name "NAI-1004", Midori Chemical Co., Ltd.), N-(pentylsulfonyloxy)naphthyldicarboxylimide, N-(hexylsulfonyloxy)naphthyldicarboxylimide, N-(heptylsulfonyloxy)naphthyldicarboxylimide, N-(octylsulfonyloxy)naphthyldicarboxylimide, and N-(nonylsulfonyloxy)naphthyldicarboxylimide.

[0059] Commercially available thermal acid generators include the San-Aid series from Sanshin Chemical Industry Co., Ltd. (e.g., SI-60, SI-80, SI-100, SI-200, SI-110, SI-145, SI-150, SI-60L, SI-80L, SI-100L, SI-110L, SI-145L, SI-150L, ​​SI-160L, SI-180L, etc.), the TA-100 series from Sunapro Co., Ltd., and the IK series from Sunapro Co., Ltd.

[0060] -Photoacid Generator- The photoacid generator is preferably a compound that reacts to active light with a wavelength of 300 nm or more, more preferably 300 to 450 nm, and generates acid. The photoacid generator is preferably a compound that generates an acid with a pKa of 4 or less upon light irradiation, more preferably a compound that generates an acid with a pKa of 3 or less, and even more preferably a compound that generates an acid with a pKa of 2 or less. Furthermore, the photoacid generator is preferably a compound that does not generate acid at temperatures below 130°C.

[0061] Examples of photoacid generators include oxime sulfonate compounds, triazine compounds, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, iminosulfonic acid ester compounds, carboxylic acid ester compounds, and sulfonimide compounds. From the viewpoint of acid generation efficiency and solubility upon exposure, it is preferable to use at least one selected from the group consisting of oxime sulfonate compounds and triazine compounds.

[0062] The oxime sulfonate compound is preferably a compound containing an oxime sulfonate structure represented by formula (B1-1).

[0063] Formula (B1-1) [ka] R in equation (B1-1) 21 The hyphen represents an alkyl or aryl group. The wavy line indicates a bond with another group.

[0064] R 21 The alkyl group represented is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. R 21 The aryl group represented is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. 21 The aryl group may be substituted with a fluorine atom, an alkyl group, an alkoxy group, or a halogen atom. R21 The alkyl and aryl groups represented by may have substituents. Examples of substituents include halogen atoms, aryl groups having 6 to 11 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and cyclic alkyl groups (including bridged alicyclic groups such as 7,7-dimethyl-2-oxonorbornyl groups, preferably bicycloalkyl groups, etc.). Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred.

[0065] Compounds containing an oximesulfonate structure represented by formula (B1-1) include the oximesulfonate compounds described in paragraphs 0081 to 0108 of Japanese Patent Publication No. 2013-210616, the contents of which are incorporated herein by reference.

[0066] Specific examples of oxime sulfonate compounds include compounds with the structures described in the examples below.

[0067] Examples of triazine compounds include compounds with the structures described in the examples below, 2-(3-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methylthiophenyl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxy-β-styryl)-bis(4,6-trichloromethyl)-s-triazine, and 2-piperonyl-bis(4,6-trichloromethyl) Examples include methyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-bis(4,6-trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-bis(4,6-trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-bis(4,6-trichloromethyl)-s-triazine, and 2-(4-methoxynaphthyl)-bis(4,6-trichloromethyl)-s-triazine.

[0068] Examples of iodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl,4-(2'-hydroxy-1'-tetradecoxy)phenyliodonium trifluoromethanesulfonate, 4-(2'-hydroxy-1'-tetradecoxy)phenyliodonium hexafluoroantimonate, and phenyl,4-(2'-hydroxy-1'-tetradecoxy)phenyliodonium-p-toluenesulfonate.

[0069] Examples of sulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, and 4-phenylthiophenyldiphenylsulfonium trifluoroacetate.

[0070] Examples of quaternary ammonium salts include tetramethylammonium butyltris(2,6-difluorophenyl) borate, tetramethylammonium hexyltris(p-chlorophenyl) borate, tetramethylammonium hexyltris(3-trifluoromethylphenyl) borate, benzyldimethylphenylammonium butyltris(2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris(p-chlorophenyl) borate, and benzyldimethylphenylammonium hexyltris(3-trifluoromethylphenyl) borate.

[0071] Examples of diazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(4-tolylsulfonyl)diazomethane, bis(2,4-xylylsulfonyl)diazomethane, bis(4-chlorophenylsulfonyl)diazomethane, methylsulfonyl-4-tolylsulfonyldiazomethane, cyclohexylsulfonyl(1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, and phenylsulfonyl(benzoyl)diazomethane.

[0072] Examples of sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, and diaryldisulfone compounds. Preferred sulfone compounds include 4-tolylphenacylsulfone, mesitylphenacylsulfone, bis(phenylsulfonyl)methane, and 4-chlorophenyl-4-tolyldisulfone compounds.

[0073] Examples of sulfonic acid ester compounds include benzoin-4-tolylsulfonate, pyrogalloltris(methylsulfonate), nitrobenzyl-9,10-diethoxyanthuryl-2-sulfonate, and 2,6-(dinitrobenzyl)phenylulfonate.

[0074] Examples of iminosulfonic acid ester compounds include benzylmonoxime-4-tolylsulfonate, benzylmonoxime-4-dodecylphenylsulfonate, benzylmonoxime-hexadecylsulfonate, 4-nitroacetophenoneoxime-4-tolylsulfonate, 4,4'-dimethylbenzylmonoxime-4-tolylsulfonate, 4,4'-dimethylbenzylmonoxime-4-dodecylphenylsulfonate, dibenzylketoneoxime-4-tolylsulfonate, α-(4-tolyloxy)imino-α-cyanoethyl acetate, furylmonoxime-4-(aminocarbonyl)phenylsulfonate, and acetoneoxime-4-benzoylphenylsulfonate. Examples include 3-(benzylsulfonyloxy)iminoacetylacetone, bis(benzylmonoxide)dioctylnaphthyldisulfonate, α-(4-tolylsulfonyloxy)iminobenzylcyanide, α-(4-tolylsulfonyloxy)imino-4-methoxybenzylcyanide ("PAI-101", trade name, manufactured by Midori Chemical Co., Ltd.), α-(10-camphorsulfonyloxy)imino-4-methoxybenzylcyanide ("PAI-106", trade name, manufactured by Midori Chemical Co., Ltd.), and 5-(4-tolylsulfonyloxy)imino-5H-thiophene-2-ylidene-(2-methylphenyl)acetonitrile ("CGI-1311", trade name, manufactured by BASF).

[0075] Examples of carboxylic acid ester compounds include 2-nitrobenzyl carboxylic acid esters.

[0076] Examples of sulfonimide compounds include N-(trifluoromethylsulfonyloxy)succinimide, N-(10-camphorsulfonyloxy)succinimide, N-(4-tolylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(10-camphorsulfonyloxy)phthalimide, and N-(2-trifluoromethylphenylsulfonyloxy) N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(10-camphorsulfonyloxy)diphenylmaleimide, N-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(trifluoromethyl N-(10-camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(4-tolylsulfonyloxy)bicyclo[2.2 .1]Hepto-5-ene-2,3-dicarboximide, N-(4-tolylsulfonyloxy)-7-oxabicyclo[2.2.1]Hepto-5-ene-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]Hepto-5-ene-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]Hepto-5-ene-2,3-dicarboximide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]Hepto-5-ene-2,3-dicarboximide, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]Hepto-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]Heptan-5,6-oxy-2,3-dicarboximide, N-(10-camphorsulfonyloxy)bicyclo[2.2.1]Heptan-5,6-oxy-2,3-dicarboximide, N-(4-tolylsulfonyloxy)bicyclo[2. 2.1]Heptane-5,6-oxy-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]Heptane-5,6-oxy-2,3-dicarboximide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]Heptane-5,6-oxy-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)naphthyldicarboximide, N-(10-camphorsulfonyloxy)naphthyldicarboximide, N-(4 Examples include N-(tolylsulfonyloxy)naphthyldicarboxyimide, N-(2-trifluoromethylphenylsulfonyloxy)naphthyldicarboxyimide, N-(4-fluorophenylsulfonyloxy)naphthyldicarboxyimide, N-(pentafluoroethylsulfonyloxy)naphthyldicarboxyimide, N-(heptafluoropropylsulfonyloxy)naphthyldicarboxyimide, N-(nonafluorobutylsulfonyloxy)naphthyldicarboxyimide, N-(ethylsulfonyloxy)naphthyldicarboxyimide, N-(propylsulfonyloxy)naphthyldicarboxyimide, N-(butylsulfonyloxy)naphthyldicarboxyimide, N-(pentylsulfonyloxy)naphthyldicarboxyimide, N-(hexylsulfonyloxy)naphthyldicarboxyimide, N-(heptylsulfonyloxy)naphthyldicarboxyimide, N-(octylsulfonyloxy)naphthyldicarboxyimide, and N-(nonylsulfonyloxy)naphthyldicarboxyimide.

[0077] (Base generator) Examples of base generators include thermal base generators and photobase generators. It is preferable that the base generator contains a photobase generator. Alternatively, the base generator may consist of both a photobase generator and a thermal base generator. When using both, the mass ratio of the thermal base generator to the photobase generator is preferably 100 to 2000 parts by mass of the photobase generator per 100 parts by mass of the thermal base generator. The lower limit is preferably 150 parts by mass or more, and more preferably 200 parts by mass or more. The upper limit is preferably 1500 parts by mass or less, and more preferably 1000 parts by mass or less. In particular, it is especially preferable that the base generator consists substantially of a photobase generator, as this allows for lower process temperatures and the formation of a film with excellent moisture resistance. In this specification, when the base generator is substantially composed of a photobase generator, it means that the content of the photobase generator in the total mass of the base generator is 99% by mass or more, preferably 99.9% by mass or more, and more preferably 100% by mass (consisting solely of the photobase generator). In this specification, a base-generating agent refers to a compound that generates a base when energy such as heat or light is applied. A thermal base-generating agent refers to a compound that generates a base by thermal decomposition. A photobase-generating agent refers to a compound that generates a base by light irradiation.

[0078] The base generator may be an ionic base generator or a nonionic base generator, but a nonionic base generator is preferred. When a nonionic base generator is used as the acid generator, malfunctions caused by ionic impurities in solid-state image sensors and image display devices can be reduced when the composition of the present invention is used in these devices.

[0079] The base generated from the base generator may be a primary, secondary, or tertiary amine, but a tertiary amine is preferred from the viewpoint of pot life stability. The boiling point of the base generated by the base generator is preferably 80°C or higher, preferably 100°C or higher, and most preferably 140°C or higher. The molecular weight of the generated base is preferably 80 to 2000, more preferably 100 or higher, and more preferably 500 or lower. Note that the molecular weight values ​​are theoretical values ​​obtained from the structural formula.

[0080] The molecular weight of the base generator is preferably 200 to 1000. The lower limit is preferably 230 or higher, and the upper limit is preferably 800 or lower. If the molecular weight of the base generator is within the above range, the base generator can be easily volatilized during baking or other processes in the production of the cured film, and the residue of the base generator or its decomposition products in the film can be suppressed.

[0081] -Thermobase generator- The base generation temperature of the thermal base generator is preferably 80°C to 130°C, and more preferably 90°C to 110°C.

[0082] Examples of thermal base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole compounds, amineimide compounds, pyridine compounds, α-aminoacetophenone compounds, quaternary ammonium salts, pyridinium salts, α-lactone ring derivative compounds, amineimide compounds, phthalimide compounds, and acyloxyimino compounds.

[0083] Furthermore, as a thermobase generator, acidic compounds that generate a base when heated above 40°C, and ammonium salts having an anion with a pKa1 of 0 to 4 and an ammonium cation can also be used. Examples of such compounds are those described in paragraphs 0045 to 0066 of International Publication No. 2017 / 141723, which are incorporated herein by reference. In this specification, an acidic compound refers to a compound in which 1 g of the compound is placed in a container, 50 mL of a mixture of deionized water and tetrahydrofuran (mass ratio of water / tetrahydrofuran = 1 / 4) is added, and the mixture is stirred at room temperature for 1 hour. The pH of the resulting solution is measured at 20°C using a pH meter and the value is less than 7.

[0084] Examples of commercially available thermal base generators include the U-CAT series manufactured by Sunapro Co., Ltd. (e.g., SA1, SA102, SA603, SA810, SA831, SA841, SA851, SA838A, etc.).

[0085] -Photobase Generator- The photobase generator is preferably a compound that reacts to active light with a wavelength of 300 nm or more, more preferably 300 to 450 nm, and generates a base. Furthermore, the photobase generator is preferably a compound that does not generate bases at temperatures below 130°C.

[0086] Examples of photobase generators include carbamate compounds, sulfonamide compounds, and acyloxime compounds, and it is preferable that the photobase generator be at least one selected from the group consisting of carbamate compounds and acyloxime compounds.

[0087] Examples of carbamate compounds include N-(2-nitrobenzyloxy)carbonyl-N-methylamine, N-(2-nitrobenzyloxy)carbonyl-Nn-propylamine, N-(2-nitrobenzyloxy)carbonyl-Nn-hexylamine, N-(2-nitrobenzyloxy)carbonyl-N-cyclohexylamine, N-(2-nitrobenzyloxy)carbonylaniline, N-(2-nitrobenzyloxy)carbonylpiperidine, N,N'-bis[(2-nitrobenzyloxy)carbonyl]-1,6-hexamethylenediamine, N,N '-Bis[(2-nitrobenzyloxy)carbonyl]-1,4-phenylenediamine, N,N'-Bis[(2-nitrobenzyloxy)carbonyl]-2,4-tolylenediamine, N,N'-Bis[(2-nitrobenzyloxy)carbonyl]-4,4'-diaminodiphenylmethane, N,N'-Bis[(2-nitrobenzyloxy)carbonyl]piperazine, N-(2,6-dinitrobenzyloxy)carbonyl-N-methylamine, N-(2,6-dinitrobenzyloxy)carbonyl-Nn-propylamine, N-(2,6-dinitrobenz N,N'-(2,6-dinitrobenzyloxy)carbonyl-N-hexylamine, N-(2,6-dinitrobenzyloxy)carbonylaniline, N-(2,6-dinitrobenzyloxy)carbonylpiperidine, N,N'-bis[(2,6-dinitrobenzyloxy)carbonyl]-1,6-hexamethylenediamine, N,N'-bis[(2,6-dinitrobenzyloxy)carbonyl]-1,4-phenylenediamine, N,N'-bis[(2,6-dinitrobenzyloxy)carbonyl]-2, 4-Tolylenediamine, N,N'-bis[(2,6-dinitrobenzyloxy)carbonyl]-4,4-diaminodiphenylmethane, N,N'-bis[(2,6-dinitrobenzyloxy)carbonyl]piperazine, N-(α,α-dimethyl-3,5-dimethoxybenzyloxy)carbonyl-N-methylamine, N-(α,α-dimethyl-3,5-dimethoxybenzyloxy)carbonyl-Nn-propylamine, N-(α,α-dimethyl-3,5-dimethoxybenzyloxy)carbonyl-Nn-hexylamine, N-(α,α-dimethyl-3,5-(Dimethoxybenzyl)oxycarbonyl-N-cyclohexylamine, N-(α,α-dimethyl-3,5-dimethoxybenzyl)oxycarbonylaniline, N-(α,α-dimethyl-3,5-dimethoxybenzyl)oxycarbonylpiperidine, N,N'-bis[(α,α-dimethyl-3,5-dimethoxybenzyl)oxycarbonyl]-1,6-hexamethylenediamine, N,N'-bis[(α,α-dimethyl-3,5-dimethoxybenzyl)oxycarbonyl]-1,4-phenylenediamine, N,N'-bis[(α,α-dimethyl-3,5-dimethoxybenzyl)oxycarbonyl]-2,4-tolylenediamine, N,N'-bis[(α,α-dimethyl-3,5-dimethoxybenzyl)oxycarbonyl]-4,4'-diaminodiphenylmethane, N,N'-bis[(α,α-dimethyl-3,5-dimethoxybenzyl)oxycarbonyl]piperazine and the like can be mentioned.,

[0088] Further, the carbamate compound is preferably a compound represented by formula (PBG-1).

Chemical formula

[0089] In formula (PEG-1), R a and R b each independently represent a hydrogen atom or a monovalent organic group, and R a and R b may be bonded to each other to form a cyclic amino group, R c represents a hydrogen atom or a methyl group, and Ar a represents an aromatic group.,

[0090] R a and R b Examples of the monovalent organic group represented by include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group composed of a combination thereof., The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. The aliphatic hydrocarbon group may be linear, branched, or cyclic. Furthermore, the cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of aliphatic hydrocarbon groups include alkyl groups, alkenyl groups, and alkynyl groups. The aromatic hydrocarbon group preferably has 6 to 18 carbon atoms, more preferably 6 to 14, and even more preferably 6 to 10 carbon atoms. The aromatic hydrocarbon group is preferably a monocyclic or fused ring with 2 to 4 condensation rings. Examples of aromatic hydrocarbon groups include aryl groups. Aliphatic hydrocarbon groups and aromatic hydrocarbon groups may have substituents. Examples of substituents include those listed as substituent T later.

[0091] R a and R b Each of these groups is preferably an aliphatic hydrocarbon group, more preferably an alkyl group, even more preferably a linear or branched alkyl group having 1 to 10 carbon atoms, even more preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group, an ethyl group, or an isopropyl group.

[0092] R a and R b These groups may bond to each other to form a cyclic amino group. Examples of the cyclic amino groups that can be formed include 1-azilidinyl group, 1-azetidinyl group, 1-pyrrolidinyl group, 1-piperidinyl group, 1-hexamethyleneimino group, 1-heptamethyleneimino group, 1-octamethyleneimino group, 1-nonameethyleneimino group, 1-1-imidazolyl group, 4,5-dihydro-1-imidazolyl group, 1-pyrrolyl group, 1-pyrazolyl group, 1-imidazolidinyl group, 1-piperazinyl group, and morpholino group. R a and R b The cyclic amino groups formed by the bonding of these groups may have substituents. Examples of substituents include those listed as substituent T later.

[0093] Ar a Aromatic groups represented by include aromatic hydrocarbon groups and aromatic heterocyclic groups. a The aromatic group represented by may be a monocyclic aromatic group, but it is preferably a fused ring aromatic group with 2 to 4 condensation rings. Examples of aromatic hydrocarbon groups include benzene ring groups, naphthalene ring groups, anthracene ring groups, and fluorene ring groups. Examples of aromatic heterocyclic groups include pyrrole rings, furan rings, thiophene rings, pyridine rings, imidazole rings, pyrazole rings, oxazole rings, thiazole rings, pyridazine rings, pyrimidine rings, pyrazine rings, indole rings, isoindole rings, benzimidazole rings, benzoxazole rings, benzothiazole rings, benzotriazole rings, quinoline rings, isoquinoline rings, quinazoline rings, quinoxaline rings, and anthraquinone rings. Ar a The aromatic group represented by may have substituents. Examples of substituents include those listed as substituent T later.

[0094] The following groups can be considered as substituents T as described above: halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms), alkenyl groups (preferably alkenyl groups having 2 to 30 carbon atoms), alkynyl groups (preferably alkynyl groups having 2 to 30 carbon atoms), aryl groups (preferably aryl groups having 6 to 30 carbon atoms), heterocyclic groups (preferably heterocyclic groups having 1 to 30 carbon atoms), amino groups (preferably amino groups having 0 to 30 carbon atoms), alkoxy groups (preferably alkoxy groups having 1 to 30 carbon atoms), aryloxy groups (preferably aryloxy groups having 6 to 30 carbon atoms) Aryloxy group), heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 30 carbon atoms), acyl group (preferably an acyl group having 2 to 30 carbon atoms), alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30 carbon atoms), aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), heterocyclic oxycarbonyl group (preferably a heterocyclic oxycarbonyl group having 2 to 30 carbon atoms), acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), acylamino group (preferably an acylamino group having 2 to 30 carbon atoms) (C1 group), aminocarbonylamino group (preferably an aminocarbonylamino group having 2 to 30 carbon atoms), alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), sulfamoylamino group (preferably a sulfamoylamino group having 0 to 30 carbon atoms), carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), alkyl Thio group (preferably an alkylthio group having 1 to 30 carbon atoms), arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), heterocyclic thio group (preferably a heterocyclic thio group having 1 to 30 carbon atoms), alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 30 carbon atoms), alkylsulfonylamino group (preferably an alkylsulfonylamino group having 1 to 30 carbon atoms), arylsulfonyl group (preferably an arylsulfonyl group having 6 to 30 carbon atoms), arylsulfonylamino group (preferably an arylsulfonylamino group having 6 to 30 carbon atoms),Heterocyclic sulfonyl group (preferably a heterocyclic sulfonyl group having 1 to 30 carbon atoms), heterocyclic sulfonylamino group (preferably a heterocyclic sulfonylamino group having 1 to 30 carbon atoms), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 30 carbon atoms), arylsulfinyl group (preferably an arylsulfinyl group having 6 to 30 carbon atoms), heterocyclic sulfinyl group (preferably a heterocyclic sulfinyl group having 1 to 30 carbon atoms), ureido group (preferably a ureido group having 1 to 30 carbon atoms) (Issula), hydroxyl, nitro, carboxyl, sulfo, phosphoric acid, carboxylic acid amide, sulfonic acid amide, imide, phosphino, mercapto, cyano, alkyl sulfino, aryl sulfino, aryl azo, heterocyclic azo, phosphinyl, phosphinyloxy, phosphinylamino, silyl, hydrazino, imino, vinyl, styrene, (meth)allyl, (meth)acryloyl, (meth)acryloyloxy. These groups may have further substituents if they are further substituted groups.

[0095] Specific examples of compounds represented by formula (PBG-1) include compounds with the structures described in the examples below.

[0096] Examples of acyl oxime compounds include acetophenone-O-propanoyloxime, benzophenone-O-propanoyloxime, acetone-O-propanoyloxime, acetophenone-O-butanoyloxime, benzophenone-O-butanoyloxime, acetone-O-butanoyloxime, bis(acetophenone)-O,O'-hexane-1,6-dioyloxime, bis(benzophenone)-O,O'-hexane-1,6-dioyloxime, bis(acetone)-O,O'-hexane-1,6-dioyloxime, acetophenone-O-acryloyloxime, benzophenone-O-acryloyloxime, and acetone-O-acryloyloxime.

[0097] Commercially available photobase generators include the WPBG series from Fujifilm Wako Pure Chemical Industries, Ltd. (for example, WPBG-018, WPBG-027, WPBG-082, WPBG-140, WPBG-165, WPBG-167, WPBG-168, WPBG-140, etc.).

[0098] The content of the generating agent in the total solid content of the composition is preferably 1 to 15% by mass, and more preferably 1 to 10% by mass, due to its excellent moisture resistance and ease of forming a cured film with a low refractive index. The lower limit is preferably 2% by mass or more, and more preferably 2.5% by mass or more. The upper limit is preferably 9% by mass or less, and more preferably 8% by mass or less. Furthermore, the total content of specific particles (particles having a silanol group) and the generating agent in the total solid content of the composition is preferably 45 to 99% by mass. The lower limit is preferably 60% by mass or more, and more preferably 80% by mass or more. The upper limit is preferably 98% by mass or less, and more preferably 97% by mass or less.

[0099] When an acid generator is used as the generating agent, the content of the acid generator (preferably the content of a photoacid generator) in the total solid content of the composition is preferably 1 to 15% by mass, and more preferably 1 to 10% by mass, for the reasons that it has excellent moisture resistance and easily forms a cured film with a low refractive index. The lower limit is preferably 2% by mass or more, and more preferably 2.5% by mass or more. The upper limit is preferably 9% by mass or less, and more preferably 8% by mass or less. Furthermore, the total content of specific particles and acid generators in the total solid content of the composition is preferably 45 to 99% by mass. The lower limit is preferably 60% by mass or more, and more preferably 80% by mass or more. The upper limit is preferably 98% by mass or less, and more preferably 97% by mass or less. Furthermore, the total content of specific particles and photoacid generator in the total solid content of the composition is preferably 45 to 99% by mass. The lower limit is preferably 60% by mass or more, and more preferably 80% by mass or more. The upper limit is preferably 98% by mass or less, and more preferably 97% by mass or less.

[0100] When a base generator is used as the generating agent, the content of the base generator in the total solid content of the composition (preferably the content of a photobase generator) is preferably 1 to 15% by mass, and more preferably 1 to 10% by mass, for the reasons that it has excellent moisture resistance and easily forms a cured film with a low refractive index. The lower limit is preferably 2% by mass or more, and more preferably 2.5% by mass or more. The upper limit is preferably 9% by mass or less, and more preferably 8% by mass or less. Furthermore, the total content of specific particles and base generating agent in the total solid content of the composition is preferably 45 to 99% by mass. The lower limit is preferably 60% by mass or more, and more preferably 80% by mass or more. The upper limit is preferably 98% by mass or less, and more preferably 97% by mass or less. Furthermore, the total content of specific particles and photobase generator in the total solid content of the composition is preferably 45 to 99% by mass. The lower limit is preferably 60% by mass or more, and more preferably 80% by mass or more. The upper limit is preferably 98% by mass or less, and more preferably 97% by mass or less.

[0101] <<Solvent>> The composition of the present invention contains a solvent. Examples of solvents include organic solvents and water, and it is preferable that the composition contains at least an organic solvent. Examples of organic solvents include aliphatic hydrocarbon solvents, halogenated hydrocarbon solvents, alcohol solvents, ether solvents, ester solvents, ketone solvents, nitrile solvents, amide solvents, sulfoxide solvents, and aromatic solvents.

[0102] Examples of aliphatic hydrocarbon solvents include hexane, cyclohexane, methylcyclohexane, pentane, cyclopentane, heptane, and octane.

[0103] Examples of halogenated hydrocarbon solvents include methylene chloride, chloroform, dichloromethane, ethane dichloride, carbon tetrachloride, trichloroethylene, tetrachloroethylene, epichlorohydrin, monochlorobenzene, orthodichlorobenzene, allyl chloride, methyl monochloroacetate, ethyl monochloroacetate, trichloroacetic acid monochloroacetate, methyl bromide, and tri(tetra)chloroethylene.

[0104] Examples of alcohol-based solvents include methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4-pentanediol, 3-methoxy-1-butanol, 1,3-butanediol, and 1,4-butanediol.

[0105] Examples of ether-based solvents include dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, cyclohexyl methyl ether, anisole, tetrahydrofuran, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, di Examples include ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol methyl-n-propyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol monomethyl ether, and polyethylene glycol dimethyl ether.

[0106] Examples of ester-based solvents include propylene carbonate, dipropylene, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, cyclohexanol acetate, dipropylene glycol methyl ether acetate, methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and triacetin.

[0107] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and 2-heptanone.

[0108] Examples of nitrile solvents include acetonitrile.

[0109] Examples of amide solvents include N,N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide.

[0110] Examples of sulfoxide-based solvents include dimethyl sulfoxide.

[0111] Examples of aromatic solvents include benzene and toluene.

[0112] It is preferable to use an alcohol-based solvent as the solvent because it is easier to form a film with less thickness variation and fewer defects. The alcohol-based solvent is preferably at least one selected from methanol, ethanol, 1-propanol, 2-propanol, and 2-butanol, and more preferably at least one selected from methanol and ethanol. In particular, it is preferable that the alcohol-based solvent contains at least methanol, and more preferably that it contains methanol and ethanol because it is easier to form a film with less defect.

[0113] The solvent content in the composition is preferably 70 to 99% by mass. The upper limit is preferably 93% by mass or less, more preferably 92% by mass or less, and even more preferably 90% by mass or less. The lower limit is preferably 75% by mass or more, more preferably 80% by mass or more, and even more preferably 85% by mass or more.

[0114] Furthermore, the content of the alcohol-based solvent in the total amount of solvent is preferably 0.1 to 10% by mass. The upper limit is preferably 8% by mass or less, more preferably 6% by mass or less, and even more preferably 4% by mass or less. The lower limit is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The alcohol-based solvent may be only one type, or two or more types may be used in combination. If the composition of the present invention contains two or more types of alcohol-based solvents, it is preferable that their total is within the above range.

[0115] It is preferable to use a solvent containing solvent A1, which has a boiling point of 190°C or higher and 280°C or lower. In this specification, the boiling point of the solvent is the value at 1 atmosphere (0.1 MPa).

[0116] The boiling point of solvent A1 is preferably 200°C or higher, more preferably 210°C or higher, and even more preferably 220°C or higher. Furthermore, the boiling point of solvent A1 is preferably 270°C or lower, and even more preferably 265°C or lower.

[0117] The viscosity of solvent A1 is preferably 10 mPa·s or less, more preferably 7 mPa·s or less, and even more preferably 4 mPa·s or less. The lower limit of the viscosity of solvent A1 is preferably 1.0 mPa·s or more, more preferably 1.4 mPa·s or more, and even more preferably 1.8 mPa·s or more, from the viewpoint of coatability.

[0118] The molecular weight of solvent A1 is preferably 100 or more, more preferably 130 or more, even more preferably 140 or more, and particularly preferably 150 or more. The upper limit is preferably 300 or less, more preferably 290 or less, even more preferably 280 or less, and particularly preferably 270 or less, from the viewpoint of coatability.

[0119] The solubility parameter of solvent A1 is 8.5~13.3 (cal / cm³). 3 ) 0.5 It is preferable that this be the case. The upper limit is 12.5 (cal / cm³). 3 ) 0.5 Preferably, it is 11.5 (cal / cm³). 3 ) 0.5 It is more preferable that the following conditions apply: 10.5 (cal / cm³) 3 ) 0.5 It is even more preferable that the following conditions are met. The lower limit is 8.7 (cal / cm³). 3 ) 0.5 It is preferable that it be 8.9 (cal / cm³) or more. 3 ) 0.5 It is more preferable that the value be greater than or equal to 9.1 (cal / cm³). 3 ) 0.5It is even more preferable that the above conditions are met. If the solubility parameter of solvent A1 is within the above range, a high affinity for specific particles such as silica particles can be obtained, and excellent coating properties can be easily achieved. Note that 1 (cal / cm 3 ) 0.5 This is 2.0455 MPa 0.5 Furthermore, the solvent solubility parameters are values ​​calculated using HSPiP.

[0120] In this specification, the solubility parameter of the solvent shall be the Hansen solubility parameter. Specifically, the value calculated using the Hansen solubility parameter software "HSPiP 5.0.09" shall be used.

[0121] Solvent A1 is preferably an aprotic solvent. By using an aprotic solvent as solvent A1, the aggregation of specific particles such as silica particles during film formation can be more effectively suppressed, making it easier to form a film with less thickness variation and fewer defects.

[0122] Solvent A1 is preferably an ether-based solvent or an ester-based solvent, with ester-based solvents being more preferred. Furthermore, the ester-based solvent used as solvent A1 is preferably a compound that does not contain hydroxyl groups or terminal alkoxy groups. By using an ester-based solvent that does not have such functional groups, it is easier to form a film with more suppressed thickness variations and defects.

[0123] Solvent A1 is preferably at least one selected from alkylenediol diacetates and cyclic carbonates, because it provides high affinity with specific particles such as silica particles and easily yields excellent coating properties. Examples of alkylenediol diacetates include propylene glycol diacetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate. Examples of cyclic carbonates include propylene carbonate and ethylene carbonate.

[0124] Specific examples of solvent A1 include propylene carbonate (boiling point 240°C), ethylene carbonate (boiling point 260°C), propylene glycol diacetate (boiling point 190°C), dipropylene glycol methyl-n-propyl ether (boiling point 203°C), dipropylene glycol methyl ether acetate (boiling point 213°C), 1,4-butanediol diacetate (boiling point 232°C), 1,3-butylene glycol diacetate (boiling point 232°C), 1,6-hexanediol diacetate (boiling point 260°C), and diethylene glycol monoethyl ether acetate. Examples include (boiling point 217°C), diethylene glycol monobutyl ether acetate (boiling point 247°C), triacetin (boiling point 260°C), dipropylene glycol monomethyl ether (boiling point 190°C), diethylene glycol monoethyl ether (boiling point 202°C), dipropylene glycol monopropyl ether (boiling point 212°C), dipropylene glycol monobutyl ether (boiling point 229°C), tripropylene glycol monomethyl ether (boiling point 242°C), and tripropylene glycol monobutyl ether (boiling point 274°C).

[0125] The solvent contained in the composition preferably contains 3% by mass or more of the above-mentioned solvent A1, more preferably 4% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less. Solvent A1 may be only one type, or two or more types may be used in combination. If two or more types of solvent A1 are included, it is preferable that their total amount is within the above range.

[0126] In addition to the solvent A1 described above, the composition may also preferably contain solvent A2 having a boiling point of 110°C or higher and less than 190°C. This embodiment makes it easier to moderately improve the drying properties of the composition and form a film with more suppressed thickness unevenness.

[0127] The boiling point of solvent A2 is preferably 115°C or higher, more preferably 120°C or higher, and even more preferably 130°C or higher. Furthermore, the boiling point of solvent A2 is preferably 170°C or lower, and even more preferably 150°C or lower. If the boiling point of solvent A2 is within the above range, the effects described above are more likely to be obtained.

[0128] The molecular weight of solvent A2 is preferably 100 or more, more preferably 130 or more, even more preferably 140 or more, and particularly preferably 150 or more, because the above-mentioned effects are more easily obtained. The upper limit is preferably 300 or less, more preferably 290 or less, even more preferably 280 or less, and particularly preferably 270 or less, from the viewpoint of coatability.

[0129] The solubility parameter of solvent A2 is 9.0~11.4 (cal / cm³). 3 ) 0.5 It is preferable that this be the case. The upper limit is 11.0 (cal / cm³). 3 ) 0.5 Preferably, it is 10.6 (cal / cm³). 3 ) 0.5 It is more preferable that the following conditions apply: 10.2 (cal / cm³) 3 ) 0.5 It is even more preferable that the following conditions are met. The lower limit is 9.2 (cal / cm³). 3 ) 0.5 Preferably, it is 9.4 (cal / cm³). 3 ) 0.5 It is more preferable that the value be greater than or equal to 9.6 (cal / cm 3 ) 0.5 It is even more preferable that the above conditions are met. If the solubility parameter of solvent A2 is within the above range, high affinity with specific particles such as silica particles can be obtained, and excellent coating properties are easily achieved. Also, the absolute value of the difference between the solubility parameter of solvent A1 and the solubility parameter of solvent A2 should be 0.01 to 1.1 (cal / cm²). 3 ) 0.5 It is preferable that this be the case. The upper limit is 0.9 (cal / cm³). 3 ) 0.5Preferably, it is 0.7 (cal / cm³). 3 ) 0.5 It is more preferable that the following conditions be met: 0.5 (cal / cm³) 3 ) 0.5 It is even more preferable that the following conditions apply. The lower limit is 0.03 (cal / cm³). 3 ) 0.5 Preferably, it should be 0.05 (cal / cm³). 3 ) 0.5 It is more preferable that the value be greater than or equal to 0.08 (cal / cm³). 3 ) 0.5 It is even more preferable that the above conditions are met.

[0130] Solvent A2 is preferably at least one selected from ether-based solvents and ester-based solvents, more preferably contains at least an ester-based solvent, and even more preferably contains both an ether-based solvent and an ester-based solvent. Specific examples of solvent A2 include cyclohexanol acetate (boiling point 173°C), dipropylene glycol dimethyl ether (boiling point 175°C), butyl acetate (boiling point 126°C), ethylene glycol monomethyl ether acetate (boiling point 145°C), propylene glycol monomethyl ether acetate (boiling point 146°C), 3-methoxybutyl acetate (boiling point 171°C), propylene glycol monomethyl ether (boiling point 120°C), 3-methoxybutanol (boiling point 161°C), propylene glycol monopropyl ether (boiling point 150°C), propylene glycol monobutyl ether (boiling point 170°C), and ethylene glycol monobutyl ether acetate (boiling point 188°C). It is preferable to include at least propylene glycol monomethyl ether acetate because it provides high affinity with specific particles such as silica particles and easily yields excellent coating properties.

[0131] When the solvent used in the composition contains solvent A2, the content of solvent A2 is preferably 500 to 5000 parts by mass per 100 parts by mass of solvent A1. The upper limit is preferably 4500 parts by mass or less, more preferably 4000 parts by mass or less, and even more preferably 3500 parts by mass or less. The lower limit is preferably 600 parts by mass or more, more preferably 700 parts by mass or more, and even more preferably 750 parts by mass or more. Furthermore, the content of solvent A2 in the total amount of solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. Solvent A2 may be only one type, or two or more types may be used in combination. When two or more types of solvent A2 are included, it is preferable that their total is within the above range.

[0132] Furthermore, the solvent used in the composition preferably contains a total of 62% by mass or more of solvent A1 and solvent A2, more preferably 72% by mass or more, and even more preferably 82% by mass or more. The upper limit may be 100% by mass, 96% by mass or less, or 92% by mass or less.

[0133] The solvent used in the composition may also preferably contain water. This embodiment allows for high affinity with specific particles such as silica particles, making it easier to obtain excellent coating properties. When the solvent used in the composition further contains water, the water content in the total amount of solvent is preferably 0.1 to 5% by mass. The upper limit is preferably 4% by mass or less, more preferably 2.5% by mass or less, and even more preferably 1.5% by mass or less. The lower limit is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and even more preferably 0.7% by mass or more. When the water content is within the above range, the effects described above are more likely to be obtained.

[0134] The solvent used in the composition may further contain solvent A3 having a boiling point exceeding 280°C. According to this embodiment, the drying properties of the composition are moderately enhanced, making it easier to form a film with reduced thickness unevenness and defects. The upper limit of the boiling point of solvent A3 is preferably 400°C or less, more preferably 380°C or less, and even more preferably 350°C or less. Solvent A3 is preferably at least one selected from ether-based solvents and ester-based solvents. Specific examples of solvent A3 include polyethylene glycol monomethyl ether. When the solvent used in the composition further contains solvent A3, the content of solvent A3 in the total amount of solvent is preferably 0.5 to 15% by mass. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less. The lower limit is preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more. It is also preferable that the solvent used in the composition substantially does not contain solvent A3. Furthermore, "substantially free of solvent A3" means that the content of solvent A3 in the total amount of solvent is 0.1% by mass or less, preferably 0.05% by mass or less, more preferably 0.01% by mass or less, and even more preferably no solvent at all.

[0135] The solvent used in the composition preferably contains 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less, of compounds with a molecular weight (or weight-average molecular weight in the case of polymers) exceeding 300. According to this embodiment, it is easier to form a film in which thickness variations and defects are more suppressed.

[0136] The solvent used in the composition preferably contains 10% by mass or less of a compound whose viscosity at 25°C exceeds 10 mPa·s, more preferably 8% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less. According to this embodiment, it is easier to form a film in which thickness variations and defects are more suppressed.

[0137] <<Silanol compounds with a molecular weight of 1000 or less>> The composition of the present invention may contain a silanol compound with a molecular weight of 1000 or less. Hereinafter, a silanol compound with a molecular weight of 1000 or less will also be referred to as a low molecular weight silanol compound. Note that a low molecular weight silanol compound is a different material from the particles having silanol groups described above.

[0138] It is preferable that the low molecular weight silanol compound is readily soluble in water. Furthermore, it is preferable that the low molecular weight silanol compound dissolves in 100 g of water at 25°C or 100 g of propylene glycol monomethyl ether acetate at 25°C in an amount of 5 g or more, and more preferably in an amount of 10 g or more.

[0139] The molecular weight of the low molecular weight silanol compound is preferably 950 or less, more preferably 900 or less, and even more preferably 800 or less.

[0140] The silanol value of a low molecular weight silanol compound is preferably 0.1 to 10 mmol / g. The upper limit of the silanol value is preferably 7 mmol / g or less, and more preferably 5 mmol / g or less. The lower limit of the silanol value is preferably 0.5 mmol / g or more, and more preferably 1 mmol / g or more. The silanol value of a low molecular weight silanol compound is a numerical value that represents the molar amount of silanol groups per gram of solid content of the low molecular weight silanol compound. The silanol value of a low molecular weight silanol compound can be calculated by dividing the number of silanol groups contained in one molecule of the low molecular weight silanol compound by the molecular weight of the low molecular weight silanol compound.

[0141] The low molecular weight silanol compound may further have functional groups such as carboxyl groups, amino groups, mercapto groups, (meth)acryloyl groups, isocyanate groups, and epoxy groups. The presence of these additional functional groups can further increase the crosslinking density of the film. The functional groups are preferably carboxyl groups, amino groups, (meth)acryloyl groups, or mercapto groups, and more preferably carboxyl groups or amino groups.

[0142] Examples of low molecular weight silanol compounds include X-12-1135, KBP-90 (both manufactured by Shin-Etsu Chemical Co., Ltd.), KBP-64, X-12-1098, X-12-1135, X-12-1139, and X-12-1126 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0143] The content of the low molecular weight silanol compound in the composition of the present invention is preferably 0.1 to 10% by mass. The lower limit is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. The upper limit is preferably 7.5% by mass or less, and more preferably 5% by mass or less. Furthermore, the content of the low molecular weight silanol compound in the total solid content of the composition of the present invention is preferably 1 to 20% by mass. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. The composition of the present invention may contain only one type of low molecular weight silanol compound, or it may contain two or more types. If the composition of the present invention contains two or more types of low molecular weight silanol compounds, it is preferable that their sum is within the above range.

[0144] <<Surfactants>> The compositions of the present invention may contain surfactants. Various surfactants can be used, such as fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants. The surfactant is preferably a fluorinated surfactant or a silicone surfactant, and more preferably a silicone surfactant. In this specification, a silicone surfactant is a compound having repeating units containing siloxane bonds in its main chain, and containing both a hydrophobic and a hydrophilic portion within a single molecule.

[0145] Examples of fluorinated surfactants include those described in paragraphs 0060 to 0064 of Japanese Patent Publication No. 2014-041318 (corresponding to paragraphs 0060 to 0064 of International Publication No. 2014 / 017669), those described in paragraphs 0117 to 0132 of Japanese Patent Publication No. 2011-132503, and those described in Japanese Patent Publication No. 2020-008634, the contents of which are incorporated herein by reference. Examples of commercially available fluorine-based surfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, R-01, R- 40, R-40-LM, R-41, R-41-LM, RS-43, R-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (all manufactured by DIC Corporation), Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by AGC Inc.), PolyFox Examples include the PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), the F-Tergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS, and the FTX-218 (all manufactured by NEOS Corporation).

[0146] Fluorine-based surfactants include acrylic compounds that have a molecular structure with a functional group containing a fluorine atom, and when heated, the fluorine-containing functional group is cleaved, causing the fluorine atom to volatilize. Examples of such fluorine-based surfactants include the MegaFac DS series manufactured by DIC Corporation (Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), such as MegaFac DS-21.

[0147] Fluorine-based surfactants may also preferably be polymers of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Examples of such fluorine-based surfactants include those described in Japanese Patent Application Publication No. 2016-216602, the details of which are incorporated herein by reference.

[0148] Block polymers can also be used as fluorine-based surfactants. Fluorine-based surfactants can also preferably be fluorine-containing polymer compounds that include repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). Furthermore, fluorine-containing surfactants described in paragraphs 0016 to 0037 of Japanese Patent Application Publication No. 2010-032698, and the following compounds are also examples of fluorine-based surfactants used in the present invention. [ka] The weight-average molecular weight of the above compounds is preferably 3,000 to 50,000, for example, 14,000. In the above compounds, the percentage indicating the proportion of repeating units is expressed as mole percent.

[0149] Furthermore, fluorinated surfactants can also be fluorinated polymers having ethylenically unsaturated bond-containing groups in their side chains. Specific examples include the compounds described in paragraphs 0050-0090 and 0289-0295 of Japanese Patent Publication No. 2010-164965, and Megafac RS-101, RS-102, RS-718K, RS-72-K, etc., manufactured by DIC Corporation. Additionally, fluorinated surfactants can also be compounds described in paragraphs 0015-0158 of Japanese Patent Publication No. 2015-117327.

[0150] Furthermore, using the surfactant described in International Publication No. 2020 / 084854 as a substitute for surfactants having a perfluoroalkyl group with 6 or more carbon atoms is also preferable from an environmental regulatory standpoint.

[0151] Furthermore, it is also preferable to use a fluorine-containing imide salt compound represented by formula (fi-1) as a surfactant. [ka] In equation (fi-1), m represents 1 or 2, n represents an integer from 1 to 4, a represents 1 or 2, and X a+ This refers to α-valent metal ions, primary ammonium ions, secondary ammonium ions, tertiary ammonium ions, quaternary ammonium ions, or NH4. + It represents.

[0152] The silicone-based surfactant is preferably a compound that does not contain fluorine atoms. The silicone-based surfactant is preferably a modified silicone compound. Examples of modified silicone compounds include compounds in which an organic group is introduced to the side chain and / or terminal of a polysiloxane. Examples of organic groups include groups containing functional groups selected from amino groups, epoxy groups, alicyclic epoxy groups, carbinol groups, mercapto groups, carboxyl groups, fatty acid ester groups, and fatty acid amide groups, as well as groups containing polyether chains, with groups containing carbinol groups and groups containing polyether chains being preferred.

[0153] Specific examples of silicone-based surfactants include, for example, DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400, SH 8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419. Examples include OIL (manufactured by Dow Toray Industries, Inc.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 (manufactured by BIC Chemie), etc.

[0154] Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acids. Examples include esters, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspers 20000 (manufactured by Lubrizol Nippon Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Fujifilm Wako Pure Chemical Industries Ltd.), Paionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.).

[0155] The surfactant content in the composition of the present invention is preferably 0.01 to 0.3% by mass. The lower limit is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.15% by mass or more, for the reason that it is easier to more effectively suppress the occurrence of wavy coating unevenness. The upper limit is preferably 0.28% by mass or less, more preferably 0.25% by mass or less, and even more preferably 0.2% by mass or less. Furthermore, the surfactant content in the total solid content of the composition of the present invention is preferably 0.05 to 5.00% by mass. The lower limit is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.2% by mass or more, for the reason that it is easier to more effectively suppress the occurrence of wavy coating unevenness. The upper limit is preferably 4% by mass or less, and even more preferably 3% by mass or less. The composition of the present invention may contain only one type of surfactant, or it may contain two or more types. If the composition of the present invention contains two or more types of surfactants, it is preferable that their total is within the above range.

[0156] <<Dispersant>> The compositions of the present invention may contain a dispersant. Examples of dispersants include polymeric dispersants (e.g., polyamidoamines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylic copolymers, naphthalene sulfonic acid formalin condensates), polyoxyethylene alkyl phosphates, polyoxyethylene alkylamines, alkanolamines, etc. Polymeric dispersants can be further classified into linear polymers, end-modified polymers, graft polymers, and block polymers based on their structure. Polymeric dispersants adsorb to the surface of particles and act to prevent re-aggregation. Therefore, end-modified polymers, graft polymers, and block polymers having anchor sites on the particle surface are preferred structures. Commercially available dispersants can also be used. For example, the products described in paragraph 0050 of International Publication No. 2016 / 190374 are examples, and this content is incorporated herein by reference.

[0157] The dispersant content is preferably 1 to 100 parts by mass, more preferably 3 to 100 parts by mass, and even more preferably 5 to 80 parts by mass, per 100 parts by mass of specific particles. Furthermore, the dispersant content is preferably 1 to 30% by mass of the total solid content of the composition. The dispersant may be of only one type, or it may contain two or more types. If two or more types of dispersants are included, it is preferable that their total content is within the above range.

[0158] <<Radical Polymerizable Monomers>> The composition of the present invention may contain a radical polymerizable monomer. Preferably, the radical polymerizable monomer is a compound having an ethylenically unsaturated bond-containing group. Furthermore, it is preferable that the radical polymerizable monomer is a compound that does not contain a silanol group.

[0159] The molecular weight of the radical polymerizable monomer is preferably between 100 and 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and even more preferably 250 or more.

[0160] Radical polymerizable monomers are preferably compounds having two or more ethylenically unsaturated bond-containing groups, and more preferably compounds having three or more ethylenically unsaturated bond-containing groups. The upper limit of the number of ethylenically unsaturated bond-containing groups is preferably 15 or less, and more preferably 6 or less. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, styrene groups, (meth)allyl groups, and (meth)acryloyl groups, with (meth)acryloyl groups being preferred. Radical polymerizable monomers are preferably 3-15 functional (meth)acrylate compounds, and more preferably 3-6 functional (meth)acrylate compounds. Specific examples of radical polymerizable monomers include the compounds described in paragraphs 0059-0079 of International Publication No. 2016 / 190374.

[0161] Examples of radically polymerizable monomers include dipentaerythritol tri(meth)acrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and compounds in which the (meth)acryloyl group of these compounds is linked via ethylene glycol and / or propylene glycol residues (e.g., SR454, SR499, commercially available from Sartomer), diglycerin EO (ethylene oxide) modified (meth)acrylate (commercial product M-460 (manufactured by Toagosei Co., Ltd.)), pentaerythritol tetraacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd., NK Ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD You can use HDDA, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronics TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc.

[0162] Furthermore, trifunctional (meth)acrylate compounds such as trimethylolpropane tri(meth)acrylate, trimethylolpropanepropylene oxide-modified tri(meth)acrylate, trimethylolpropaneethylene oxide-modified tri(meth)acrylate, isocyanurate ethylene oxide-modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate can also be used as radical polymerizable monomers. Commercially available trifunctional (meth)acrylate compounds include Aronics M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.).

[0163] Radical polymerizable monomers can also be compounds containing acidic groups. Examples of acidic groups include carboxyl groups, sulfol groups, and phosphate groups, with carboxyl groups being preferred. Commercially available radical polymerizable monomers containing acidic groups include Arronix M-510, M-520, and Arronix TO-2349 (manufactured by Toagosei Co., Ltd.). The preferred acid value of radical polymerizable monomers containing acidic groups is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. If the acid value of the radical polymerizable monomer is 0.1 mgKOH / g or higher, it has good solubility in the developer, and if it is 40 mgKOH / g or lower, it is advantageous in terms of manufacturing and handling.

[0164] Radical polymerizable monomers can also be compounds having a caprolactone structure. Radical polymerizable monomers having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, including DPCA-20, DPCA-30, DPCA-60, DPCA-120, and others.

[0165] Radical polymerizable monomers can also be radical polymerizable monomers having alkylene oxy groups. Of the radical polymerizable monomers having alkylene oxy groups, radical polymerizable monomers having ethylene oxy groups and / or propylene oxy groups are preferred, radical polymerizable monomers having ethylene oxy groups are more preferred, and 3-6 functional (meth)acrylate compounds having 4-20 ethylene oxy groups are even more preferred. Examples of commercially available radical polymerizable monomers having alkylene oxy groups include SR-494, a tetrafunctional (meth)acrylate having 4 ethylene oxy groups manufactured by Sartomer, and KAYARAD TPA-330, a trifunctional (meth)acrylate having 3 isobutylene oxy groups manufactured by Nippon Kayaku Co., Ltd.

[0166] Radical polymerizable monomers can also be radical polymerizable monomers having a fluorene skeleton. Commercially available radical polymerizable monomers having a fluorene skeleton include Ogusol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).

[0167] As radical polymerizable monomers, it is also preferable to use compounds that are substantially free of environmentally regulated substances such as toluene. Examples of commercially available such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).

[0168] When the composition of the present invention contains a radical polymerizable monomer, the content of the radical polymerizable monomer in the composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.5% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. Furthermore, the content of the radical polymerizable monomer in the total solid content of the composition is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. The composition of the present invention may contain only one type of radical polymerizable monomer, or it may contain two or more types. When two or more types of radical polymerizable monomers are included, it is preferable that their total is within the above range. Furthermore, it is preferable that the composition of the present invention substantially does not contain radical polymerizable monomers. When the composition of the present invention substantially does not contain radical polymerizable monomers, it is easier to form a film with a lower refractive index. Moreover, it is easier to form a film with less haze. When the composition of the present invention substantially does not contain radical polymerizable monomers, it means that the content of radical polymerizable monomers in the total solid content of the composition of the present invention is 0.05% by mass or less, preferably 0.01% by mass or less, and more preferably no radical polymerizable monomers at all.

[0169] <Photoradical polymerization initiator> The composition of the present invention may contain a photoradical polymerization initiator. When the composition of the present invention contains a radically polymerizable monomer and a photoradical polymerization initiator, the composition of the present invention can be preferably used as a composition for pattern formation in photolithography.

[0170] Examples of photoradical polymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, and α-aminoketone compounds. From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, hexaarylbiimidazole compound, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound, and 3-arylsubstituted coumarin compound, more preferably a compound selected from oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds, and even more preferably an oxime compound. Furthermore, as photoradical polymerization initiators, the compounds described in paragraphs 0065-0111 of JP 2014-130173, the compounds described in Japanese Patent No. 6301489, the peroxide-based photoradical polymerization initiator described in MATERIAL STAGE 37-60p, vol.19, No.3, 2019, the photoradical polymerization initiator described in International Publication No. 2018 / 221177, the photoradical polymerization initiator described in International Publication No. 2018 / 110179, the photoradical polymerization initiator described in JP 2019-043864, the photoradical polymerization initiator described in JP 2019-044030, and JP 2019-167 Examples include peroxide-based initiators described in Japanese Patent Publication No. 313, aminoacetophenone-based initiators having an oxazolidine group described in Japanese Patent Application Publication No. 2020-055992, oxime-based photoradical polymerization initiators described in Japanese Patent Application Publication No. 2013-190459, polymers described in Japanese Patent Application Publication No. 2020-172619, and compounds represented by Formula 1 described in International Publication No. 2020 / 152120, the contents of which are incorporated herein by reference.

[0171] Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.

[0172] Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins BV), and Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins BV), and Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF). Commercially available acylphosphine compounds include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins BV), and Irgacure 819 and Irgacure TPO (both manufactured by BASF).

[0173] Examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, the compounds described in Japanese Patent Publication No. 2000-080068, the compounds described in Japanese Patent Publication No. 2006-342166, the compounds described in JCSPerkin II (1979, pp. 1653-1660), the compounds described in JCSPerkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2006-342166, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent Publication No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, and compounds described in International Publication No. 2013 / 167515. Specific examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one, and 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime). Examples of commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (all manufactured by BASF), TR-PBG-304, TR-PBG-327 (manufactured by Tronley), and ADEKA Optomer N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in Japanese Patent Publication No. 2012-014052).Furthermore, it is preferable to use oxime compounds that do not produce color or compounds that are highly transparent and resistant to discoloration. Examples of commercially available products include ADEKA Arclus NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).

[0174] As a photoradical polymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include the compound described in Japanese Patent Publication No. 2014-137466, the compound described in Japanese Patent No. 6636081, and the compound described in Korean Published Patent No. 10-2016-0109444.

[0175] As a photoradical polymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is replaced by a naphthalene ring can also be used. Specific examples of such oxime compounds include those described in International Publication No. 2013 / 083505.

[0176] As a photoradical polymerization initiator, an oxime compound containing a fluorine atom can also be used. Specific examples of oxime compounds containing a fluorine atom include the compound described in Japanese Patent Publication No. 2010-262028, compounds 24, 36-40 described in Japanese Patent Publication No. 2014-500852, and compound (C-3) described in Japanese Patent Publication No. 2013-164471.

[0177] As a photoradical polymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably in dimer form. Specific examples of oxime compounds having a nitro group include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Publication No. 2014-137466, the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, and ADEKA Arclus NCI-831 (manufactured by ADEKA Corporation).

[0178] Oxime compounds having a benzofuran skeleton can also be used as photoradical polymerization initiators. Specific examples include OE-01 to OE-75, described in International Publication No. 2015 / 036910.

[0179] As photoradical polymerization initiators, oxime compounds in which a substituent having a hydroxyl group is attached to a carbazole skeleton can also be used. Examples of such photoradical polymerization initiators include the compounds described in International Publication No. 2019 / 088055.

[0180] The oxime compound is preferably one having a maximum absorption wavelength in the range of 350 to 500 nm, and more preferably one having a maximum absorption wavelength in the range of 360 to 480 nm. Furthermore, from the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably 1,000 to 300,000, even more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000. The molar extinction coefficient of the compound can be measured using known methods. For example, it is preferable to measure it using a spectrophotometer (Cary-5 spectrophotometer, Varian) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0181] As the photoradical polymerization initiator, a bifunctional or trifunctional or more photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thus providing good sensitivity. Furthermore, when an asymmetric compound is used, the crystallinity decreases and solubility in solvents etc. improves, making precipitation less likely over time and improving the long-term stability of the composition. Specific examples of bifunctional or trifunctional or more photoradical polymerization initiators include the dimers of oxime compounds described in JP 2010-527339, JP 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of JP 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680, as well as compounds (E) and (G) described in JP 2013-522445, and International Publication No. Examples include Cmpd1-7 described in Patent Publication No. 2016 / 034963, oxime ester photoinitiators described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators described in paragraphs 0020-0033 of Japanese Patent Publication No. 2017-167399, photopolymerization initiators (A) described in paragraphs 0017-0026 of Japanese Patent Publication No. 2017-151342, and oxime ester photoinitiators described in Japanese Patent Publication No. 6469669.

[0182] When the composition of the present invention contains a photoradical polymerization initiator, the content of the photoradical polymerization initiator in the composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.5% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. Furthermore, the content of the photoradical polymerization initiator in the total solid content of the composition is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. Furthermore, it is preferable to contain 10 to 1000 parts by mass of the photoradical polymerization initiator per 100 parts by mass of the radically polymerizable monomer. The upper limit is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and even more preferably 100 parts by mass or less. The lower limit is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, and even more preferably 60 parts by mass or more. The composition of the present invention may contain only one type of photoradical polymerization initiator, or it may contain two or more types. When two or more types of photoradical polymerization initiators are included, it is preferable that their total number is within the above range. Furthermore, it is preferable that the composition of the present invention substantially does not contain a photoradical polymerization initiator. When the composition of the present invention substantially does not contain a photoradical polymerization initiator, this means that the content of the photoradical polymerization initiator in the total solid content of the composition is 0.005% by mass or less, preferably 0.001% by mass or less, and more preferably no photoradical polymerization initiator at all.

[0183] <<Resin>> The composition of the present invention may contain a resin. The weight-average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more. The number-average molecular weight (Mn) of the resin is also preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more.

[0184] Examples of resins include (meth)acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene etherphosphine oxide resins, polyimide resins, polyamide resins, polyamide-imide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polyurethane resins, polyurea resins, and siloxane resins. One of these resins may be used alone, or two or more may be used in mixture form. Among cyclic olefin resins, norbornene resin is preferred from the viewpoint of improving heat resistance. Examples of commercially available norbornene resins include the ARTON series (e.g., ARTON F4520) manufactured by JSR Corporation. Examples of siloxane resins include the Cylaprene series (e.g., FM-DA21, FM-3321) manufactured by JNC Corporation.

[0185] The resins include those described in the examples of International Publication No. 2016 / 088645, the resins described in Japanese Patent Publication No. 2017-057265, the resins described in Japanese Patent Publication No. 2017-032685, the resins described in Japanese Patent Publication No. 2017-075248, the resins described in Japanese Patent Publication No. 2017-066240, the resins described in Japanese Patent Publication No. 2017-167513, the resins described in Japanese Patent Publication No. 2017-173787, and those described in paragraphs 0041 to 0060 of Japanese Patent Publication No. 2017-206689. Resins, resins described in paragraphs 0022 to 0071 of Japanese Patent Publication No. 2018-010856, block polyisocyanate resins described in Japanese Patent Publication No. 2016-222891, resins described in Japanese Patent Publication No. 2020-122052, resins described in Japanese Patent Publication No. 2020-111656, resins described in Japanese Patent Publication No. 2020-139021, and resins containing constituent units having a ring structure in the main chain and constituent units having biphenyl groups in the side chains as described in Japanese Patent Publication No. 2017-138503 can also be used. Furthermore, resins having a fluorene skeleton can also be preferably used as resins. For resins having a fluorene skeleton, the description in U.S. Patent Application Publication No. 2017 / 0102610 can be referenced, and this content is incorporated herein by reference. Furthermore, as the resin, the resin described in paragraphs 0199 to 0233 of Japanese Patent Publication No. 2020-186373, the alkali-soluble resin described in Japanese Patent Publication No. 2020-186325, and the resin represented by Formula 1 described in Korean Published Patent No. 10-2020-0078339 can also be used.

[0186] It is also preferable to use a resin having acidic groups as the resin. According to this embodiment, the developability can be further improved when forming patterns by photolithography. Examples of acidic groups include carboxyl groups, phosphate groups, sulfo groups, and phenolic hydroxyl groups, with carboxyl groups being preferred. Resins having acidic groups can be used, for example, as alkali-soluble resins.

[0187] Resins having acidic groups preferably contain repeating units having acidic groups in their side chains, and more preferably contain repeating units having acidic groups in their side chains in an amount of 5 to 70 mol% of the total repeating units of the resin. The upper limit of the content of repeating units having acidic groups in their side chains is preferably 50 mol% or less, and more preferably 30 mol% or less. The lower limit of the content of repeating units having acidic groups in their side chains is preferably 10 mol% or more, and more preferably 20 mol% or more.

[0188] The acid value of the resin containing acid groups is preferably 30 to 500 mg KOH / g. The lower limit is preferably 50 mg KOH / g or more, and more preferably 70 mg KOH / g or more. The upper limit is preferably 400 mg KOH / g or less, more preferably 300 mg KOH / g or less, and even more preferably 200 mg KOH / g or less. The weight-average molecular weight (Mw) of the resin containing acid groups is preferably 5,000 to 100,000. The number-average molecular weight (Mn) of the resin containing acid groups is preferably 1,000 to 20,000.

[0189] The resin content in the total solids of the composition is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less, for which the effects of the present invention are more pronounced. The composition of the present invention may contain only one type of resin, or it may contain two or more types. If it contains two or more types of resin, it is preferable that their sum is within the above range. The composition of the present invention may preferably contain substantially no resin. In this specification, "substantially resin-free" means that the resin content in the total solids of the composition is 0.1% by mass or less, preferably 0.05% by mass or less, and more preferably no resin at all.

[0190] <<Adhesion enhancer>> The composition of the present invention may contain an adhesion modifier. By including an adhesion modifier, a cured film with excellent adhesion to the support can be formed. Suitable adhesion modifiers include, for example, those described in Japanese Patent Publication No. 05-011439, Japanese Patent Publication No. 05-341532, and Japanese Patent Publication No. 06-043638. Specifically, examples include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzuxazole, 2-mercaptobenzuthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thion, 3-morpholinomethyl-5-phenyl-oxadiazole-2-thion, 5-amino-3-morpholinomethyl-thiadiazole-2-thion, and 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, and silane coupling agents. As adhesion improvers, silane coupling agents are preferred. In this specification, a silane coupling agent is a compound having a hydrolyzable group. The silane coupling agent is preferably a silane compound having a hydrolyzable group and other functional groups. Furthermore, a hydrolyzable group is a substituent that is directly bonded to a silicon atom and can form a siloxane bond through at least one of hydrolysis and / or condensation reactions. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, and acyloxy groups, with alkoxy groups being preferred.

[0191] The silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of alkoxysilyl groups include monoalkoxysilyl groups, dialkoxysilyl groups, and trialkoxysilyl groups, with trialkoxysilyl groups being preferred. Furthermore, the number of carbon atoms in the alkyl portion of the alkoxysilyl group is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, even more preferably 1 or 2, and preferably 1. Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and phenyl groups, with amino groups, (meth)acryloyl groups, and epoxy groups being preferred. The curability of the composition of the present invention can be further improved by including a compound having an alkoxysilyl group. The reason for this effect is presumed to be that the compound having the alkoxysilyl group undergoes hydrolysis condensation due to the base or acid generated from the generating agent. In particular, when a photoacid generator or a photobase generator is used as the generating agent, a composition with excellent photocurability can be obtained. Such a composition can be preferably used as a composition for pattern formation in photolithography.

[0192] Specific examples of silane coupling agents include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N-β-aminoethyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxypropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-502), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name Examples include KBM-503), 8-glycidoxyoctyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-4803), 1,8-bis(trimethoxysilyl)octane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-3086), tris(trimethoxysilylpropyl)isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-9659), X-12-5263HP (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Specific examples of silane coupling agents include the compounds described in paragraphs 0018 to 0036 of Japanese Patent Publication No. 2009-288703 and the compounds described in paragraphs 0056 to 0066 of Japanese Patent Publication No. 2009-242604, the contents of which are incorporated herein by reference.

[0193] When the composition of the present invention contains an adhesion improver, the content of the adhesion improver in the total solid content of the composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and particularly preferably 0.1% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. The composition of the present invention may contain only one type of adhesion improver, or it may contain two or more types. When two or more types of adhesion improvers are included, it is preferable that their total is within the above range.

[0194] <<Component B>> The composition of the present invention may optionally contain sensitizers, fillers, thermosetting accelerators, plasticizers, and other auxiliary agents (e.g., conductive particles, defoamers, flame retardants, leveling agents, peel accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101-0104, 0107-0109, etc., of Japanese Patent Application Publication No. 2008-250074, and these contents are incorporated herein. The composition may also optionally contain latent antioxidants. Examples of latent antioxidants include compounds in which the antioxidant portion is protected by a protecting group, and which function as antioxidants when heated at 100-250°C or at 80-200°C in the presence of an acid / base catalyst, thereby removing the protecting group. Examples of latent antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Publication No. 2017-008219. Examples of commercially available latent antioxidants include ADEKA Arclus GPA-5001 (manufactured by ADEKA Corporation).

[0195] The composition of the present invention may contain a coloring agent. Examples of coloring agents include green coloring agents, red coloring agents, yellow coloring agents, purple coloring agents, blue coloring agents, orange coloring agents, and black coloring agents.

[0196] The coloring agent may be a pigment or a dye. The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, and more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less.

[0197] The content of colorants in the total solid content of the composition is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 1% by mass or less. The composition of the present invention may contain only one type of colorant, or it may contain two or more types. If two or more colorants are included, it is preferable that their total is within the above range. Furthermore, it is preferable that the composition of the present invention substantially contains no colorants. When the composition of the present invention substantially contains no colorants, this means that the content of colorants in the total solid content of the composition is 0.1% by mass or less, preferably 0.05% by mass or less, and more preferably no colorants at all.

[0198] From an environmental regulatory standpoint, the use of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts may be restricted. When reducing the content of the above-mentioned compounds in a composition, the content of perfluoroalkyl sulfonic acid (particularly perfluoroalkyl sulfonic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts, and perfluoroalkyl carboxylic acid (particularly perfluoroalkyl carboxylic acid with 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts is preferably in the range of 0.01 ppb to 1,000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, relative to the total solid content of the composition. The composition may not substantially contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts. For example, by using compounds that can substitute for perfluoroalkyl sulfonic acid and its salts, and compounds that can substitute for perfluoroalkyl carboxylic acid and its salts, a composition that substantially does not contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts may be selected. Compounds that may substitute for regulated compounds include, for example, compounds that have been excluded from regulation due to differences in the number of carbon atoms in the perfluoroalkyl group. However, the above does not preclude the use of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts. The composition may contain perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts, to the maximum permissible extent.

[0199] <container> There are no particular limitations on the container used to house the composition of the present invention, and any known container can be used. Furthermore, to suppress the incorporation of impurities into the raw materials and composition, it is preferable to use a multilayer bottle with an inner wall made of six types of resin in six layers, or a bottle with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351. In addition, it is preferable to make the inner wall of the container out of glass or stainless steel to prevent metal leaching from the inner wall, to improve the storage stability of the composition, and to suppress deterioration of its components.

[0200] <Method for producing the composition> The composition of the present invention can be prepared by mixing the aforementioned components. When preparing the composition, all components may be dissolved and / or dispersed simultaneously in a solvent, or, if necessary, each component may be prepared as two or more solutions or dispersions and mixed at the time of use (application) to prepare the composition.

[0201] In the production of the composition, it is preferable to filter the composition with a filter for purposes such as removing foreign matter and reducing defects. Any filter that has been conventionally used for filtration purposes can be used without particular limitations. For example, filters made of materials such as fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (e.g., nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight polyolefin resins) can be used. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

[0202] The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. If the filter pore size is within the above range, fine foreign matter can be removed more reliably. The nominal value of the filter pore size can be referred to from the filter manufacturer. Various filters provided by Nippon Pall Co., Ltd. (DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.), Advantec Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), and KITZ Microfilter Corporation can be used.

[0203] Furthermore, it is also preferable to use fibrous filter media as a filter. Examples of fibrous filter media include polypropylene fiber, nylon fiber, and glass fiber. Commercially available products include the SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) from Rokitechno Co., Ltd.

[0204] When using filters, different filters (for example, a first filter and a second filter) may be combined. In this case, filtration with each filter may be performed only once or two or more times. Filters with different pore sizes within the range described above may also be combined. Furthermore, filtration with the first filter may be performed only on the dispersion, and then filtration with the second filter may be performed after mixing in other components. In addition, filters can be selected as appropriate according to the hydrophilicity and hydrophobicity of the composition.

[0205] <Cured film> The cured film of the present invention is a cured film obtained from the composition of the present invention described above.

[0206] The refractive index of the cured film of the present invention at a wavelength of 633 nm is preferably 1.45 or less, more preferably 1.4 or less, even more preferably 1.35 or less, even more preferably 1.3 or less, and even more preferably 1.27 or less. The above refractive index values ​​are obtained at a measurement temperature of 25°C.

[0207] The cured film of the present invention preferably has sufficient hardness. Furthermore, the Young's modulus of the cured film is preferably 2 or higher, more preferably 3 or higher, and particularly preferably 4 or higher. The upper limit is preferably 10 or lower.

[0208] The thickness of the cured film of the present invention can be appropriately selected depending on the application. For example, the film thickness is preferably 3 μm or less, more preferably 1.5 μm or less, and particularly preferably 1.0 μm or less. There is no lower limit, but it is preferably 50 nm or more.

[0209] The cured film of the present invention can be used in optical functional layers in image display devices and solid-state image sensors. Examples of optical functional layers include anti-reflective layers, low refractive index layers, and waveguides.

[0210] The cured film of the present invention can also be used as a component adjacent to a pixel in an optical filter having multiple pixels. For example, the cured film of the present invention can be used as a partition to separate pixels of an optical filter. Examples of pixels include colored pixels, transparent pixels, pixels of the near-infrared transmission filter layer, and pixels of the near-infrared cut filter layer. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. Furthermore, the cured film of the present invention can also be used by placing it on the light incident side or the light exit side of an optical filter.

[0211] Furthermore, in solid-state image sensors and image display devices having microlenses, the cured film of the present invention can also be formed on the microlenses and used.

[0212] <Method for manufacturing a cured film> The method for manufacturing a cured film of the present invention includes a step of applying the composition of the present invention described above onto a support to form a composition layer, and a step of curing the composition layer, and obtains a cured film which is a film obtained by curing the composition layer at a temperature of 150°C or lower throughout all steps. The method for manufacturing a cured film is characterized in that the step of curing the composition layer includes a step of generating an acid or a base from an acid generator or a base generator contained in the composition layer by irradiating light or heating the composition layer. There is no particular limitation on the support for forming the composition layer, and it can be appropriately selected according to the application. For example, substrates such as wafers made of materials such as silicon, non-alkali glass, soda glass, Pyrex (registered trademark) glass, and quartz glass can be mentioned. It is also preferable to use an InGaAs substrate or the like. Further, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the support. Further, a black matrix made of a light-shielding material such as tungsten may be formed on the support. Further, an underlayer may be provided on the support for improving adhesion to an upper layer, preventing diffusion of substances, or flattening the substrate surface. Further, a microlens can also be used for the support.

[0214] ​​​​As a method for applying the composition, known methods can be used. For example, the drop casting method; the slit coating method; the spray method; the roll coating method; the spin coating method; the casting coating method; the slit and spin method; the prewet method (for example, the method described in JP-A-2009-145395); ejection system printing such as inkjet (for example, the on-demand method, the piezo method, the thermal method), nozzle jet, etc., flexographic printing, screen printing, gravure printing, reverse offset printing, various printing methods such as the metal mask printing method; the transfer method using a mold, etc.; the nanoimprint method, etc. The application method in inkjet is not particularly limited, and for example, the method shown in "Spreading and Usable Inkjet - Infinite Possibilities in Patents -", published in February 2005, Sumitomo Precision Research (especially pages 115 to 133), and the methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, etc. can be mentioned. Further, regarding the method for applying the composition for the optical sensor, the descriptions of WO 2017 / 030174 and WO 2017 / 018419 can be referred to, and the contents thereof are incorporated into this specification.

[0215] The composition layer formed on the support may be dried (prebaked). When prebaking is performed, the prebaking temperature is 150°C or lower, preferably 120°C or lower, and more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher. The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. The prebaking can be performed using a hot plate, an oven, etc.

[0216] When the composition of the present invention uses a photoacid generator or a photobase generator as a generator, the above-mentioned curing treatment step preferably includes a step of irradiating the composition layer with light for exposure.

[0217] Examples of light that can be used for exposure include g-line and i-line light. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), with KrF line (wavelength 248 nm) being preferred. Long-wave light sources with wavelengths of 300 nm or more can also be used.

[0218] Furthermore, exposure may be performed by continuously irradiating with light, or by irradiating in pulses (pulsed exposure). Pulsed exposure is an exposure method that involves repeatedly irradiating and pausing with light in short cycles (for example, at the millisecond level or less).

[0219] The irradiation dose (exposure dose) is, for example, 0.03 to 2.5 J / cm². 2 Preferably, 0.05 to 1.0 J / cm² 2 This is more preferable. The oxygen concentration during exposure can be appropriately selected. In addition to exposure in air, exposure may be carried out in a low-oxygen atmosphere with an oxygen concentration of 19 vol% or less (e.g., 15 vol%, 5 vol%, or substantially oxygen-free), or in a high-oxygen atmosphere with an oxygen concentration exceeding 21 vol% (e.g., 22 vol%, 30 vol%, or 50 vol%). Furthermore, the exposure intensity can be appropriately set, usually 1000 W / m². 2 ~100,000 W / m 2 (For example, 5000W / m 2 , 15000W / m 2 , or 35000W / m 2 The oxygen concentration and exposure intensity can be combined as appropriate; for example, an oxygen concentration of 10% by volume and an illuminance of 10,000 W / m². 2 At an oxygen concentration of 35% by volume, the illuminance is 20,000 W / m². 2 This can be done as follows.

[0220] When the composition of the present invention uses a photoacid generator or a photobase generator as the generating agent, the curing treatment step preferably includes a step of irradiating the composition layer with light to expose it.

[0221] When the composition of the present invention uses a thermal acid generator or a thermal base generator as the generating agent, the curing treatment step preferably includes a heating step for the composition layer. The heating temperature is 150°C or lower, preferably 120°C or lower, and more preferably 110°C or lower. The lower limit can be, for example, 80°C or higher. The heating time is preferably 60 to 1800 seconds, more preferably 120 to 900 seconds, and even more preferably 180 to 600 seconds. The heating treatment can be carried out using a hot plate, oven, etc. If post-baking is performed when forming the composition layer, the post-baking step may be the heating step in the curing treatment step. That is, during post-baking, the composition layer may be dried, and an acid or base may be generated from the thermal acid generator or thermal base generator contained in the composition layer to perform the curing treatment of the composition layer.

[0222] The method for manufacturing a cured film according to the present invention can also be used to manufacture optical filters, image display devices, solid-state image sensors, and the like.

[0223] <Method for forming patterns> Next, a method for forming a pattern using the composition of the present invention will be described. Methods for forming a pattern include a pattern formation method using photolithography and a pattern formation method using etching.

[0224] The pattern formation by photolithography preferably includes the steps of: applying the composition of the present invention to a support to form a composition layer; exposing the composition layer in a patterned manner; and developing and removing the unexposed parts of the composition layer to form a pattern. If necessary, a step of baking the composition layer (pre-bake step) and a step of baking the developed pattern (post-bake step) may be provided.

[0225] In the step of forming the composition layer, the composition of the present invention is applied to a support to form the composition layer. Examples of the support include the support described above. Examples of the application method for the composition include the application method described above.

[0226] The composition layer formed on the support may be dried (pre-baked). When pre-baking is performed, the pre-baking temperature is 150°C or lower, preferably 120°C or lower, and more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher. The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, oven, etc.

[0227] Next, the composition layer is exposed in a pattern (exposure step). For example, the composition layer can be exposed in a pattern by using a stepper exposure machine or a scanner exposure machine to expose it through a mask having a predetermined mask pattern. This allows the exposed areas to be cured.

[0228] Examples of light that can be used for exposure include g-line and i-line light. Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), with KrF line (wavelength 248 nm) being preferred. Long-wave light sources with wavelengths of 300 nm or more can also be used.

[0229] Furthermore, exposure may be performed by continuously irradiating with light, or by irradiating in pulses (pulsed exposure). Pulsed exposure is an exposure method that involves repeatedly irradiating and pausing with light in short cycles (for example, at the millisecond level or less).

[0230] The irradiation dose (exposure dose) is, for example, 0.03 to 2.5 J / cm². 2 Preferably, 0.05 to 1.0 J / cm² 2This is more preferable. The oxygen concentration during exposure can be appropriately selected. In addition to exposure in air, exposure may be carried out in a low-oxygen atmosphere with an oxygen concentration of 19 vol% or less (e.g., 15 vol%, 5 vol%, or substantially oxygen-free), or in a high-oxygen atmosphere with an oxygen concentration exceeding 21 vol% (e.g., 22 vol%, 30 vol%, or 50 vol%). Furthermore, the exposure intensity can be appropriately set, usually 1000 W / m². 2 ~100,000 W / m 2 (For example, 5000W / m 2 , 15000W / m 2 , or 35000W / m 2 The oxygen concentration and exposure intensity can be combined as appropriate; for example, an oxygen concentration of 10% by volume and an illuminance of 10,000 W / m². 2 At an oxygen concentration of 35% by volume, the illuminance is 20,000 W / m². 2 This can be done as follows.

[0231] Next, the unexposed areas of the composition layer are developed and removed to form a pattern. The development and removal of the unexposed areas of the composition layer can be done using a developer. This causes the unexposed areas of the composition layer in the exposure process to dissolve in the developer, leaving only the photocured parts. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, to improve the removal of residue, the developer may be emptied every 60 seconds, and the process of supplying fresh developer may be repeated several times.

[0232] Examples of developing solutions include organic solvents and alkaline developers, with alkaline developers being preferred. As the alkaline developer, an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferred. Examples of alkaline agents include organic alkaline compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene, as well as inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. Alkaline agents with larger molecular weights are preferred from an environmental and safety perspective. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The developer may also contain a surfactant. For convenience of transport and storage, the developer may be manufactured as a concentrated solution and then diluted to the required concentration at the time of use. The dilution ratio is not particularly limited, but can be set in the range of 1.5 to 100 times, for example. It is also preferable to wash (rinse) with pure water after development. It is preferable to supply the rinsing solution to the developed composition layer while rotating the support on which the developed composition layer has formed. It is also preferable to move the nozzle that discharges the rinsing solution from the center of the support to the periphery of the support. In this case, when moving the nozzle from the center to the periphery of the support, the speed of movement of the nozzle may be gradually reduced. By performing rinsing in this manner, in-plane variation of the rinse can be suppressed. A similar effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the center to the periphery of the support.

[0233] After development and drying, additional exposure treatment or heat treatment (post-bake) may be performed.

[0234] When performing post-bake, the post-bake temperature is preferably 150°C or lower. The upper limit of the post-bake temperature is more preferably 120°C or lower, and even more preferably 100°C or lower. The lower limit of the post-bake temperature is not particularly limited as long as it can promote the curing of the film, but it is preferably 50°C or higher, and more preferably 75°C or higher. The post-bake time is preferably 1 minute or longer, more preferably 5 minutes or longer, and even more preferably 10 minutes or longer. The upper limit is not particularly limited, but from the perspective of productivity, it is preferably 20 minutes or shorter.

[0235] When performing additional exposure treatment, the light used for exposure is preferably light with a wavelength of 400 nm or shorter. Also, the additional exposure treatment may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

[0236] Pattern formation by an etching method includes the steps of applying the composition of the present invention to a support and forming a cured product layer, which is the cured film of the present invention, on the support using the above-described method for producing the cured film of the present invention; forming a photoresist layer on this cured product layer; exposing the photoresist layer in a pattern and then developing to form a resist pattern; etching the cured product layer using this resist pattern as a mask; and peeling and removing the resist pattern from the cured product layer.

[0237] The resist used to form the resist pattern is not particularly limited, but for example, a resist containing an alkali-soluble phenolic resin and naphthoquinone diazide, as described on pages 16 to 22 of the book "Polymer New Materials One Point 3 Microfabrication and Resists" (Author: Saburo Nonogaki, Publisher: Kyoritsu Shuppan Co., Ltd., First Edition, First Printing, November 15, 1987), can be used. In addition, resists described in the examples of Japanese Patent Publication No. 2568883, No. 2761786, No. 2711590, No. 2987526, No. 3133881, No. 3501427, No. 3373072, No. 3361636, and Japanese Patent Application Publication No. 06-054383 can also be used. Furthermore, so-called chemically amplified resists can also be used as the resist. Regarding chemically amplified resists, for example, we can refer to the resists described on page 129 onwards of "New Developments in Photo-Functional Polymer Materials, First Edition, May 31, 1996, Supervised by Kunihiro Ichimura, Published by CMC Corporation" (particularly preferred are the resists containing resins in which the hydroxyl groups of polyhydroxystyrene resin are protected with acid-degradable groups, as described around page 131, and the ESCAP resist (Environmentally Stable Chemical Amplification Positive Resist), also described around page 131). Furthermore, resists described in the examples of Japanese Patent Publication No. 2008-268875, Japanese Patent Publication No. 2008-249890, Japanese Patent Publication No. 2009-244829, Japanese Patent Publication No. 2011-013581, Japanese Patent Publication No. 2011-232657, Japanese Patent Publication No. 2012-003070, Japanese Patent Publication No. 2012-003071, Japanese Patent Publication No. 3638068, Japanese Patent Publication No. 4006492, Japanese Patent Publication No. 4000407, and Japanese Patent Publication No. 4194249 can also be used.

[0238] The etching method used on the cured layer may be dry etching or wet etching. Dry etching is preferred.

[0239] Dry etching of the cured layer is preferably performed using a mixed gas of fluorine-based gas and O2 as the etching gas. The mixing ratio of fluorine-based gas to O2 (fluorine-based gas / O2) is preferably 4 / 1 to 1 / 5 in terms of flow rate ratio, and more preferably 1 / 2 to 1 / 4. Examples of fluorine-based gases include CF4, C2F6, C3F8, C2F4, C4F8, C4F6, C5F8, CHF3, etc., with C4F6, C5F8, C4F8, and CHF3 being preferred, C4F6 and C5F8 being more preferred, and C4F6 being even more preferred. One gas can be selected from the above group as the fluorine-based gas, and two or more may be included in the mixed gas.

[0240] From the viewpoint of maintaining the stability of partial pressure control of the etching plasma and the perpendicularity of the specific etching shape, the above mixed gas may further contain noble gases such as helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe) in addition to the fluorine-based gas and O2. One or more gases from the above group can be selected as other gases that may be mixed. The mixing ratio of the other gases, when O2 is considered as 1 in flow rate ratio, is preferably greater than 0 and 25 or less, preferably between 10 and 20, and particularly preferably 16.

[0241] The internal pressure of the chamber during dry etching is preferably 0.5 to 6.0 Pa, and more preferably 1 to 5 Pa.

[0242] Regarding dry etching conditions, examples include those described in paragraphs 0102-0108 of International Publication No. 2015 / 190374 and Japanese Patent Publication No. 2016-014856, the details of which are incorporated herein by reference.

[0243] <Structure> Next, the structure of the present invention will be described with reference to the drawings. Figure 2 is a side cross-sectional view showing one embodiment of the structure of the present invention, and Figure 3 is a plan view of the support in the same structure as seen from directly above. As shown in Figures 2 and 3, the structure 100 of the present invention has a support 11, a partition wall 12 provided on the support 11, and pixels 14 provided on the support 11 in a region partitioned by the partition wall 12. Examples of pixels include colored pixels, transparent pixels, pixels with a near-infrared transmission filter layer, and pixels with a near-infrared cut filter layer. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.

[0244] In the structure of the present invention, there are no particular limitations on the type of support 11. Substrates used in various electronic devices such as solid-state image sensors (silicon wafers, silicon carbide wafers, silicon nitride wafers, sapphire wafers, glass wafers, etc.) can be used. In addition, substrates for solid-state image sensors on which photodiodes are formed can also be used. Furthermore, if necessary, an underlayer may be provided on these substrates to improve adhesion with the upper layer, prevent diffusion of materials, or flatten the surface.

[0245] As shown in Figures 2 and 3, partition walls 12 are formed on the support 11. In this embodiment, as shown in Figure 3, the partition walls 12 are formed in a grid pattern in a plan view taken from directly above the support 11. In this embodiment, the shape of the area partitioned by the partition walls 12 on the support 11 (hereinafter also referred to as the shape of the opening of the partition wall) is square, but the shape of the opening of the partition wall is not particularly limited and may be rectangular, circular, elliptical, or polygonal, for example.

[0246] The partition wall 12 can be formed using the composition of the present invention. Specifically, it can be formed by the steps of forming a composition layer using the composition of the present invention and forming a pattern on the composition layer by photolithography or dry etching.

[0247] The width W1 of the partition wall 12 is preferably 20 to 500 nm. The lower limit is preferably 30 nm or more, more preferably 40 nm or more, and even more preferably 50 nm or more. The upper limit is preferably 300 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less. Furthermore, the height H1 of the partition wall 12 is preferably 200 nm or more, more preferably 300 nm or more, and even more preferably 400 nm or more. The upper limit is preferably 200% or less of the thickness of the pixel 14, more preferably 150% or less of the thickness of the pixel 14, and even more preferably substantially the same as the thickness of the pixel 14. The ratio of the height to the width of the partition wall 12 (height / width) is preferably 1 to 100, more preferably 5 to 50, and even more preferably 5 to 30.

[0248] Pixels 14 are formed on the support 11 in areas partitioned by partition walls 12 (openings in the partition walls).

[0249] The width L1 of the pixel 14 can be appropriately selected depending on the application. For example, it is preferably 500 to 2000 nm, more preferably 500 to 1500 nm, and even more preferably 500 to 1000 nm. The height (thickness) H2 of the pixel 14 can be appropriately selected depending on the application. For example, it is preferably 300 to 1000 nm, more preferably 300 to 800 nm, and even more preferably 300 to 600 nm. Furthermore, the height H2 of the pixel 14 is preferably 50 to 150% of the height H1 of the partition wall 12, more preferably 70 to 130%, and even more preferably 90 to 110%.

[0250] In the structure of the present invention, it is also preferable that a protective layer is provided on the surface of the partition wall. By providing a protective layer on the surface of the partition wall 12, the adhesion between the partition wall 12 and the pixels 14 can be improved. Various inorganic and organic materials can be used as the material for the protective layer. For example, examples of organic materials include acrylic resins, polystyrene resins, polyimide resins, and organic SOG (Spin On Glass) resins. It can also be formed using a composition containing a compound having an ethylenically unsaturated bond-containing group.

[0251] The structure of the present invention can be preferably used in optical filters, solid-state image sensors, and image display devices.

[0252] <Optical filters> The optical filter of the present invention has the cured film of the present invention described above. Examples of optical filters having the cured film of the present invention include optical filters in which each pixel is embedded in a region partitioned by a partition made of the film of the present invention. Examples of pixels include colored pixels, transparent pixels, pixels of the near-infrared transmission filter layer, and pixels of the near-infrared cut filter layer.

[0253] The width of the pixels included in the optical filter is preferably 0.4 to 10.0 μm. The lower limit is preferably 0.4 μm or more, more preferably 0.5 μm or more, and even more preferably 0.6 μm or more. The upper limit is preferably 5.0 μm or less, more preferably 2.0 μm or less, even more preferably 1.0 μm or less, and even more preferably 0.8 μm or less. The Young's modulus of the pixels is preferably 0.5 to 20 GPa, and more preferably 2.5 to 15 GPa.

[0254] Each pixel included in the optical filter preferably has high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although the lower limit is not defined, for example, it is preferably 0.1 nm or more. The surface roughness of the pixel can be measured using, for example, an AFM (atomic force microscope) Dimension 3100 manufactured by Veeco. Also, the contact angle of water on the pixel can be set to an appropriate preferable value, but typically, it is in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT·A type (manufactured by Kyowa Interface Science Co., Ltd.). Also, the volume resistivity of the pixel is preferably high. Specifically, the volume resistivity of the pixel is preferably 10 9 Ω·cm or more, and more preferably 10 11 Ω·cm or more. Although the upper limit is not defined, for example, it is preferably 10 14 Ω·cm or less. The volume resistivity of the pixel can be measured using a high resistance meter 5410 (manufactured by Advantest Corporation).

[0255] A protective layer may be provided on the surface of the pixel of the optical filter. By providing the protective layer, various functions such as oxygen barrier, antireflection, hydrophilic / hydrophobic modification, and shielding of light of a specific wavelength (ultraviolet light, near-infrared light, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm. Examples of the method for forming the protective layer include a method of applying a composition for forming the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive. Also, as the protective layer, the protective layer described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.

[0256] <Solid-state imaging device> The solid-state imaging device of the present invention includes the cured film of the present invention described above. The configuration of the solid-state imaging device is not particularly limited as long as it is a configuration that functions as a solid-state imaging device.

[0257] <Image display device> The cured film of the present invention can also be used in image display devices. Examples of image display devices include liquid crystal displays and organic electroluminescent displays. For definitions of image display devices and details of each type of image display device, see, for example, "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990) and "Display Devices" (by Yoshiaki Ibuki, Sangyo Tosho Co., Ltd., published in 1989). Liquid crystal displays are described in, for example, "Next-Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994). There are no particular limitations on the liquid crystal display devices to which the present invention can be applied; for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next-Generation Liquid Crystal Display Technology".

[0258] Furthermore, the organic electroluminescent display device may be a microdisplay. The diagonal length of the display surface of the microdisplay can be, for example, 4 inches or less, 2 inches or less, 1 inch or less, or 0.2 inches or less. There are no particular limitations on the applications of the microdisplay, but examples include electronic viewfinders, smart glasses, and head-mounted displays.

[0259] An organic electroluminescent display device may have a light source made of white organic electroluminescent elements. The white organic electroluminescent elements are preferably in a tandem structure. The tandem structure of organic electroluminescent elements is described in Japanese Patent Publication No. 2003-045676, supervised by Akiyoshi Mikami, "The Cutting Edge of Organic EL Technology Development - High Brightness, High Precision, Long Lifespan, and Know-how Collection," Japan Technical Information Association, pp. 326-328, 2008, etc. The spectrum of white light emitted by the organic EL element is preferably one that has strong maximum emission peaks in the blue region (430nm-485nm), the green region (530nm-580nm), and the yellow region (580nm-620nm). In addition to these emission peaks, it is even more preferable to have a maximum emission peak in the red region (650nm-700nm).

[0260] An organic electroluminescent display device may have a color filter. The color filter may be provided on a substrate layer. In an organic electroluminescent display device that extracts light of the three primary colors by combining a color filter and a white organic electroluminescent element, a transparent pixel may be provided to directly utilize white light for emission. This can increase the brightness of the display device. An organic electroluminescent display device may also have a lens on the color filter. The shape of the lens can be various shapes derived from the optical system design, such as a convex shape or a concave shape. For example, a concave shape (concave lens) makes it easier to improve the light-gathering ability. The lens may be in direct contact with the color filter, or other layers such as an adhesion layer or a planarization layer may be provided between the lens and the color filter. The lens may also be used in the manner described in International Publication No. 2018 / 135189. [Examples]

[0261] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0262] <Production of the composition> The raw materials listed in the table below were mixed and filtered using a DFA4201NIEY (0.45 μm nylon filter) manufactured by Nippon Pall to produce the composition.

[0263] [Table 1]

[0264] [Table 2]

[0265] [Table 3]

[0266] [Table 4]

[0267] [Table 5]

[0268] [Table 6]

[0269] [Table 7]

[0270] [Table 8]

[0271] [Table 9]

[0272] The details of the ingredients listed in the table above, indicated by abbreviations, are as follows:

[0273] [Silica particle liquid] P1: A propylene glycol monomethyl ether solution (silica particle concentration 20% by mass) containing silica particles (beaded silica) in which multiple spherical silica particles with an average particle diameter of 15 nm are linked together in a bead-like manner by metal oxide-containing silica (binding material). P2: Through-Ria 4110 (manufactured by JGC Catalysts & Chemicals Co., Ltd., a silica particle liquid with a hollow structure and an average particle diameter of 60 nm, silica particle concentration of 20% by mass. This silica particle liquid does not contain silica particles in which multiple spherical silica particles are linked in a bead-like manner, nor silica particles in which multiple spherical silica particles are linked in a planar manner.) P3: MIBK-ST (Manufactured by Nissan Chemical Industries, Ltd., solid silica particle liquid with an average particle diameter of 15 nm, silica particle concentration of 20% by mass. This silica particle liquid does not contain silica particles in which multiple spherical silica particles are linked in a bead-like manner, silica particles in which multiple spherical silica particles are linked in a planar manner, or silica particles with a hollow structure.)

[0274] Furthermore, all silica particles contained in silica particle liquids P1 to P3 are particles that contain silanol groups. Furthermore, in silica particle liquid P1, the average particle size of spherical silica was determined by calculating the number average of the equivalent circle diameters in the projection images of the spherical portions of 50 spherical silica particles measured by transmission electron microscopy (TEM). In addition, in silica particle liquid P1, it was investigated using TEM observation to determine whether it contained silica particles in a bead-like structure with multiple spherical silica particles linked together.

[0275] [Acid generators, base generators] B-1: IRGACURE PAG-103 (manufactured by BASF, compound with the structure shown below, oxime sulfonate compound, photoacid generator) [ka] B-2: WPBG-018 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., a compound with the structure shown below, a carbamate compound, a photobase generator) [ka] B-3: MOP-triazine (manufactured by Sanwa Chemical Co., Ltd., a compound with the structure shown below, a triazine compound, a photoacid generator) [ka] B-4: WPBG-165 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., a compound with the structure shown below, a carbamate compound, a photobase generator) [ka] B-5: San-Aid SI-60 (manufactured by Sanshin Chemical Industry Co., Ltd., SbF6) - (Sulfonium salts, thermal acid generators) B-6: U-CAT SA1 (Manufactured by Sunapro Co., Ltd., a compound with the structure shown below, a quaternary ammonium salt, a thermobase generator) [ka] B-7:SI-106 (Midori Chemical Co., Ltd., N-(camphasulfonyloxy)succinimide, sulfonimide compound, thermoacid generator)

[0276] [resin] C-1: Cyraplane FM-DA21 (manufactured by JNC Corporation, number average molecular weight 5000, resin with the structure shown below) [ka] C-2: Cyraplane FM-3321 (manufactured by JNC Corporation, number average molecular weight 5000, resin with the structure shown below) [ka] C-3: Polysiloxane resin solution prepared by the following method 74.23 g (0.55 mol) of methyltrimethoxysilane, 69.41 g (0.35 mol) of phenyltrimethoxysilane, 21.82 g (0.1 mol) of trifluoropropyltrimethoxysilane, and 132.4 g of diacetone alcohol were charged into a 500 mL three-necked flask. An aqueous solution of phosphoric acid, prepared by dissolving 0.319 g of phosphoric acid in 52.02 g of water, was added over 30 minutes while stirring at room temperature. The flask was then immersed in a 40°C oil bath and stirred for 30 minutes, after which the oil bath was heated to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100°C, and it was heated and stirred for another 35 minutes (internal temperature 100-110°C). Diacetone alcohol was added to the obtained polysiloxane resin diacetone alcohol solution to obtain a polysiloxane resin solution with a polysiloxane concentration of 40% by mass. The weight-average molecular weight of the obtained polysiloxane resin was 4300.

[0277] [Silanol compounds] D-1:X-12-1135 (manufactured by Shin-Etsu Chemical Co., Ltd., a compound with a molecular weight of 1000 or less) D-2: KBP-90 (manufactured by Shin-Etsu Chemical Co., Ltd., a compound with a molecular weight of 1000 or less)

[0278] [Silane coupling agent] E-1: KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd., a compound with the structure shown below, a compound containing an alkoxysilyl group) E-2: KBM-4803 (manufactured by Shin-Etsu Chemical Co., Ltd., a compound with the structure shown below, a compound containing an alkoxysilyl group) E-3: KBM-3086 (manufactured by Shin-Etsu Chemical Co., Ltd., a compound with the structure shown below, a compound containing an alkoxysilyl group) E-4: KBM-9659 (manufactured by Shin-Etsu Chemical Co., Ltd., a compound with the structure shown below, a compound containing an alkoxysilyl group) E-5:X-12-5263HP (manufactured by Shin-Etsu Chemical Co., Ltd., a compound with the following structure, a compound having an alkoxysilyl group) [ka]

[0279] [Surfactants] F-1: Compound with the following structure (silicone-based surfactant, carbinol-modified silicone compound. Weight-average molecular weight 3000, kinematic viscosity at 25°C 45 mmHg). 2 / s) [ka] F-2: Compound with the following structure (fluorinated surfactant, weight-average molecular weight 14000, the percentage indicating the proportion of repeating units is in mole percent) [ka]

[0280] [solvent] S-1: 1,4-Butanediol diacetate (boiling point 232°C, viscosity 3.1 mPa·s, molecular weight 174) S-2: Propylene glycol monomethyl ether acetate (boiling point 146°C, viscosity 1.1 mPa·s, molecular weight 132) S-3: Propylene glycol monomethyl ether (boiling point 120°C, viscosity 1.8 mPa·s, molecular weight 90) S-4: Methanol (boiling point 64°C, viscosity 0.6 mPa·s) S-5: Ethanol (boiling point 78°C, viscosity 1.2 mPa·s) S-6: Water (boiling point 100℃, viscosity 0.9mPa·s)

[0281] <Evaluation of refractive index> For the compositions of Examples 1-9 and 12-23, each composition was applied by spin coating onto an 8-inch (20.32 cm) diameter silicon wafer to a film thickness of 0.4 μm. Then, exposure was performed using an ultra-high pressure mercury lamp at an irradiance of 20 mW / cm². 2 Exposure dose 1000 mJ / cm² 2 The sample was exposed to light under the specified conditions. Next, it was heated on a 100°C hot plate for 20 minutes, then allowed to cool to form a cured film. For the compositions of Examples 10, 11, 24, 25 and Comparative Examples 1 and 2, the compositions were spin-coated on a silicon wafer with a diameter of 8 inches (20.32 cm) so that the film thickness after coating was 0.4 μm. Then, it was heated on a hot plate at 100 °C for 20 minutes and allowed to cool to form a cured film. The refractive index of the obtained cured film for light with a wavelength of 633 nm was measured using an ellipsometer (manufactured by J.A. Woollam, VUV-vase) (measurement temperature: 25 °C), and the refractive index was evaluated according to the following criteria. 5: The refractive index is 1.300 or less 4: The refractive index exceeds 1.300 and is 1.350 or less 3: The refractive index exceeds 1.350 and is 1.400 or less 2: The refractive index exceeds 1.400 and is 1.450 or less 1: The refractive index exceeds 1.450

[0282] <Evaluation of moisture resistance> For the compositions of Examples 1 to 9, 12 to 23, and 26 to 38, each composition was spin-coated on a silicon wafer with a diameter of 8 inches (20.32 cm) so that the film thickness after coating was 0.4 μm. Then, using an ultra-high pressure mercury lamp, it was exposed under the conditions of an exposure illuminance of 2 20 mW / cm 2 and an exposure dose of <耐湿性の評価>1000 mJ / cm 2 . Then, it was heated on a hot plate at 100 °C for 20 minutes and allowed to cool to form a cured film. For the compositions of Examples 10, 11, 24, 25 and Comparative Examples 1 and 2, the compositions were spin-coated on a silicon wafer with a diameter of 8 inches (20.32 cm) so that the film thickness after coating was 0.4 μm. Then, it was heated on a hot plate at 100 °C for 20 minutes and allowed to cool to form a cured film. The obtained cured film was subjected to a moisture resistance test for 168 hours under the conditions of a temperature of 130 °C and a humidity of 85% using a highly accelerated life test device (manufactured by ESPEC, EHS-212). The refractive index of the cured film for light with a wavelength of 633 nm before and after the moisture resistance test was measured using an ellipsometer (manufactured by J.A. Woollam, VUV-vase) (measurement temperature: 25 °C), and the change amount of the refractive index of the cured film before and after the moisture resistance test was calculated, and the moisture resistance was evaluated according to the following criteria. Change in refractive index = |Refractive index of the cured film before the humidity test - Refractive index of the cured film after the humidity test| 5: Change in refractive index is 0.005 or less. 4: The change in refractive index is greater than 0.005 and less than or equal to 0.010. 3: The change in refractive index is greater than 0.010 and less than or equal to 0.020. 2: The change in refractive index is greater than 0.020 and less than or equal to 0.030. 1: The change in refractive index exceeds 0.030.

[0283] The evaluation results described above are shown in the table below. In addition, the content of silica particles in the total solid content of the composition is indicated in the "Silica Particle Content" column of the table below. In addition, the content of acid generators or base generators in the total solid content of the composition is indicated in the "Acid Generator or Base Generator Content" column. [Table 10]

[0284] As shown in the table above, all of the examples were able to form cured films with reduced moisture resistance compared to the comparative examples. For the compositions of Examples 26 to 38, a silicon wafer with a diameter of 8 inches was coated by spin coating to a film thickness of 0.4 μm. Then, exposure was performed using an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon Inc.) through a mask having an island pattern aperture of 100 μm × 100 μm. Next, paddle development was performed at 23°C for 60 seconds using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide. After that, rinsing was performed with a spin shower and then washed with pure water. Next, the wafer was heated on a hot plate at 100°C for 15 minutes and allowed to cool to form a 100 μm × 100 μm island pattern, and a good pattern was formed.

[0285] <Manufacturing of color filters> The composition of Example 1 was applied to the surface of an 8-inch (20.32 cm) diameter silicon wafer by spin coating, then heated on a hot plate at 90°C for 120 seconds (pre-baking), and then exposed to 1000 mJ / cm² using an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon Inc.). 2 The material was irradiated with a certain exposure dose and heated at 100°C for 1200 seconds (post-bake) to form a partition material layer with a thickness of 1.2 μm. On this partition material layer, a KrF-compatible positive photoresist was applied using a spin coater and heated at 100°C for 2 minutes to form a photoresist layer with a thickness of 1.0 μm. Next, the corresponding area was scanned using a KrF scanner at 30 mJ / cm². 2 After exposure in a patterned manner with the specified exposure dose, the material was heat-treated at 110°C for 1 minute. Subsequently, it was developed with a developer for 1 minute, followed by a post-bake treatment at 100°C for 1 minute to remove the photoresist from the areas where the partitions were to be formed. Next, the partition material layer was treated under the following dry etching conditions to form partitions with a width of 0.6 μm in a grid pattern with a pitch width of 3.6 μm. The width of the partition openings was 3.0 μm. Note that the pitch width of the partitions is the sum of the width of the partition openings and the width of the partitions. -Dry etching conditions- Equipment used: Hitachi High-Technologies Corporation U-621 Pressure: 2.0 Pa Gas used: Ar / C4F6 / O2 = 1000 / 20 / 50 mL / min Processing temperature: 20℃ Power source: 500W Upper bias / Electrode bias = 500 / 1000W Processing time: 220 seconds

[0286] Next, a green pixel-forming coloring composition was applied to the silicon wafer with these partitions formed on it and to the surface of the partitions by spin coating so that the film thickness after deposition was 1.2 μm. Then, it was heated at 90°C for 120 seconds using a hot plate. Next, using an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed at 200 mJ / cm² through a patterned mask. 2The samples were exposed to light at the specified exposure level. Next, paddle development was performed at 23°C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide. After that, the samples were rinsed with a spin shower and then washed with pure water. Next, a green colored pattern (green pixels) was formed by heating on a hot plate at 100°C for 900 seconds. Similarly, the samples were sequentially patterned using a coloring composition for red pixels and a coloring composition for blue pixels to form red colored patterns (red pixels) and blue colored patterns (blue pixels), respectively, and color filters were manufactured. For green pixel formation, the following coloring compositions were used: Green Pixel Formation Coloring Composition 1, Green Pixel Formation Coloring Composition 2, or Green Pixel Formation Coloring Composition 3. For red pixel formation, the following coloring compositions were used: Red Pixel Formation Coloring Composition 1 or Red Pixel Formation Coloring Composition 2. For blue pixel formation, the following coloring composition was used: Blue Pixel Formation Coloring Composition 1. The obtained color filter was incorporated into an organic electroluminescent display device according to a known method. This organic electroluminescent display device exhibited suitable image recognition capabilities.

[0287] (Coloring composition 1 for green pixel formation) The following components were mixed and stirred, then filtered through a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a coloring composition 1 for green pixel formation. Green pigment dispersion 1 ···76.80 parts by mass Photopolymerization initiator 1 ···0.97 parts by mass Photopolymerization initiator 2 ···0.58 parts by mass Resin solution 1...1.57 parts by mass Polymerizable compound 1...0.97 parts by mass Polymerizable compound 2...0.97 parts by mass Surfactant 1 ···0.001 parts by mass Cyclohexanone ···18.14 parts by mass

[0288] (Coloring composition for green pixel formation 2) A coloring composition 2 for green pixel formation was prepared in the same manner as coloring composition 1 for green pixel formation, except that the green pigment dispersion 1 of coloring composition 1 was replaced with a green pigment dispersion 2.

[0289] (Coloring composition 3 for green pixel formation) A coloring composition 3 for green pixel formation was prepared in the same manner as coloring composition 1 for green pixel formation, except that the green pigment dispersion 1 in coloring composition 1 for green pixel formation was replaced with a green pigment dispersion 3.

[0290] (Coloring composition 1 for forming red pixels) The following components were mixed and stirred, then filtered through a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a coloring composition 1 for red pixel formation. Red pigment dispersion 1 ···60.31 parts by mass Photopolymerization initiator 1 ···0.83 parts by mass Photopolymerization initiator 2 ···0.58 parts by mass Resin solution 1...3.26 parts by mass Polymerizable compound 1...0.83 parts by mass Polymerizable compound 2...0.83 parts by mass Surfactant 1 ···0.004 parts by mass Propylene glycol monomethyl ether ··· 16.68 parts by mass Cyclopentanone ···16.68 parts by mass

[0291] (Coloring composition for red pixel formation 2) A coloring composition 2 for forming red pixels was prepared in the same manner as coloring composition 1 for forming red pixels, except that the red pigment dispersion 1 of coloring composition 1 was replaced with a red pigment dispersion 2.

[0292] (Coloring composition 1 for blue pixel formation) The following components were mixed and stirred, then filtered through a nylon filter with a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.) to prepare a coloring composition 1 for blue pixel formation. Blue pigment dispersion 1 ···56.7 parts by mass Purple dye solution 1...16.28 parts by mass Photopolymerization initiator 3 ··· 1.19 parts by mass Photopolymerization initiator 2 ···0.64 parts by mass Resin solution 1...0.93 parts by mass Polymerizable compound 3...2.97 parts by mass Epoxy compound 1 ··· 1.40 parts by mass Surfactant 1 ···0.006 parts by mass Cyclohexanone ···19.89 parts by mass

[0293] The materials used in each pixel-forming coloring composition are as follows:

[0294] Green pigment dispersion 1: Green pigment dispersion 1 prepared by the following method A mixture consisting of 7.59 parts by mass of CIPigment Green 36, 4.41 parts by mass of CIPigment Yellow 185, 1.33 parts by mass of pigment derivative 1, 6.77 parts by mass of dispersant 1, and 80.00 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was mixed and dispersed for 3 hours using a bead mill (zirconia beads, 0.3 mm diameter) to prepare a pigment dispersion. Subsequently, the dispersion was further processed using a high-pressure disperser with a vacuum mechanism, NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.), at a pressure of 2000 kg / cm³. 2 The dispersion treatment was carried out under pressure at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain green pigment dispersion 1. Pigment derivative 1: Compound with the following structure [ka] Dispersant 1: Resin with the following structure (the numbers in parentheses in the main chain represent the molar ratio of each repeating unit, and the numbers in parentheses in the side chain represent the number of repeats in the repeating unit. The weight-average molecular weight is 20,000.) [ka]

[0295] Green pigment dispersion 2: Green pigment dispersion 2 prepared by the following method A mixture consisting of 1.31 parts by mass of CIPigment Green 36, 3.03 parts by mass of CIPigment Green 7, 1.24 parts by mass of CIPigment Blue 15:4, 2.32 parts by mass of CIPigment Yellow 185, 0.35 parts by mass of CIPigment Yellow 150, 3.74 parts by mass of CIPigment Yellow 139, 1.33 parts by mass of pigment derivative 1, 6.77 parts by mass of dispersant 1, and 80.00 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads, 0.3 mm diameter) to prepare a pigment dispersion. Subsequently, the dispersion was further processed using a high-pressure disperser with a vacuum mechanism, NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.), at a pressure of 2000 kg / cm³. 2 The dispersion treatment was carried out under pressure at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain green pigment dispersion 2.

[0296] Green pigment dispersion 3: Green pigment dispersion 3 prepared by the following method A mixture consisting of 5.81 parts by mass of CIPigment Green 36, 1.64 parts by mass of CIPigment Blue 15:4, 1.94 parts by mass of CIPigment Yellow 185, 2.61 parts by mass of CIPigment Yellow 139, 1.33 parts by mass of pigment derivative 1, 6.77 parts by mass of dispersant 1, and 80.00 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads, 0.3 mm diameter) to prepare a pigment dispersion. Subsequently, the dispersion was further processed using a high-pressure disperser with a vacuum mechanism, NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.), at a pressure of 2000 kg / cm³. 2 The dispersion treatment was carried out under pressure at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain green pigment dispersion 3.

[0297] Red pigment dispersion 1: Red pigment dispersion 1 prepared by the following method A mixture consisting of 10.68 parts by mass of CIPigment Red 254, 2.82 parts by mass of CIPigment Yellow 139, 1.50 parts by mass of pigment derivative 1, 5.25 parts by mass of dispersant 1, and 80.00 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads, 0.3 mm diameter) to prepare a pigment dispersion. Subsequently, the dispersion was further processed using a high-pressure disperser with a vacuum mechanism, NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.), at a pressure of 2000 kg / cm³. 2 The dispersion treatment was carried out under pressure at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain red pigment dispersion 1.

[0298] Red pigment dispersion 2: Red pigment dispersion 2 prepared by the following method A mixture consisting of 10.68 parts by mass of CIPigment Red 264, 2.82 parts by mass of CIPigment Yellow 139, 1.50 parts by mass of pigment derivative 1, 5.25 parts by mass of dispersant 1, and 80.00 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads, 0.3 mm diameter) to prepare a pigment dispersion. Subsequently, the dispersion was further processed using a high-pressure disperser with a vacuum mechanism, NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.), at a pressure of 2000 kg / cm³. 2 The dispersion treatment was carried out under pressure at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain red pigment dispersion 2.

[0299] Blue pigment dispersion 1: Blue pigment dispersion 1 prepared by the following method A mixture consisting of 10.00 parts by mass of CIPigment Blue 15:6, 3.50 parts by mass of dispersant 2, and 86.50 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads, 0.3 mm diameter) to prepare a pigment dispersion. Subsequently, the dispersion was further processed using a high-pressure disperser with a vacuum mechanism, NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.), at a pressure of 2000 kg / cm³. 2 The dispersion treatment was carried out under pressure at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain blue pigment dispersion 1. Dispersant 2: Resin with the following structure (the numbers in parentheses in the main chain represent the molar ratio of each repeating unit. The weight-average molecular weight is 11000.) [ka]

[0300] Purple dye solution 1: 20% by mass cyclohexanone solution of the dye with the following structure (in the structural formula shown below, iPr is an isopropyl group) [ka]

[0301] Photopolymerization initiator 1: Irgacure OXE03 (manufactured by BASF) Photopolymerization initiator 2: Omnirad 2959 (manufactured by IGM Resins BV) Photopolymerization initiator 3: Compound with the following structure [ka] Resin Solution 1: A 40% by mass PGMEA solution of a resin with the following structure (weight-average molecular weight 11000, the values ​​appended to the main chain are molar ratios). [ka] Polymerizable compound 1: A compound with the following structure [ka] Polymerizable compound 2: Compound with the following structure [ka] Polymerizable compound 3: Compound with the following structure [ka] Epoxy compound 1: EHPE3150 (manufactured by Daicel Corporation) Surfactant 1: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., silicone-based surfactant) [Explanation of symbols]

[0302] 1: Spherical silica, 2: Joint, 11: Support, 12: Partition, 14: Pixel, 100: Structure

Claims

1. Particles having a silanol group, At least one generating agent selected from the group consisting of acid generating agents and base generating agents, A composition comprising a solvent, The silica particles include at least one selected from the group consisting of silica particles in which a plurality of spherical silica particles are linked together in a bead-like manner, and silica particles in which a plurality of spherical silica particles are linked together in a planar manner. The content of the particles having the silanol group in the total solid content of the composition is 90% by mass or more. A composition wherein the content of the generating agent in the total solid content of the composition is 2.5 to 9% by mass.

2. The aforementioned generating agent is an acid generating agent. The composition according to claim 1, wherein the acid generating agent comprises a photoacid generating agent.

3. The composition according to claim 2, wherein the photoacid generator comprises at least one selected from the group consisting of oximesulfonate compounds and triazine compounds.

4. The aforementioned generating agent is a base generating agent. The composition according to claim 1, wherein the base generating agent comprises a photobase generating agent.

5. The composition according to claim 4, wherein the photobase generator comprises at least one selected from the group consisting of carbamate compounds and acyloxime compounds.

6. Furthermore, the composition according to any one of claims 1 to 5, comprising a silanol compound with a molecular weight of 1000 or less.

7. Furthermore, the composition according to any one of claims 1 to 5, comprising a surfactant.

8. Furthermore, the composition according to any one of claims 1 to 5, comprising a compound having an alkoxysilyl group.

9. The composition according to any one of claims 1 to 5, wherein the resin content in the total solid content of the composition is 0.1% by mass or less.

10. The composition according to any one of claims 1 to 5, which is a composition for forming a member adjacent to a pixel in an optical filter having a plurality of pixels.

11. A composition for forming a partition wall, according to any one of claims 1 to 5.

12. The composition according to any one of claims 1 to 5, wherein when the composition is applied to a silicon wafer and heated at 100°C for 5 minutes to form a film with a thickness of 0.4 μm, the refractive index of the film at a wavelength of 633 nm is 1.4 or less.

13. A cured film obtained from the composition according to any one of claims 1 to 5.

14. Support and A partition wall provided on the support, obtained from the composition according to any one of claims 1 to 5, A structure having pixels provided in a region partitioned by the aforementioned partition wall.

15. An optical filter having a cured film as described in claim 13.

16. A solid-state image sensor having the cured film described in claim 13.

17. An image display device having a cured film according to claim 13.

18. A step of applying the composition according to any one of claims 1 to 5 onto a support to form a composition layer, The process includes curing the aforementioned composition layer, A method for producing a cured film, wherein the composition layer is cured at a temperature of 150°C or lower throughout the entire process, The step of curing the composition layer includes a step of generating an acid or a base from an acid generator or a base generator contained in the composition layer by irradiating the composition layer with light or heating it. A method for manufacturing a cured film.

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