Dispersion liquid, composition, cured film, color filter, solid-state imaging element, and image display device

Abstract

The present invention provides a dispersion having excellent storage stability, a composition containing the dispersion, a cured film obtained using the dispersion, a color filter, a solid-state imaging element, and an image display device. The dispersion contains: A1 )(X A1 )3 and the compound represented by the formula Si(R A2 )(R A20 )(X A2 ) 2 represents at least one of the compounds subjected to surface treatment of inorganic oxide particles; having the formula [R B1 SiO 3 / 2 ] and the T unit represented by the formula [R B2 R B20 SiO] represents at least one D unit of polysiloxane; and an organic solvent, the content of the polysiloxane relative to the total amount of the inorganic oxide particles and the polysiloxane is 0.5 to 39% by mass. In the formula, R A1 、R A2 、R B1 、R B2 represents a functional group, X A1 、X A2 represents a hydroxyl group or a hydrolyzable group, R A20 、R B20 represents an alkyl group or an aryl group.

Description

Technical Field

[0001] The present invention relates to a dispersion liquid, a composition, a cured film, a color filter, a solid-state imaging element, and an image display device. Background Art

[0002] Dispersions of inorganic oxide particles, such as silica particles, dispersed in organic solvents have been used in various applications. For example, Patent Document 1 discloses the use of an insulating film-forming composition containing silica particles, polysiloxane, and an organic solvent to form an insulating film having mechanical properties and insulating properties.

[0003] Previous technical literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2005-184011 Summary of the Invention

[0006] Technical issues to be solved by the invention

[0007] The present inventors studied a dispersion containing inorganic oxide particles, polysiloxane, and an organic solvent with reference to the composition described in Patent Document 1. As a result, they found that the viscosity of the dispersion changes over time and that the storage stability of the dispersion has room for improvement.

[0008] Therefore, the present invention aims to provide a dispersion having excellent storage stability and a composition containing the dispersion. Furthermore, the present invention aims to provide a cured film, a color filter, a solid-state imaging element, and an image display device obtained using the composition.

[0009] Means for solving technical problems

[0010] As a result of intensive research to achieve the above-mentioned problems, the present inventors have discovered that, in a dispersion containing inorganic oxide particles, polysiloxane, and an organic solvent, when inorganic oxide particles surface-treated with a predetermined compound and polysiloxane containing predetermined units are used, and when the content of the polysiloxane relative to the total amount of the inorganic oxide particles and polysiloxane is within a predetermined range, a dispersion having excellent storage stability can be obtained, leading to the completion of the present invention.

[0011] That is, the present inventors have discovered that the above-mentioned problems can be solved by the following configuration. [1]

[0013] A dispersion comprising:

[0014] Inorganic oxide particles obtained by surface treatment with at least one compound selected from the group consisting of a compound represented by the following formula A1 and a compound represented by the following formula A2;

[0015] A polysiloxane having at least one unit selected from the group consisting of a T unit represented by the following formula B1 and a D unit represented by the following formula B2; and

[0016] organic solvents,

[0017] The content of the polysiloxane is 0.5 to 39% by mass relative to the total amount of the inorganic oxide particles and the polysiloxane.

[0018] Formula A1 Si(R A1 )(X A1 )3

[0019] Formula A2 Si(R A2 )(R A20 )(X A2 )2

[0020] Formula B1 [R B1 SiO 3 / 2 ]

[0021] Formula B2 [R B2 R B20 SiO]

[0022] In the above formula A1, R A1 represents a monovalent functional group, X A1 represents a hydroxyl group or a monovalent hydrolyzable group. A1 They may be the same as or different from each other.

[0023] In the above formula A2, R A2 Represents a monovalent functional group, R A20 represents an alkyl or aryl group, X A2 In the above formula A2, two X A2 They may be the same as or different from each other.

[0024] In the above formula B1, R B1 It represents a monovalent functional group.

[0025] In the above formula B2, R B2 Represents a monovalent functional group, R B20 represents an alkyl group or an aryl group. [2]

[0027] The dispersion according to [1], wherein the content of the polysiloxane is 1 to 25% by mass relative to the total amount of the inorganic oxide particles and the polysiloxane. [3]

[0029] The dispersion according to [1] or [2], further comprising water,

[0030] The content of the water is 0.01 to 5% by mass relative to the total mass of the dispersion. [4]

[0032] The dispersion according to [3], wherein the content of the water is 0.1 to 3% by mass relative to the total mass of the dispersion. [5]

[0034] The dispersion according to any one of [1] to [4], wherein R A1 、R in the above formula A2 A2 、R in the above formula B1 B1 And R of the above formula B2 B2 Each independently contains at least one group selected from an aliphatic hydrocarbon group, an aryl group, an acryloyloxy group, a methacryloyloxy group, a fluoroalkyl group, a group having a polysiloxane structure, an epoxy group, an amino group, a quaternary ammonium group or a group having a salt thereof, a cyano group, and a thiol group. [6]

[0036] The dispersion according to any one of [1] to [5], wherein R A1 、R in the above formula A2 A2 、R in the above formula B1 B1 And R of the above formula B2 B2 Each independently contains at least one group selected from the group consisting of a fluoroalkyl group and a group having a polysiloxane structure. [7]

[0038] The dispersion according to any one of [1] to [6], wherein the inorganic oxide particles are surface-treated with the compound represented by the formula A1, and the polysiloxane contains the T unit represented by the formula B1.

[0039] R in the above formula A1 A1 R of the above formula B1 B1 are the same group. [8]

[0041] The dispersion according to any one of [1] to [7], wherein the inorganic oxide particles are surface-treated with the compound represented by the formula A2, and the polysiloxane contains the D unit represented by the formula B2.

[0042] R in the above formula A2 A2 With the R of the above formula B2 B2are the same group. [9]

[0044] The dispersion according to any one of [1] to [8], wherein the inorganic oxide particles contain silicon dioxide.

[10]

[0046] The dispersion according to any one of [1] to [9], wherein the inorganic oxide particles are silica particles.

[11]

[0048] A composition comprising the dispersion according to any one of [1] to

[10] and a polymerizable compound.

[12]

[0050] The composition according to

[11] , further comprising a resin.

[13]

[0052] The composition according to

[11] or

[12] , further comprising a polymerization initiator.

[14]

[0054] The composition according to any one of

[11] to

[13] , further comprising a colorant.

[15]

[0056] A cured film formed using the composition according to any one of

[11] to

[14] .

[16]

[0058] A color filter comprising the cured film according to

[15] .

[17]

[0060] A solid-state imaging element comprising the cured film described in

[15] .

[18]

[0062] An image display device comprising the cured film described in

[15] .

[0063] Effects of the Invention

[0064] The present invention provides a dispersion having excellent storage stability and a composition containing the dispersion. Furthermore, the present invention provides a cured film, a color filter, a solid-state imaging element, and an image display device obtained using the composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1 It is a schematic cross-sectional view showing a configuration example of a solid-state imaging device.

[0066] Figure 2 It is an enlarged representation Figure 1Schematic cross-sectional view of an imaging unit included in the solid-state imaging device shown in FIG.

[0067] Figure 3 It is a schematic cross-sectional view showing a configuration example of an infrared sensor.

[0068] Figure 4 It is a schematic diagram showing a configuration example of a headlamp unit.

[0069] Figure 5 It is a schematic perspective view showing a configuration example of a light shielding portion of a headlight unit.

[0070] Figure 6 Schematic diagram showing an example of a light distribution pattern by a light shielding portion of a headlamp unit.

[0071] Figure 7 It is a schematic diagram showing another example of a light distribution pattern by the light shielding portion of the headlamp unit.

[0072] Figure 8 This is a graph showing the transmission spectrum of the black resist film produced in the Example column.

[0073] Figure 9 This is a graph showing the transmission spectrum of the black resist film produced in the Example column.

[0074] Figure 10 This is a graph showing the transmission spectrum of the black resist film produced in the Example column.

[0075] Figure 11 This is a graph showing the reflection spectrum of the black resist film produced in the Example column.

[0076] Figure 12 This is a graph showing the reflection spectrum of the black resist film produced in the Example column.

[0077] Figure 13 This is a graph showing the reflection spectrum of the black resist film produced in the Example column.

[0078] Figure 14 This is a schematic perspective view showing the light-shielding film for fingerprint authentication produced in the Example column.

[0079] Figure 15 This is a schematic end view showing the light-shielding film for fingerprint authentication produced in the Example column.

[0080] Figure 16 This is a schematic perspective view showing the light-shielding film for fingerprint authentication produced in the Example column.

[0081] Figure 17 This is a schematic end view showing the light-shielding film for fingerprint authentication produced in the Example column. DETAILED DESCRIPTION

[0082] Hereinafter, the present invention will be described in detail.

[0083] The description of the constituent elements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0084] In addition, in this specification, the numerical range expressed with "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0085] Furthermore, in the present specification, the term "group (atomic group)" not indicating "substituted" or "unsubstituted" includes both groups without substituents and groups with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).

[0086] In this specification, "active light" or "radiation" refers to, for example, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams. Furthermore, in this specification, "light" refers to both active light and radiation. Unless otherwise specified, "exposure" in this specification includes not only exposure using far ultraviolet light, X-rays, and EUV light, but also drawing using particle beams such as electron beams and ion beams.

[0087] Furthermore, in this specification, "(meth)acrylate" refers to both acrylate and methacrylate. In this specification, "(meth)acrylic acid" refers to both acrylic acid and methacrylic acid. In this specification, "(meth)acryloyl" refers to both acryloyl and methacryloyl. In this specification, "(meth)acrylamide" refers to both acrylamide and methacrylamide. In this specification, "monomer" and "monomer" have the same meaning.

[0088] In this manual, "ppm" means "parts per million (10 -6 ): One in a million (10 -6 )”, “ppb” means “parts per billion (10 -9 ): One billionth (10 -9 )”, “ppt” means “parts per trillion(10 -12 ): one part in a trillion (10 -12 )”.

[0089] In addition, in this specification, the weight average molecular weight (Mw) is a polystyrene conversion value based on the GPC (Gel Permeation Chromatography) method.

[0090] In this specification, the GPC method is based on the following method: using HLC-8020GPC (manufactured by TOSOH CORPORATION), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6 mm ID×15 cm) as columns, and THF (tetrahydrofuran) as an eluent.

[0091] Unless otherwise specified, the bonding direction of a divalent group (e.g., -COO-) indicated in this specification is not limited. For example, in a compound represented by the general formula "XYZ," where Y is -COO-, the compound may be "XO-CO-Z" or "X-CO-OZ."

[0092] In this specification, the "total solid content" of the dispersion liquid means all components other than the solvent when a solvent (organic solvent, water, etc.) is contained.

[0093] In this specification, the "total solids" of a composition refers to the components that form a cured film. If the composition contains a solvent (organic solvent, water, etc.), it refers to all components other than the solvent. Furthermore, liquid components are also considered solids as long as they form a cured film.

[0094] [Dispersion]

[0095] The dispersion of the present invention contains: inorganic oxide particles surface-treated with at least one compound selected from the group consisting of a compound represented by Formula A1 described below (hereinafter also referred to as "Compound A1") and a compound represented by Formula A2 described below (hereinafter also referred to as "Compound A2"); a polysiloxane having at least one unit selected from the group consisting of a T unit represented by Formula B1 described below and a D unit represented by Formula B2 described below; and an organic solvent, wherein the content of the polysiloxane is 0.5 to 39% by mass relative to the total amount of the inorganic oxide particles and the polysiloxane.

[0096] The dispersion of the present invention has excellent storage stability. While the detailed reason for this is not yet clear, it is generally presumed as follows. Specifically, it is presumed that by including a predetermined amount of polysiloxane in a dispersion containing inorganic oxide particles surface-treated with a predetermined compound, the polysiloxane acts as a dispersant, thereby suppressing the aggregation of the inorganic oxide particles over time.

[0097] In the following description, excellent storage stability of the dispersion is also referred to as excellent effect of the present invention.

[0098] 〔Inorganic oxide particles〕

[0099] The dispersion of the present invention contains inorganic oxide particles. The inorganic oxide particles in the present invention are surface-treated with at least one compound selected from Compound A1 and Compound A2.

[0100] In the following description, Compound A1 and Compound A2 may be collectively referred to as "Compound A." Furthermore, inorganic oxide particles surface-treated with Compound A are also referred to as "surface-modified particles." Furthermore, inorganic oxide particles not surface-treated with Compound A are also referred to as "unmodified particles."

[0101] From the viewpoint of achieving more excellent effects of the present invention, the content of the surface-modified particles in the dispersion is preferably 1 to 100% by mass, more preferably 10 to 100% by mass, and even more preferably 20 to 100% by mass relative to the total solid content of the dispersion.

[0102] When the particle size of the surface-modified particles is large, the surface unevenness of the cured film (especially, the light-shielding film) obtained using the composition containing the dispersion tends to become larger, and the low reflectivity of the cured film is more excellent. On the other hand, when the particle size of the inorganic particles is small, since the inorganic particles are more likely to be unevenly present on the surface side of the cured film, it is easy to increase the proportion of the colorant present inside the cured film to make the light-shielding property of the cured film more excellent. From the viewpoint of the excellent balance between the low reflectivity and the light-shielding property of the cured film (especially, the light-shielding film) obtained in this way, the particle size of the inorganic particles is preferably 1 to 200 nm, more preferably 10 to 100 nm, and even more preferably 15 to 78 nm.

[0103] In this specification, the particle size of particles (surface-modified particles or colorants described below) refers to the average primary particle size of the particles measured by the following method. The average primary particle size can be measured using a scanning electron microscope (SEM).

[0104] The maximum length of the particle image obtained using the SEM (Dmax: the maximum length between two points on the particle image outline) and the length perpendicular to the maximum length (DV-max: the shortest length perpendicular to two straight lines parallel to the maximum length when the image is sandwiched) were measured and the average value was multiplied (Dmax × DV-max). 1 / 2 The particle diameters of 100 particles were measured using this method, and the arithmetic mean value was defined as the average primary particle diameter of the particles.

[0105] The refractive index of the surface-modified particles is not particularly limited, but is preferably 1.10 to 1.60, more preferably 1.15 to 1.45, from the viewpoint of achieving excellent low reflectivity of the cured film.

[0106] Furthermore, the surface-modified particles may be hollow particles or solid particles.

[0107] Hollow particles are particles with a cavity inside. Hollow particles can be composed of an internal cavity and a shell surrounding the cavity. Furthermore, hollow particles can be particles with multiple cavities inside.

[0108] Solid particles refer to particles in which substantially no cavity exists inside the particles.

[0109] The porosity of the hollow particles is preferably 3% or more, and the porosity of the solid particles is preferably less than 3%.

[0110] From the viewpoint of achieving more excellent effects of the present invention, the surface-modified particles are preferably hollow particles.

[0111] Since hollow particles have a cavity inside and have a lower specific gravity than particles without a hollow structure, they float on the surface of a coating film formed using the composition, further enhancing the effect of uneven distribution on the surface of the cured film.

[0112] Furthermore, the refractive index of the hollow particles is lower than that of the particles without a hollow structure. For example, in the case of silica composed of hollow particles, since the hollow silica particles have air with a low refractive index (refractive index = 1.0), the refractive index of the particles themselves becomes 1.2 to 1.4, which is significantly lower than that of conventional silica (refractive index = 1.6). Therefore, it is believed that by forming a cured film using a composition containing hollow particles, hollow particles with a low refractive index are unevenly present on the surface of the cured film, obtaining an AR (Anti-Reflection) type low-reflection effect and improving the low reflectivity of the cured film.

[0113] Examples of the hollow particles include hollow silica particles described in Japanese Patent Application Laid-Open No. 2001-233611 and Japanese Patent No. 3272111.

[0114] As the hollow particles, for example, Thrylya 4110 (product name, manufactured by JGC Catalysts and Chemicals Ltd.) can also be used.

[0115] As solid particles, IPA-ST, IPA-ST-L, IPA-ST-ZL, MIBK-ST, MIBK-ST-L, CHO-ST-M, PGM-AC-2140Y, PGM-AC-4130Y (all product names manufactured by NISSAN CHEMICAL CORPORATION) and the like can be used as preferred embodiments.

[0116] Surface-modified particles can be formed by chain-linking a plurality of silica particles, i.e., beaded silica particles. Preferably, the beaded silica particles are formed by linking a plurality of spherical colloidal silica particles having a particle size of 5 to 50 nm through silica containing a metal oxide.

[0117] Examples of the beaded colloidal silica particles include silica sols described in Japanese Patent No. 4328935 and Japanese Patent Application Laid-Open No. 2013-253145.

[0118] The surface-modified particles are preferably not black. The surface-modified particles may have colors such as red, blue, yellow, green, purple, orange, or white, or may be colorless. Among them, the surface-modified particles are preferably white or colorless.

[0119] Examples of the inorganic oxide that constitutes at least a portion of the surface-modified particles include silicon dioxide (silicon oxide), titanium dioxide (titania), aluminum oxide (alumina), zirconium dioxide (zirconium oxide), zinc oxide, and tin oxide. Among these, silicon dioxide, titanium dioxide, and zirconium dioxide are preferred, and silicon dioxide is more preferred, from the perspective of achieving a more excellent effect of the present invention.

[0120] In other words, the surface-modified particles preferably contain silicon dioxide, and more preferably are silicon dioxide particles.

[0121] The surface-modified particles may contain components other than the inorganic oxide. The content of the inorganic oxide in the surface-modified particles is preferably 75 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 99 to 100% by mass relative to the total mass of the surface-modified particles.

[0122] The surface-modified particles can be regarded as particles obtained by surface-treating unmodified particles with Compound A.

[0123] Therefore, generally, when the surface-modified particles are solid particles, the unmodified particles are also solid particles, and when the surface-modified particles are hollow particles, the unmodified particles are also hollow particles.

[0124] Components constituting the unmodified particles include the above-mentioned inorganic oxides, and preferred aspects thereof are the same as those for the surface-modified particles.

[0125] Compound A1 is a compound represented by the following formula A1. Compound A1 is used as a so-called silane coupling agent.

[0126] Formula A1 Si(R A1 )(X A1 )3

[0127] R A1 It represents a monovalent functional group.

[0128] Examples of the monovalent functional group include a group containing at least one group selected from an aliphatic hydrocarbon group, an aryl group, an acryloyloxy group, a methacryloyloxy group, a fluoroalkyl group, a group having a polysiloxane structure, an epoxy group, an amino group, a quaternary ammonium group or a group having a salt thereof, a cyano group, a thiol group, and an oxetanyl group.

[0129] Among these, a group containing at least one group selected from a fluoroalkyl group and a group having a polysiloxane structure is more preferred from the viewpoint that a cured film obtained using a composition containing the dispersion has excellent peeling resistance.

[0130] Examples of the aliphatic hydrocarbon group include an alkyl group and an alkenyl group.

[0131] The number of carbon atoms in the alkyl group is preferably 1 to 25, more preferably 3 to 20, and even more preferably 5 to 18. The alkyl group may have any structure of linear, branched, or cyclic, but is preferably linear in view of further improving the effects of the present invention.

[0132] The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 5. The alkenyl group may have any structure of linear, branched, or cyclic, but is preferably linear from the viewpoint of achieving better effects of the present invention.

[0133] Furthermore, the aliphatic hydrocarbon group may be a norbornene group or a cyclic hydrocarbon group having a bridge structure such as a norbornyl group.

[0134] The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may be a single ring or may have a condensed structure of two or more rings. The aryl group may have a substituent, and examples of the substituent include a vinyl group and a halogen atom.

[0135] The number of carbon atoms in the fluoroalkyl group is preferably 1-10, more preferably 1-5, and even more preferably 1-3.

[0136] The number of carbon atoms in the amino group is preferably 0-20, more preferably 0-10, and even more preferably 0-8.

[0137] Examples of the group having a polysiloxane structure include a group represented by the following formula (S1).

[0138] [Chemical Formula 1]

[0139]

[0140] In formula S1, * represents a bonding position.

[0141] In formula S1, sa represents an integer from 2 to 1000.

[0142] In formula S1, R S3 It represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a group represented by the formula S2 described later.

[0143] In formula S1, there are multiple R S3 They can be the same or different.

[0144] The hydrocarbon group has 1 to 20 carbon atoms, preferably 1 to 10, and more preferably 1 to 5. The carbon number mentioned here refers to the number of carbon atoms counted including the carbon atoms that may be present in the substituents, if the hydrocarbon group contains substituents. The hydrocarbon group is preferably an alkyl group. The alkyl group may be linear or branched. Furthermore, the alkyl group may be entirely cyclic or partially contain cyclic structures.

[0145] Among them, R bonded to Si on the right side of formula S1 S3 Preferably, they are each independently the above-mentioned hydrocarbon group.

[0146] “-(-SiR S3 2-O-) sa -"There are "2×sa" R S3 In the formula S2, the group represented by R S3 The number is preferably 0-1000, more preferably 0-10, and even more preferably 0-2.

[0147] The following shows that R S3 The group represented by formula S2 is represented.

[0148] [Chemical Formula 2]

[0149]

[0150] In formula S2, * represents a bonding position.

[0151] In formula S2, sb represents an integer from 0 to 300.

[0152] In formula S2, R S4 It represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.

[0153] In formula S2, there are multiple R S4 They can be the same or different.

[0154] As can be done by R S4 The hydrocarbon group represented by the above-mentioned R S3 represents a hydrocarbon group of a substituent.

[0155] X A1 represents a hydroxyl group or a monovalent hydrolyzable group, preferably a monovalent hydrolyzable group. A1 They may be the same as or different from each other.

[0156] Examples of the hydrolyzable group include alkoxy groups, aryloxy groups, and halogen atoms. From the perspective of achieving superior effects of the present invention, alkoxy groups and halogen atoms are preferred, with alkoxy groups being more preferred. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 2 carbon atoms. The aryloxy group is preferably an aryloxy group having 6 to 10 carbon atoms. The halogen atom is preferably a chlorine atom.

[0157] Compound A2 is a compound represented by the following formula A2. Compound A2 is used as a so-called silane coupling agent.

[0158] Formula A2 Si(R A2 )(R A20 )(X A2 )2

[0159] R A2 Represents a monovalent functional group, and R in formula A1 A1 have the same meaning.

[0160] R A20 represents an alkyl group or an aryl group, and is preferably an alkyl group from the viewpoint of further improving the effects of the present invention.

[0161] R A20 The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear from the viewpoint of achieving better effects of the present invention.

[0162] R A20 The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, further preferably 6 to 12, and particularly preferably 6 (i.e., phenyl). The aryl group may be a monocyclic ring or may have a condensed ring structure of two or more rings, but is preferably a monocyclic ring.

[0163] X A2 represents a hydroxyl group or a monovalent hydrolyzable group, and X in formula A1A1 In formula A2, 2 X A2 They may be the same as or different from each other.

[0164] Surface-modified particles can be obtained by surface-treating unmodified particles with Compound A.

[0165] The surface treatment method is not particularly limited, and examples include a method of contacting compound A with unmodified particles in the presence of water, and a method of contacting a self-condensate of compound A with unmodified particles in the presence of water. In this case, it can be considered that a layer (coating layer) formed by a reaction (preferably a hydrolysis reaction) of compound A and / or a self-condensate of compound A with an inorganic oxide constituting the unmodified particles is formed on the surface of the surface-modified particles. In other words, the surface-modified particles can be considered to have: particles comprising an inorganic oxide; and a coating layer formed on the surface of the particles comprising the inorganic oxide.

[0166] 〔Polysiloxane〕

[0167] The dispersion of the present invention contains a polysiloxane (hereinafter also referred to as a specific polysiloxane) having at least one unit selected from the group consisting of a T unit represented by the following formula B1 and a D unit represented by the following formula B2.

[0168] The content of the specific polysiloxane is 0.5 to 39 mass % relative to the total amount of the surface-modified particles and the specific polysiloxane, preferably 1 to 25 mass %, and particularly preferably 2 to 20 mass % from the viewpoint of further improving the effects of the present invention.

[0169] From the viewpoint of achieving more excellent effects of the present invention, the weight average molecular weight of the specific polysiloxane is preferably 500 to 30,000, more preferably 1,000 to 20,000, and even more preferably 1,500 to 10,000.

[0170] The T unit that may be contained in the specific polysiloxane is a unit represented by the following formula B1.

[0171] Formula B1 [R B1 SiO 3 / 2 ]

[0172] R B1 Represents a monovalent functional group, and R in formula A1 A1 have the same meaning.

[0173] The D unit that may be contained in the specific polysiloxane is a unit represented by the following formula B2.

[0174] Formula B2 [R B2 R B20 SiO]

[0175] R B2 Represents a monovalent functional group, and R in formula A2 A2 have the same meaning.

[0176] R B20 represents an alkyl group or an aryl group, and R A20 have the same meaning.

[0177] The surface-modified particles are particles surface-treated with compound A1, and when the specific polysiloxane contains a T unit represented by formula B1, it is preferred that R of formula A1 is A1 With R in formula B1 B1 are the same group.

[0178] The surface-modified particles are particles surface-treated with compound A2, and when the specific polysiloxane contains a D unit represented by formula B2, it is preferred that R of formula A2 is A2 With R in formula B2 B2 are the same group.

[0179] Polysiloxane can be obtained, for example, by hydrolyzing and condensing a silane coupling agent in the presence of water. Known silane coupling agents can be used as the silane coupling agent, but from the perspective of achieving better effects of the present invention, at least one compound selected from the above-mentioned compound A1 and compound A2 is preferred.

[0180] [Organic solvent]

[0181] The dispersion of the present invention contains an organic solvent.

[0182] The content of the organic solvent is preferably 10 to 97% by mass relative to the total mass of the dispersion. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 70% by mass or more. The upper limit is preferably 96% by mass or less, more preferably 95% by mass or less. The dispersion may contain only one organic solvent or two or more. When containing two or more organic solvents, the total amount of these organic solvents is preferably within the above range.

[0183] As organic solvents, ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents etc. can be mentioned. For details about these, reference can be made to paragraph 0223 of International Publication No. 2015 / 166779, and the content is incorporated into this specification. In addition, ester solvents substituted by cyclic alkyl groups and ketone solvents substituted by cyclic alkyl groups can also be preferably used. As specific examples of organic solvents, polyethylene glycol monomethyl ether, dichloromethane, 3-ethoxymethyl propionic acid ester, 3-ethoxyethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxymethyl propionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monomethyl ether acetate etc. can be mentioned. Among them, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents are sometimes better to be reduced for environmental reasons (for example, relative to the total amount of organic solvents, it can be set to less than 50 mass ppm (parts per million: one part per million) or less than 10 mass ppm or less than 1 mass ppm).

[0184] In the present invention, it is preferred to use an organic solvent with a low metal content. For example, the metal content of the organic solvent is preferably 10 parts per billion (ppb) or less. If necessary, organic solvents with a ppt (parts per trillion) mass content can be used. Such organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

[0185] Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation or thin film distillation) or filtration using a filter. The pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0186] The organic solvent may contain isomers (compounds having the same number of atoms but different structures). The isomers may be present in one or more forms.

[0187] The peroxide content in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide is contained.

[0188] 〔water〕

[0189] The dispersion of the present invention may contain water.

[0190] The water content is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.1 to 1% by mass relative to the total mass of the dispersion. When the water content is within this range, the deterioration of the viscosity stability of the components in the dispersion over time is easily suppressed, thereby further enhancing the effects of the present invention.

[0191] [Other ingredients]

[0192] The dispersion of the present invention may further contain other components in addition to the above-mentioned components.

[0193] Examples of other components include metal atoms and halogen atoms.

[0194] [Method for producing dispersion]

[0195] The dispersion can be prepared by mixing the above-mentioned components using a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet grinder, a wet disperser, or the like).

[0196] When preparing the dispersion, the components can be mixed all at once, or they can be dissolved or dispersed in a solvent and mixed sequentially. Furthermore, the order of addition and the operating conditions during mixing are not particularly limited.

[0197] For the purpose of removing foreign matter and reducing defects, the dispersion can be filtered with a filter. As a filter, for example, as long as it is a filter that has always been used for filtering purposes, it can be used without particular restriction. For example, filters made of polyamide resins such as fluororesins such as PTFE (polytetrafluoroethylene), nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (including high density, ultra-high molecular weight) can be enumerated. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

[0198] The pore size of the filter is preferably 0.1 to 7.0 μm, more preferably 0.2 to 2.5 μm, further preferably 0.2 to 1.5 μm, and particularly preferably 0.3 to 0.7 μm.

[0199] When using filters, different filters can be combined. In this case, filtration based on the first filter can be performed only once or twice or more. When combining different filters and performing filtration twice or more, it is preferred that the pore size after the second filtration is equal to or larger than the pore size of the first filtration. In addition, first filters with different pore sizes within the above range can also be combined. The pore size here can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, it is possible to select from various filters provided by NIHON PALL LTD., Advantec Toyo Kaisha, Ltd., Nihon Entegris KK (Formerly Nippon microsquirrel Co., Ltd.) and KITZMICROFILTER CORPORATION.

[0200] The second filter may be made of the same material as the first filter. The pore size of the second filter is preferably 0.2 to 10.0 μm, more preferably 0.2 to 7.0 μm, and even more preferably 0.3 to 6.0 μm.

[0201] The dispersion preferably contains no impurities such as metals, halogen-containing metal salts, acids, and bases. The content of impurities contained in these materials is preferably 1 ppm by mass or less, more preferably 1 ppb by mass or less, further preferably 100 ppt by mass or less, particularly preferably 10 ppt by mass or less, and most preferably substantially free (below the detection limit of the measuring device).

[0202] The impurities can be measured using an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Inc., Agilent 7500cs model).

[0203] [Composition]

[0204] The composition of the present invention contains the above-mentioned dispersion and polymerizable compound, and may further contain a resin, a polymerization initiator, a colorant, a polymerization inhibitor, a solvent, etc. As needed, the components contained in the composition of the present invention and the components that may be contained are described below.

[0205] 〔Dispersion〕

[0206] The composition of the present invention contains the above-mentioned dispersion. Since the dispersion is as described above, its description is omitted.

[0207] From the viewpoint of further improving the effects of the present invention, the content of the dispersion is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and even more preferably 15 to 85% by mass relative to the total mass of the composition.

[0208] 〔Polymerizable compounds〕

[0209] The composition of the present invention contains a polymerizable compound.

[0210] The content of the polymerizable compound is not particularly limited, but is preferably 5 to 60% by mass, more preferably 7 to 35% by mass, and even more preferably 9 to 20% by mass relative to the total solid content of the composition.

[0211] The polymerizable compound may be used alone or in combination of two or more. When two or more polymerizable compounds are used, the total content is preferably within the above range.

[0212] The molecular weight (or weight average molecular weight) of the polymerizable compound is not particularly limited, but is preferably 2500 or less.

[0213] The polymerizable compound is preferably a compound containing an ethylenically unsaturated group (a group containing an ethylenically unsaturated bond).

[0214] That is, the composition of the present invention preferably contains a low-molecular compound containing an ethylenically unsaturated group as a polymerizable compound.

[0215] The polymerizable compound is preferably a compound containing one or more ethylenically unsaturated bonds, more preferably a compound containing two or more, further preferably a compound containing three or more, and particularly preferably a compound containing four or more. The upper limit is, for example, 15 or less. Examples of the ethylenically unsaturated group include vinyl, (meth)allyl, and (meth)acryloyl groups.

[0216] As the polymerizable compound, for example, the compounds described in paragraph 0050 of JP-A-2008-260927 and paragraph 0040 of JP-A-2015-68893 can be used, and the contents thereof are incorporated into this specification.

[0217] The polymerizable compound may be in any chemical form, for example, a monomer, a prepolymer, an oligomer, a mixture thereof, or a multimer thereof.

[0218] The polymerizable compound is preferably a tri- to penta-functional (meth)acrylate compound, more preferably a tri- to hexa-functional (meth)acrylate compound, and still more preferably a penta- to hexa-functional (meth)acrylate compound.

[0219] The polymerizable compound is also preferably a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100° C. or higher at normal pressure. For example, reference can be made to the compounds described in paragraph 0227 of JP-A-2013-29760 and paragraphs 0254 to 0257 of JP-A-2008-292970, the contents of which are incorporated herein.

[0220] Preferred polymerizable compounds include dipentaerythritol triacrylate (commercially available products, for example, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available products, for example, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available products, for example, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products, for example, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and structures in which these (meth)acryloyl groups are separated by ethylene glycol residues or propylene glycol residues (for example, SR454 and SR499 commercially available from Sartomer Company, Inc.). These oligomer types can also be used. Furthermore, NK EsterA-TMMT (pentaerythritol tetraacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), KAYARAD RP-1040, KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060, and KAYARAD DPEA-12 (all product names, manufactured by Nippon Kayaku Co., Ltd.) can be used. Furthermore, as the polymerizable compound, a urethane (meth)acrylate-based compound having both a (meth)acryloyl group and a urethane bond can be used, such as KAYARAD DPHA-40H (product name, manufactured by Nippon Kayaku Co., Ltd.).

[0221] Preferred embodiments of the polymerizable compound are shown below.

[0222] The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group. The polymerizable compound containing an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. More preferably, it is a polymerizable compound having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. Even more preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Commercially available products include, for example, ARONIXTO-2349, M-305, M-510, and M-520 manufactured by TOAGOSEI CO., LTD.

[0223] The acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g. An acid value of 0.1 mgKOH / g or greater provides excellent development and dissolution properties, while an acid value of 40 mgKOH / g or less provides advantages in production and / or handling. Furthermore, the polymerizable compound exhibits excellent photopolymerization performance and curability.

[0224] A compound containing a caprolactone structure is also a preferred embodiment of the polymerizable compound.

[0225] The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule. Examples thereof include ε-caprolactone-modified polyfunctional (meth)acrylates obtained by esterifying a polyol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, or trimethylolmelamine with (meth)acrylic acid and ε-caprolactone. Among them, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.

[0226] [Chemical Formula 3]

[0227]

[0228] In formula (Z-1), all six Rs are groups represented by the following formula (Z-2), or one to five of the six Rs are groups represented by the following formula (Z-2), and the rest are groups represented by the following formula (Z-3).

[0229] [Chemical Formula 4]

[0230]

[0231] In formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bonding bond.

[0232] [Chemical Formula 5]

[0233]

[0234] In formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and “*” indicates a bonding position.

[0235] Polymerizable compounds containing a caprolactone structure are commercially available, for example, from Nippon Kayaku Co., Ltd. as the KAYARADDPCA series, and examples thereof include DPCA-20 (in the above formulas (Z-1) to (Z-3), m = 1, the number of groups represented by formula (Z-2) = 2, and R 1 All of the compounds are hydrogen atoms), DPCA-30 (in the above formula, m = 1, the number of groups represented by formula (Z-2) = 3, R 1 All of the compounds are hydrogen atoms), DPCA-60 (in the above formula, m = 1, the number of groups represented by formula (Z-2) = 6, R 1 All of the compounds are hydrogen atoms) and DPCA-120 (in the above formula, m = 2, the number of groups represented by formula (Z-2) = 6, R 1 All of the compounds are hydrogen atoms) etc. Further, as a commercially available product of a polymerizable compound containing a caprolactone structure, for example, M-350 (product name) (trimethylolpropane triacrylate) manufactured by TOAGOSEI CO., LTD. can also be mentioned.

[0236] As the polymerizable compound, a compound represented by the following formula (Z-4) or (Z-5) can also be used.

[0237] [Chemical Formula 6]

[0238]

[0239] In formula (Z-4) and (Z-5), E represents -((CH2) y CH2O)- or ((CH2) y CH(CH3)O)-, y represents an integer of 0 to 10, and X represents a (meth)acryloyl group, a hydrogen atom or a carboxylic acid group.

[0240] In formula (Z-4), the total number of the (meth)acryloyl groups is 3 or 4, m represents an integer of 0 to 10, and the total number of each m is an integer of 0 to 40.

[0241] In formula (Z-5), the total number of the (meth)acryloyl groups is 5 or 6, n represents an integer of 0 to 10, and the total number of each n is an integer of 0 to 60.

[0242] In formula (Z-4), m is preferably an integer of 0-6, more preferably an integer of 0-4.

[0243] Furthermore, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and even more preferably an integer of 4 to 8.

[0244] In formula (Z-5), n is preferably an integer of 0-6, more preferably an integer of 0-4.

[0245] Furthermore, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12.

[0246] Furthermore, preferably, -((CH2) y CH2O)- or ((CH2) y CH(CH3)O)- is a form in which the terminal on the oxygen atom side is bonded to X.

[0247] The compound represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, preferred are a configuration in which all six X's in formula (Z-5) are acryloyl groups, or a mixture of a compound in which all six X's in formula (Z-5) are acryloyl groups and a compound in which at least one of the six X's is a hydrogen atom. This configuration can further improve developability.

[0248] Furthermore, the total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, more preferably 50% by mass or more.

[0249] Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferred.

[0250] Furthermore, the polymerizable compound may contain a cardo skeleton.

[0251] As the polymerizable compound containing a cardo skeleton, a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable.

[0252] Examples of the polymerizable compound containing a cardo skeleton include the ONCOATEX series (manufactured by NAGASE & CO., LTD.) and OGSOL (manufactured by Osaka Gas Chemicals Co., Ltd.).

[0253] The polymerizable compound is preferably a compound containing an isocyanuric acid skeleton as a central core. Examples of such a polymerizable compound include NK Ester A-9300 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.).

[0254] The ethylenically unsaturated bond equivalent of the polymerizable compound (a value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g / mol) of the polymerizable compound) is preferably 5.0 mmol / g or greater. The upper limit is not particularly limited, but is generally 20.0 mmol / g or less.

[0255] 〔Resin〕

[0256] The composition of the present invention preferably contains a resin. The resin is incorporated, for example, to disperse particles such as pigments in the composition or as a binder. Resins used primarily to disperse particles such as pigments are also referred to as dispersants. These uses of resins are merely examples, and resins can also be used for purposes other than these.

[0257] The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3,000 or more, more preferably 5,000 or more.

[0258] As resin, can enumerate (meth) acrylic resin, epoxy resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin etc..Can use one alone from these resins, also can mix and use two or more.As cyclic olefin resin, from the viewpoint of improving heat resistance, preferably norbornene resin.As the commercial product of norbornene resin, for example, can enumerate ARTON series (for example, ARTON F4520) etc. manufactured by JSR Corporation. Examples of epoxy resins include epoxy resins that are glycidyl ethers of phenolic compounds, epoxy resins that are glycidyl ethers of various novolac resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, glycidyl ester epoxy resins, glycidylamine epoxy resins, epoxy resins obtained by glycidylating halogenated phenols, condensates of silicon compounds having epoxy groups with other silicon compounds, copolymers of polymerizable unsaturated compounds having epoxy groups with other polymerizable unsaturated compounds, etc. Furthermore, Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (manufactured by NOF CORPORATION, epoxy group-containing polymers) can also be used as epoxy resins. Furthermore, the resins described in the Examples of International Publication No. 2016 / 088645 can also be used. Furthermore, when the resin has an ethylenically unsaturated group, particularly a (meth)acryloyl group, in a side chain, it is also preferred that the main chain and the ethylenically unsaturated group be bonded via a divalent linking group having an alicyclic structure.

[0259] The composition of the present invention preferably includes an alkali-soluble resin. The composition of the present invention improves its developability by including an alkali-soluble resin. When the composition of the present invention is used to form a pattern using photolithography, the generation of development residue can be effectively suppressed. Examples of the alkali-soluble resin include resins having an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, with a carboxyl group being preferred. The alkali-soluble resin may contain only one acid group or two or more acid groups. Furthermore, the alkali-soluble resin can also be used as a dispersant.

[0260] The alkali-soluble resin preferably contains repeating units having acid groups in their side chains, and more preferably contains 5 to 70 mol% of repeating units having acid groups in their side chains among all repeating units in the resin. The upper limit of the content of repeating units having acid groups in their side chains is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of repeating units having acid groups in their side chains is preferably 10 mol% or more, more preferably 20 mol% or more.

[0261] The alkali-soluble resin is preferably an alkali-soluble resin having a polymerizable group. Examples of the polymerizable group include a (meth)allyl group (representing both an allyl group and a methallyl group) and a (meth)acryloyl group. The alkali-soluble resin having a polymerizable group is preferably a resin containing repeating units having a polymerizable group in a side chain and repeating units having an acid group in a side chain.

[0262] The alkali-soluble resin also preferably includes repeating units derived from monomer components including a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may also be referred to as "ether dimers").

[0263] [Chemical Formula 7]

[0264]

[0265] In formula (ED1), R 1 and R 2 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

[0266] [Chemical Formula 8]

[0267]

[0268] In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of formula (ED2), reference can be made to the description of Japanese Patent Application Laid-Open No. 2010-168539, the contents of which are incorporated herein.

[0269] As specific examples of the ether dimer, for example, reference can be made to the description in paragraph 0317 of JP-A-2013-029760, the contents of which are incorporated herein.

[0270] The alkali-soluble resin also preferably includes a repeating unit derived from a compound represented by the following formula (X).

[0271] [Chemical Formula 9]

[0272]

[0273] In formula (X), R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 2 to 10 carbon atoms, and R3 represents an alkyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring. n represents an integer of 1 to 15.

[0274] Regarding the alkali-soluble resin, reference can be made to paragraphs 0558 to 0571 of Japanese Patent Application Laid-Open No. 2012-208494 (paragraphs 0685 to 0700 of the corresponding U.S. Patent Application Publication No. 2012 / 0235099) and paragraphs 0076 to 0099 of Japanese Patent Application Laid-Open No. 2012-198408, the contents of which are incorporated herein.

[0275] The acid value of the resin (especially the alkali-soluble resin) is preferably 10 to 500 mgKOH / g. The lower limit is preferably 30 mgKOH / g or higher, more preferably 50 mgKOH / g or higher, and even more preferably 70 mgKOH / g or higher. The upper limit is preferably 400 mgKOH / g or lower, more preferably 300 mgKOH / g or lower, even more preferably 200 mgKOH / g or lower, and particularly preferably 100 mgKOH / g or lower.

[0276] The ethylenically unsaturated bond equivalent weight (a value representing the number of ethylenically unsaturated groups in a polymerizable compound divided by the molecular weight (g / mol) of the polymerizable compound) of the resin (especially an alkali-soluble resin) is preferably 0.4 to 2.5 mmol / g. The lower limit is preferably 1.0 mmol / g, and more preferably 1.2 mmol / g. The upper limit is preferably 2.3 mmol / g, and more preferably 2.0 mmol / g.

[0277] In particular, when the composition of the present invention contains a resin having an acid value of 10 to 100 mgKOH / g and an ethylenically unsaturated bond equivalent of 1.0 to 2.0 mmol / g, peeling after a humidity resistance test can be further suppressed.

[0278] Specific examples of the alkali-soluble resin include resins having the following structures. In the following structural formula, Me represents a methyl group.

[0279] [Chemical Formula 10]

[0280]

[0281] The composition of the present invention also preferably contains a resin having a basic group. Examples of the basic group include amino groups and ammonium salt groups. A resin having a basic group may further have an acidic group in addition to the basic group. Furthermore, if a resin having a basic group further has an acidic group, such a resin is also an alkali-soluble resin.

[0282] As the resin having a basic group, a resin having a tertiary amino group and a quaternary ammonium salt group can be cited. The resin having a tertiary amino group and a quaternary ammonium salt group is preferably a resin having a repeating unit having a tertiary amino group and a repeating unit having a quaternary ammonium salt group. In addition, the resin having a tertiary amino group and a quaternary ammonium salt group may further have a repeating unit having an acid group. The resin having a tertiary amino group and a quaternary ammonium salt group also preferably has a block structure. The resin having a tertiary amino group and a quaternary ammonium salt group is preferably a resin having an amine value of 10 to 250 mgKOH / g and a quaternary ammonium salt value of 10 to 90 mgKOH / g, more preferably a resin having an amine value of 50 to 200 mgKOH / g and a quaternary ammonium salt value of 10 to 50 mgKOH / g. The weight average molecular weight (Mw) of the resin having a tertiary amino group and a quaternary ammonium salt group is preferably 3,000 to 300,000, more preferably 5,000 to 30,000. The resin with a tertiary amino group and a quaternary ammonium salt group can be manufactured by copolymerizing an ethylenically unsaturated monomer with a tertiary amino group, an ethylenically unsaturated monomer with a quaternary ammonium salt group, and other ethylenically unsaturated monomers as needed. About the ethylenically unsaturated monomer with a tertiary amino group and the ethylenically unsaturated monomer with a quaternary ammonium salt group, the contents described in paragraphs 0150 to 0170 of International Publication No. 2018 / 230486 can be cited, and the contents are incorporated into this specification. In addition, the resin with the acidic group described in paragraphs 0079 to 0160 of Japanese Patent Application Publication No. 2018-87939 can be used simultaneously.

[0283] Furthermore, as the resin with a basic group, it is also preferred that the resin comprises a nitrogen atom in the main chain. The resin comprising a nitrogen atom in the main chain (hereinafter also referred to as oligoimine resin) preferably comprises at least one repeating unit with a nitrogen atom selected from poly (lower alkylene imine) repeating units, polyallylamine repeating units, polydiallylamine repeating units, meta-xylene diamine-epichlorohydrin polycondensate repeating units and polyvinylamine repeating units. Furthermore, as the oligoimine resin, it is preferred that the resin comprises a repeating unit having a partial structure X with a functional group having a pKa of less than 14 and a repeating unit having a side chain of an oligomer chain or polymer chain Y having 40 to 10000 atoms. The oligoimine resin can further comprise a repeating unit having an acid group. As the oligoimine resin, reference can be made to the description in paragraphs 0102 to 0166 of Japanese Patent Application Publication No. 2012-255128, and the content is incorporated into this specification.

[0284] The composition of the present invention can also contain a resin as a dispersant, preferably a resin as a dispersant. Examples of dispersants include acidic dispersants (acidic resins) and alkaline dispersants (alkaline resins). Here, an acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of alkaline groups. When the total amount of the amount of acid groups and the amount of alkaline groups is set to 100 mol%, an acidic dispersant (acidic resin) preferably has an amount of acid groups of more than 70 mol%, and more preferably a resin that substantially only contains acid groups. The acid groups possessed by the acidic dispersant (acidic resin) are preferably carboxyl groups. Furthermore, an alkaline dispersant (alkaline resin) refers to a resin in which the amount of alkaline groups is greater than the amount of acid groups. When the total amount of the amount of acid groups and the amount of alkaline groups is set to 100 mol%, an alkaline dispersant (alkaline resin) preferably has an amount of alkaline groups exceeding 50 mol%. As a dispersant, a resin with alkaline groups is preferred, and an alkaline dispersant is more preferred.

[0285] Examples of the resin used as a dispersant include the above-mentioned resins having a tertiary amino group and a quaternary ammonium salt group, oligoimide resins, and the like. Furthermore, the resin used as a dispersant is preferably a grafted resin. Examples of the grafted resin include resins having repeating units having a grafted chain. The grafted resin may further have repeating units having an acid group. Details of the grafted resin can be found in paragraphs 0025 to 0094 of Japanese Patent Application Publication No. 2012-255128, and such contents are incorporated herein by reference.

[0286] In order to improve the interaction between the graft chain and the solvent and thereby improve the dispersibility of the colorant, etc., the graft chain is preferably a graft chain containing at least one selected from a polyester structure, a polyether structure and a poly(meth)acrylate structure, and more preferably a graft chain containing at least one of a polyester structure and a polyether structure.

[0287] Furthermore, the resin used as a dispersant is preferably a resin containing repeating units having an acid group. Furthermore, the resin used as a dispersant is preferably a resin having a structure in which multiple polymer chains are bonded to a core. Examples of such resins include dendritic polymers (including star polymers). Specific examples of dendritic polymers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Laid-Open No. 2013-043962. Furthermore, the above-mentioned alkali-soluble resins can also be used as dispersants.

[0288] Dispersants are also commercially available, and specific examples thereof include Disperbyk-111 (manufactured by BYK-Chemie GmbH) and SOLSPERSE 76500 (manufactured by Japan Lubrizol Corporation). Furthermore, dispersants described in paragraphs 0041 to 0130 of JP-A-2014-130338 can also be used, and the contents of these are incorporated herein.

[0289] It is also preferable to use the dispersants described in Japanese Patent Application Laid-Open No. 2019-078878.

[0290] The resin content in the total solids content of the composition is preferably 1 to 50% by mass. The lower limit is preferably 5% by mass or more, more preferably 7% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.

[0291] Furthermore, when the composition of the present invention contains an alkali-soluble resin, the content of the alkali-soluble resin in the total solids content of the composition is preferably 1 to 50% by mass. The lower limit is preferably 5% by mass or more, more preferably 7% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less. Furthermore, the content of the alkali-soluble resin in the resin contained in the composition is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, and even more preferably 90 to 100% by mass.

[0292] Furthermore, when the composition of the present invention contains a resin as a dispersant, the content of the resin as a dispersant in the total solids content of the composition is preferably 0.1 to 40% by mass. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.

[0293] The composition of the present invention may contain only one resin or two or more resins. When containing two or more resins, the total amount thereof is preferably within the above range.

[0294] 〔Polymerization initiator〕

[0295] The composition of the present invention preferably contains a polymerization initiator.

[0296] As the polymerization initiator, for example, a known polymerization initiator can be used. Examples of the polymerization initiator include photopolymerization initiators and thermal polymerization initiators, and photopolymerization initiators are preferred.

[0297] The content of the polymerization initiator is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, and even more preferably 1.5 to 8% by mass, based on the total solid content of the composition.

[0298] The polymerization initiator may be used alone or in combination of two or more. When two or more polymerization initiators are used in combination, the total content is preferably within the above range.

[0299] Thermal polymerization initiator

[0300] Examples of the thermal polymerization initiator include azo compounds such as 2,2′-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalononitrile, and dimethyl-(2,2′)-azobis(2-methylpropionate) [V-601]; and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate.

[0301] Specific examples of the thermal polymerization initiator include the polymerization initiators described in "Ultraviolet Curing System" by Kato Kiyoshi (published by Sogo Techno Center Co., Ltd. in 1989), pages 65 to 148.

[0302] <Photopolymerization initiator>

[0303] The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, a compound that is photosensitized to light from the ultraviolet region to the visible region is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0304] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound. More preferred are compounds selected from the group consisting of oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, and acylphosphine compounds, and even more preferred are oxime compounds. Examples of the photopolymerization initiator include compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173 and Japanese Patent No. 6301489, and the contents thereof are incorporated herein.

[0305] Examples of commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins BV) (in that order, Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127, all manufactured by the former BASF Corporation). Examples of commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.) (in that order, Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG, all manufactured by the former BASF Corporation). Examples of commercially available acylphosphine compounds include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins BV) (these are Irgacure 819 and Irgacure TPO manufactured by the former BASF Corporation, respectively).

[0306] Examples of the oxime compound include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, compounds described in JCS Perkin II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), and compounds described in Journal of Photopolymer Science and Technology. Technology (1995, pp. 202-232), compounds described in Japanese Patent Application Laid-Open No. 2000-066385, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, compounds described in Japanese Patent Application Laid-Open No. 2004-534797, compounds described in Japanese Patent Application Laid-Open No. 2006-342166, compounds described in Japanese Patent Application Laid-Open No. 2017-019766, Japanese Patent No. 60655 Compounds described in International Publication No. 96, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Application Laid-Open No. 2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, compounds described in International Publication No. 2019 / 088055, etc. Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutyl-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. Examples of commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (all manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Trolly New Electronic Materials Co., Ltd.), and ADEKA OPTOMERN-1919 (manufactured by ADEKA Corporation, a photopolymerization initiator 2 described in Japanese Patent Application Laid-Open No. 2012-014052). Furthermore, as the oxime compound, a non-coloring compound or a compound that is highly transparent and resistant to discoloration is preferably used.Examples of commercially available products include ADEKA ARKLS NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA CORPORATION).

[0307] In the present invention, an oxime compound having a fluorene ring can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466.

[0308] Furthermore, as a photopolymerization initiator, an oxime compound having a carbazole ring and a naphthalene ring as the skeleton of at least one benzene ring can also be used. Specific examples of such oxime compounds include the compounds described in International Publication No. 2013 / 083505.

[0309] In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of oxime compounds having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and compound (C-3) described in JP-A-2013-164471.

[0310] In the present invention, an oxime compound having a nitro group can be used as a photopolymerization initiator. The oxime compound having a nitro group is preferably also a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of Japanese Patent Application Laid-Open No. 2013-114249, paragraphs 0008 to 0012 and paragraphs 0070 to 0079 of Japanese Patent Application Laid-Open No. 2014-137466, the compounds described in paragraphs 0007 to 0025 of Japanese Patent Application No. 4223071, and ADEKA ARKL SNC1-831 (manufactured by ADEKA CORPORATION).

[0311] In the present invention, an oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator. Specific examples include OE-01 to OE-75 described in International Publication No. 2015 / 036910.

[0312] Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited thereto.

[0313] [Chemical Formula 11]

[0314]

[0315] [Chemical Formula 12]

[0316]

[0317] The oxime compound preferably has a maximum absorption wavelength in the range of 350 to 500 nm, more preferably a compound with a maximum absorption wavelength in the range of 360 to 480 nm. In addition, from the perspective of sensitivity, the molar absorptivity of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high, more preferably 1000 to 300,000, further preferably 2000 to 300,000, and particularly preferably 5000 to 200,000. The molar absorptivity of the compound can be measured using a known method. For example, it is measured using a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian), preferably using an ethyl acetate solvent at a concentration of 0.01 g / L.

[0318] As the photopolymerization initiator, a difunctional or trifunctional or higher photoradical polymerization initiator can be used. By using such a photoradical polymerization initiator, two or more free radicals are generated from one molecule of the photoradical polymerization initiator, and therefore good sensitivity can be obtained. In addition, when using a compound with an asymmetric structure, crystallinity decreases and solubility in solvents etc. is improved, becoming difficult to separate out over time, and thus the temporal stability of the composition can be improved. Specific examples of bifunctional or trifunctional or higher-functional photoradical polymerization initiators include dimers of oxime compounds described in JP-A-2010-527339, JP-A-2011-524436, International Publication No. 2015 / 004565, paragraphs 0407 to 0412 of JP-A-2016-532675, and paragraphs 0039 to 0055 of International Publication No. 2017 / 033680, and JP-A-2013-522445. The compounds (E) and (G) described in International Publication No. 2016 / 034963, Cmpd1 to 7 described in International Publication No. 2016 / 034963, the oxime ester photoinitiator described in paragraph 0007 of JP-A-2017-523465, the photoinitiator described in paragraphs 0020 to 0033 of JP-A-2017-167399, and the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of JP-A-2017-151342.

[0319] The photopolymerization initiator also preferably contains an oxime compound and an α-aminoketone compound. Using both improves developability and facilitates formation of a pattern with excellent rectangularity. When using both an oxime compound and an α-aminoketone compound, the amount of the α-aminoketone compound is preferably 50 to 600 parts by mass, more preferably 150 to 400 parts by mass, per 100 parts by mass of the oxime compound.

[0320] The content of the photopolymerization initiator in the total solid content of the composition is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, and even more preferably 1 to 20% by mass. The composition may contain only one type of photopolymerization initiator or two or more types. When containing two or more types, the total amount of these initiators is preferably within the above range.

[0321] Pigment

[0322] The composition of the present invention may contain a colorant. In addition, the inorganic oxide particles and the colorant may be made of different materials. The colorants may be used alone or in combination of two or more.

[0323] Examples of colorants include chromatic colorants, colorless colorants, and infrared absorbers. In the present invention, chromatic colorants refer to colorants other than white colorants and black colorants. Chromatic colorants are preferably colorants that absorb light in a wavelength range of 400 nm to less than 650 nm.

[0324] The content of the colorant is preferably 10 to 80% by mass, more preferably 20 to 75% by mass, and even more preferably 30 to 70% by mass relative to the total solid content of the composition.

[0325] The composition of the present invention may contain only one coloring material or two or more coloring materials. When two or more coloring materials are contained, the total amount thereof is preferably within the above range.

[0326] Colorants

[0327] Examples of color colorants include red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants. Color colorants may be pigments or dyes. Pigments and dyes may also be used simultaneously. Furthermore, the pigment may be either an inorganic pigment or an organic pigment. Furthermore, pigments obtained by substituting a portion of an inorganic pigment or an organic-inorganic pigment with an organic chromophore may be used. By substituting an organic chromophore for an inorganic pigment or an organic-inorganic pigment, hue design can be facilitated.

[0328] The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and further preferably 100 nm or less. As long as the average primary particle size of the pigment is within the above range, the dispersion stability of the pigment in the composition is good. In addition, in the present invention, the primary particle size of the pigment can be obtained by observing the primary particles of the pigment with a transmission electron microscope and obtaining the image photograph. Specifically, the projected area of ​​the primary particles of the pigment is obtained, and the corresponding circle equivalent diameter is calculated as the primary particle size of the pigment. In addition, the average primary particle size in the present invention is set to the arithmetic mean of the primary particle sizes of 400 primary particles of the pigment. In addition, the primary particles of the pigment refer to independent particles that are not agglomerated.

[0329] The coloring agent preferably contains a pigment. The content of the pigment in the coloring agent is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more. Examples of the pigment include the following.

[0330] Color Index (CI) Pigment Yellow (hereinafter also referred to as "PY") 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 124 5, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232 (methine series), 233 (quinoline series), 234 (aminoketone series), 235 (aminoketone series), 236 (aminoketone series) etc. (the above are yellow pigments),

[0331] CI Pigment Orange (hereinafter also referred to as "PO") 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (the above are orange pigments),

[0332] CI Pigment Red (hereinafter also referred to as "PR") 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146 , 149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,294 (xanthene series, Organo Ultramarine, Bluish Red), 295 (azo series), 296 (azo series), 297 (aminoketone series), etc. (the above are red pigments),

[0333] CI Pigment Green (hereinafter also referred to as "PG") 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine), 65 (phthalocyanine), 66 (phthalocyanine), etc. (the above are green pigments),

[0334] CI Pigment Violet (Pigment Violet) (hereinafter also referred to as "PV") 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane series), 61 (xanthene series) etc. (the above are violet pigments),

[0335] CI Pigment Blue (Pigment Blue) (hereinafter also referred to as "PB") 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo series), 88 (methine series), etc. (the above are blue pigments).

[0336] Furthermore, green pigments can be used, for example, zinc phthalocyanine halides containing an average of 10 to 14 halogen atoms, 8 to 12 bromine atoms, and 2 to 5 chlorine atoms per molecule. Specific examples include the compounds described in International Publication No. 2015 / 118720. Furthermore, green pigments can be used, for example, compounds described in the specification of Chinese Patent Application No. 106909027 and phthalocyanine compounds containing a phosphate ester as a ligand, as described in International Publication No. 2012 / 102395.

[0337] Furthermore, as a blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A-2012-247591 and paragraph 0047 of JP-A-2011-157478.

[0338] Furthermore, as yellow pigments, pigments described in Japanese Patent Application Laid-Open No. 2008-074985, compounds described in Japanese Patent Application Laid-Open No. 2008-074987, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2013-061622, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2013-181015, colorants described in Japanese Patent Application Laid-Open No. 2014-085565, and colorants described in Japanese Patent Application Laid-Open No. 2014-085565 can also be used. Pigments described in Japanese Patent Application Publication No. 016-145282, pigments described in Japanese Patent Application Publication No. 2017-201003, pigments described in Japanese Patent Application Publication No. 2017-197719, pigments described in paragraphs 0011 to 0062 and 0137 to 0276 of Japanese Patent Application Publication No. 2017-171912, and pigments described in paragraphs 0010 to 0062 and 0138 to 0295 of Japanese Patent Application Publication No. 2017-171913 Pigments described therein, pigments described in paragraphs 0011 to 0062 and 0139 to 0190 of Japanese Patent Application Laid-Open No. 2017-171914, pigments described in paragraphs 0010 to 0065 and 0142 to 0222 of Japanese Patent Application Laid-Open No. 2017-171915, quinophthalone compounds described in Japanese Patent Application Laid-Open No. 2017-197640, quinophthalone pigments described in Japanese Patent Application Laid-Open No. 2018-040835 , pigments described in Japanese Patent Application Publication No. 2018-203798, pigments described in Japanese Patent Application Publication No. 2018-062578, quinophthalone yellow pigments described in Japanese Patent Application Publication No. 2018-155881, compounds described in Japanese Patent Application Publication No. 2018-062644, quinophthalone compounds described in Japanese Patent No. 6432077, and pigments described in Japanese Patent No. 6443711.

[0339] Furthermore, as a yellow pigment, a compound described in Japanese Patent Application Laid-Open No. 2018-062644 can also be used. This compound can also be used as a pigment derivative.

[0340] As red pigments, diketopyrrolopyrrole compounds in which at least one bromine atom is substituted in the structure described in Japanese Patent Application Laid-Open No. 2017-201384, diketopyrrolopyrrole compounds described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838, diketopyrrolopyrrole compounds described in International Publication No. 2012 / 102399, diketopyrrolopyrrole compounds described in International Publication No. 2012 / 117965, naphthol azo compounds described in Japanese Patent Application Laid-Open No. 2012-229344, etc. can also be used. In addition, as red pigments, compounds having a structure in which an aromatic ring group having an oxygen atom, a sulfur atom, or a nitrogen atom bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used.

[0341] Furthermore, as red pigments, compounds described in Japanese Patent No. 6516119 and Japanese Patent No. 6525101 can also be used. These compounds can also be used as pigment derivatives.

[0342] In the present invention, dyes can also be used in color colorants. There is no particular limitation on the dyes, and known dyes can be used. For example, pyrazole azo systems, anilino azo systems, triarylmethane systems, anthraquinone systems, anthrapyridone systems, benzylidene systems, oxonol systems, pyrazolotriazole azo systems, pyridone azo systems, cyanine systems, phenothiazine systems, pyrrolopyrazole azomethine systems, xanthene systems, phthalocyanine systems, benzopyran systems, indigo systems, pyrromethene systems, etc. dyes. In addition, thiazole compounds described in Japanese Patent Application Laid-Open No. 2012-158649 Gazette, azo compounds described in Japanese Patent Application Laid-Open No. 2011-184493 Gazette, and azo compounds described in Japanese Patent Application Laid-Open No. 2011-145540 Gazette can also be preferably used. Furthermore, as yellow dyes, quinophthalone compounds described in paragraphs 0011 to 0034 of JP-A-2013-054339 and quinophthalone compounds described in paragraphs 0013 to 0058 of JP-A-2014-026228 can also be used.

[0343] <Colorless colorant>

[0344] Examples of the colorless colorant include black colorants and white colorants.

[0345] (black colorant)

[0346] Examples of the black colorant include one or more selected from black pigments and black dyes.

[0347] Furthermore, a black colorant may be formed by combining a plurality of colorants that cannot be used as a black colorant individually and adjusting the overall color to black.

[0348] For example, a plurality of pigments that individually have colors other than black can be combined to use as a black pigment. Similarly, a plurality of dyes that individually have colors other than black can be combined to use as a black dye, or a pigment that individually has a color other than black and a dye that individually has a color other than black can be combined to use as a black dye.

[0349] In this specification, a black colorant refers to a colorant having absorption over the entire wavelength range of 400 to 700 nm.

[0350] More specifically, for example, a black colorant that satisfies the evaluation criteria Z described below is preferred.

[0351] First, a composition containing a colorant, a transparent resin matrix (acrylic resin, etc.) and a solvent, wherein the content of the colorant is 60% by mass relative to the total solids, is prepared. On a glass substrate, the obtained composition is applied in a manner such that the film thickness of the dried coating becomes 1 μm to form a coating. A spectrophotometer (such as UV-3600 manufactured by SHIMADZU CORPORATION) is used to evaluate the light-shielding properties of the dried coating. If the maximum value of the transmittance of the dried coating at a wavelength of 400 to 700 nm is less than 10%, it can be determined that the colorant is a black colorant that meets evaluation standard Z. In evaluation standard Z, the maximum value of the transmittance of the dried coating at a wavelength of 400 to 700 nm is more preferably less than 8%, and further preferably less than 5%.

[0352] Black pigment

[0353] As the black pigment, various known black pigments can be used. The black pigment may be an inorganic pigment or an organic pigment.

[0354] From the viewpoint of achieving more excellent light resistance of the light-shielding film, the black colorant is preferably a black pigment.

[0355] The black pigment is preferably a pigment that exhibits black color alone, and more preferably a pigment that exhibits black color alone and absorbs infrared rays.

[0356] Here, the infrared absorbing black pigment has absorption in the infrared region (preferably a wavelength of 650 to 1300 nm), for example, and preferably has a maximum absorption wavelength in the wavelength region of 675 to 900 nm.

[0357] The particle size of the black pigment is not particularly limited, but is preferably 5 to 100 nm, more preferably 5 to 50 nm, and even more preferably 5 to 30 nm from the viewpoint of achieving a better balance between handleability and temporal stability of the composition (no sedimentation of the black pigment).

[0358] In addition, in this specification, the particle size of the black pigment represents the average primary particle size of the particles measured using the following method. The average primary particle size can be measured using a transmission electron microscope (TEM). As a transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.

[0359] The maximum length (Dmax: the maximum length between two points on the particle image contour) and the perpendicular length (DV-max: the shortest length perpendicular to the maximum length when two straight lines parallel to the maximum length are sandwiched between the image) of the particle image obtained using a transmission electron microscope were measured and the average value (Dmax × DV-max) was multiplied. 1 / 2 The particle diameters of 100 particles were measured using this method, and the arithmetic mean value was defined as the average primary particle diameter of the particles.

[0360] Inorganic pigments used as black colorants

[0361] The inorganic pigment used as the black colorant is not particularly limited as long as it has light-shielding properties and contains particles of an inorganic compound, and known inorganic pigments can be used.

[0362] From the viewpoint of achieving excellent low reflectivity and light-shielding properties of the light-shielding film, an inorganic pigment is preferred as the black colorant.

[0363] Examples of the inorganic pigment include metal elements selected from Group 4 such as titanium (Ti) and zirconium (Zr), Group 5 such as vanadium (V) and niobium (Nb), cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn) and silver (Ag), and metal oxides, metal nitrides and metal oxynitrides.

[0364] As the metal oxides, metal nitrides, and metal oxynitrides, particles containing other atoms may be used. For example, particles containing metal nitrides containing atoms selected from elements in Groups 13 to 17 of the periodic table (preferably oxygen and / or sulfur atoms) may be used.

[0365] The method for producing the metal nitride, metal oxide, or metal oxynitride is not particularly limited as long as it is a method for producing a black pigment having desired physical properties, and a known production method such as a gas phase reaction method can be used. Examples of the gas phase reaction method include an electric furnace method and a thermal plasma method. The thermal plasma method is preferred because it has less impurities, can easily achieve uniform particle size, and can improve productivity.

[0366] The metal nitride, metal oxide, or metal oxynitride may be surface-modified. For example, the surface-modified particles may be treated with a surface treatment agent having both a polysiloxy group and an alkyl group. Examples of such inorganic particles include the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0367] Among these, from the perspective of suppressing undercutting during the formation of the light-shielding film, nitrides or oxynitrides of one or more metals selected from titanium, vanadium, zirconium, and niobium are more preferred. Furthermore, from the perspective of providing a light-shielding film with even better moisture resistance, oxynitrides of one or more metals selected from titanium, vanadium, zirconium, and niobium are even more preferred, with titanium oxynitride (titanium black), zirconium nitride, or zirconium oxynitride being particularly preferred.

[0368] Titanium black is black particles containing titanium oxynitride. The surface of titanium black can be modified as needed to improve dispersibility, inhibit agglomeration, and so on. Titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and can also be treated with a hydrophobic substance as described in Japanese Patent Application Laid-Open No. 2007-302836.

[0369] Methods for producing titanium black include: a method of heating a mixture of titanium dioxide and metallic titanium under a reducing atmosphere and reducing the mixture (Japanese Patent Publication No. 49-5432); a method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride in a reducing atmosphere containing hydrogen (Japanese Patent Publication No. 57-205322); a method of high-temperature reducing titanium dioxide or titanium hydroxide in the presence of ammonia (Japanese Patent Publication No. 60-65069, Japanese Patent Publication No. 61-201610); and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing the mixture at high temperature in the presence of ammonia (Japanese Patent Publication No. 61-201610), etc., but are not limited to these.

[0370] The particle size of titanium black is not particularly limited, but is preferably 10 to 45 nm, more preferably 12 to 20 nm. The specific surface area of ​​titanium black is not particularly limited, but in order to achieve the desired water repellency after surface treatment with a water repellent, the value measured by the BET (Brunauer, Emmett, Teller) method is preferably 5 to 150 nm. 2 / g, more preferably 20 to 100 m 2 / g.

[0371] Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, and 13M-T (product names, manufactured by Mitsubishi Materials Corporation), Tilack D (product name, manufactured by AkoKasei Co., Ltd.), and MT-150A (product name, manufactured by Tayca Corporation).

[0372] The composition also preferably contains titanium black as a dispersed body containing titanium black and Si atoms. In this form, titanium black is contained as a dispersed body in the composition. The ratio of Si atoms to Ti atoms in the dispersed body (Si / Ti) is preferably 0.05 to 0.5, more preferably 0.07 to 0.4, calculated on a mass basis. Here, the dispersed body includes both the state of titanium black as primary particles and the state of agglomerates (secondary particles).

[0373] Furthermore, when the Si / Ti ratio of the dispersion is above a predetermined value, residue is less likely to remain in the removed portion when a coating film using the dispersion is patterned by photolithography or the like, and when the Si / Ti ratio of the dispersion is below a predetermined value, the light shielding capability is likely to be improved.

[0374] To adjust the Si / Ti ratio of the dispersed material (e.g., to 0.05 or greater), the following mechanism can be used. First, titanium oxide and silicon dioxide particles are dispersed using a disperser to obtain a dispersion. This mixture is then subjected to a reduction treatment at a high temperature (e.g., 850-1000°C) to obtain a dispersed material containing titanium black particles as the main component and Si and Ti. Titanium black with adjusted Si / Ti ratios can be produced, for example, using the methods described in paragraphs 0005 and 0016-0021 of Japanese Patent Application Laid-Open No. 2008-266045.

[0375] The content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersed body can be measured using, for example, the method (2-1) or method (2-3) described in paragraphs 0054 to 0056 of International Publication No. 2011 / 049090.

[0376] In the dispersed body containing titanium black and Si atoms, titanium black can be used as described above. Furthermore, in this dispersed body, one or more black pigments composed of composite oxides of multiple metals selected from Cu, Fe, Mn, V, and Ni, cobalt oxide, iron oxide, carbon black, and aniline black, etc., can be used in combination with titanium black to adjust dispersibility and colorability. In this case, the dispersed body composed of titanium black preferably accounts for 50% by mass or more of the total dispersed body.

[0377] As zirconium nitride and zirconium oxynitride, the composites or powders described in Japanese Patent No. 4931011, Japanese Patent Application Laid-Open No. 2017-222559, and Japanese Patent Application Laid-Open No. 2018-203599 can be used.

[0378] Carbon black can also be mentioned as an inorganic pigment.

[0379] Examples of carbon black include furnace black, channel black, thermal black, acetylene black, and lamp black.

[0380] Carbon black can be produced by a known method such as an oil furnace method, or a commercially available product can be used. Specific examples of commercially available carbon black include organic pigments such as CI Pigment Black 1 and inorganic pigments such as CI Pigment Black 7.

[0381] Carbon black that has been surface-treated is preferred. Surface treatment can alter the surface condition of carbon black particles and improve dispersion stability in the composition. Examples of surface treatments include coating with a resin, surface treatment to introduce acidic groups, and surface treatment with a silane coupling agent.

[0382] Carbon black that has been coated with a resin is preferred. Coating the carbon black particles with an insulating resin can improve the light-shielding and insulating properties of the light-shielding film. Furthermore, this can improve the reliability of image displays by reducing leakage current. Therefore, it is suitable for applications requiring insulating properties in light-shielding films.

[0383] Examples of the coating resin include epoxy resins, polyamides, polyamideimides, novolac resins, phenolic resins, urea resins, melamine resins, polyurethanes, dibutyl phthalate resins, alkylbenzene resins, polystyrene, polycarbonate, polybutylene terephthalate, and modified polyphenylene ether.

[0384] From the viewpoint of further improving the light-shielding property and insulating property of the light-shielding film, the content of the coating resin is preferably 0.1 to 40% by mass, more preferably 0.5 to 30% by mass, relative to the total of the carbon black and the coating resin.

[0385] Furthermore, zirconium nitride described in Japanese Patent Application Laid-Open No. 2017-222559 and International Publication No. 2019 / 130772 can also be preferably used.

[0386] Organic pigments used as black colorants

[0387] The organic pigment used as the black colorant is not particularly limited as long as it has light-shielding properties and contains particles of an organic compound, and a known organic pigment can be used.

[0388] In the present invention, examples of the organic pigment include bisbenzofuranone compounds, methine azo compounds, perylene compounds, and azo compounds, and bisbenzofuranone compounds and perylene compounds are preferred.

[0389] Examples of the bisbenzofuranone compound include compounds described in JP-A-2010-534726, JP-A-2012-515233, and JP-A-2012-515234. The bisbenzofuranone compound is available as "Irgaphor Black" (product name) manufactured by BASF.

[0390] Examples of the perylene compound include compounds described in JP-A-62-1753 and JP-B-63-26784. The perylene compound is available as CI Pigment Black 21, 30, 31, 32, 33, and 34.

[0391] Black dye

[0392] As the black dye, a dye that alone exhibits black can be used, for example, pyrazole azo compounds, pyrromethene compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, and pyrrolopyrazole azo methine compounds can be used.

[0393] In addition, as black dyes, reference can be made to compounds described in Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, Japanese Patent No. 2592207, U.S. Patent No. 4808501, U.S. Patent No. 5667920, U.S. Patent No. 505950, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application Laid-Open No. 6-35183, Japanese Patent Application Laid-Open No. 6-51115 and Japanese Patent Application Laid-Open No. 6-194828, etc., and these contents are incorporated into this specification.

[0394] Specific examples of these black dyes include dyes specified in the color index (CI) of Solvent Black 27 to 47, and dyes specified in the CI of Solvent Black 27, 29, or 34 are preferred.

[0395] Commercially available products of these black dyes include Spiron Black MH, Black BH (manufactured by Hodogaya Chemical Co., Ltd.), VALIFAST Black 3804, 3810, 3820, 3830 (manufactured by ORIENT CHEMICAL INDUSTRIES CO., LTD.), Savinyl Black RLSN (manufactured by CLARIANT), KAYASET Black KR, K-BL (manufactured by Nippon Kayaku Co., Ltd.), and the like.

[0396] Furthermore, as a black dye, a pigment multimer can also be used. Examples of pigment multimers include compounds described in Japanese Patent Application Laid-Open No. 2011-213925 and Japanese Patent Application Laid-Open No. 2013-041097. Furthermore, polymerizable dyes having polymerizability within the molecule can be used. Commercially available products include, for example, the RDW series manufactured by Wako Pure Chemical Industries, Ltd.

[0397] Furthermore, as described above, a plurality of dyes each having a color other than black can be combined to form a black dye. Examples of such coloring dyes include, in addition to chromatic dyes (color dyes) such as R (red), G (green), and B (blue), the dyes described in paragraphs 0027 to 0200 of Japanese Patent Application Laid-Open No. 2014-42375.

[0398] (white colorant)

[0399] Examples of the white colorant include one or more selected from white pigments and white dyes. From the viewpoint of weather resistance and the like, white pigments are preferred.

[0400] As white pigment, for example, titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silicon dioxide, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, zinc sulfide etc. can be enumerated.White pigment is preferably a particle with titanium atoms, more preferably titanium oxide.As titanium oxide, the titanium oxide described in "Titanium Oxide Physical Properties and Application Technology, Manabu Seino, June 25, 1991, GIHODO SHUPPAN Co., Ltd. Issue" can also be preferably used.

[0401] Furthermore, as white pigment, CI Pigment White 1, 3, 6, 16, 18, and 21 can be used.

[0402] <Infrared absorber>

[0403] The infrared absorber refers to a compound that absorbs in the infrared region (preferably a wavelength of 650 to 1300 nm). As the infrared absorber, a compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is preferred.

[0404] Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quartacene compounds, dithiol metal complex compounds, and crotonium compounds.

[0405] Phthalocyanine compounds, naphthalocyanine compounds, iminium compounds, cyanine compounds, squarylium compounds, and crotonium compounds disclosed in paragraphs 0010 to 0081 of Japanese Patent Application Laid-Open No. 2010-111750 can be used, and the contents are incorporated into this specification. For cyanine compounds, reference can be made, for example, to "Functional Pigments, by Okawara Nobuyuki, Matsuoka Ken, Kitao Teijiro, and Hirashima Tsuneaki, Kodansha Scientific Ltd.", and the contents are incorporated into this specification.

[0406] As colorants having the above-mentioned spectral characteristics, compounds disclosed in paragraphs 0004 to 0016 of Japanese Patent Application Laid-Open No. 07-164729 and / or compounds disclosed in paragraphs 0027 to 0062 of Japanese Patent Application Laid-Open No. 2002-146254, and near-infrared absorbing particles comprising microcrystals of Cu and / or P oxides and having a number average aggregated particle size of 5 to 200 nm disclosed in paragraphs 0034 to 0067 of Japanese Patent Application Laid-Open No. 2011-164583 can also be used.

[0407] The compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is preferably at least one compound selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, and naphthalocyanine compounds.

[0408] The infrared absorber is preferably a compound that dissolves 1% by mass or more in water at 25° C., more preferably a compound that dissolves 10% by mass or more in water at 25° C. By using such a compound, solvent resistance is improved.

[0409] For pyrrolopyrrole compounds, reference may be made to paragraphs 0049 to 0062 of Japanese Patent Application Publication No. 2010-222557, and the contents are incorporated into this specification. For cyanine compounds and squaric acid compounds, reference may be made to paragraphs 0022 to 0063 of International Publication No. 2014 / 088063, paragraphs 0053 to 0118 of International Publication No. 2014 / 030628, paragraphs 0028 to 0074 of Japanese Patent Application Publication No. 2014-59550, paragraphs 0013 to 0091 of International Publication No. 2012 / 169447, and paragraphs 0017 to 0018 of Japanese Patent Application Publication No. 2014-088063. Paragraphs 0019 to 0033 of Japanese Patent Application Publication No. 2015-176046, paragraphs 0053 to 0099 of Japanese Patent Application Publication No. 2014-63144, paragraphs 0085 to 0150 of Japanese Patent Application Publication No. 2014-52431, paragraphs 0076 to 0124 of Japanese Patent Application Publication No. 2014-44301, paragraphs 0045 to 0078 of Japanese Patent Application Publication No. 2012-8532, Paragraphs 0027 to 0067 of Japanese Patent Application Laid-Open No. 2015-172102, paragraphs 0029 to 0067 of Japanese Patent Application Laid-Open No. 2015-172004, paragraphs 0029 to 0085 of Japanese Patent Application Laid-Open No. 2015-40895, paragraphs 0022 to 0036 of Japanese Patent Application Laid-Open No. 2014-126642, paragraphs 001 to 0026 of Japanese Patent Application Laid-Open No. 2014-148567 1 to 0017, paragraphs 0010 to 0025 of Japanese Patent Application Laid-Open No. 2015-157893, paragraphs 0013 to 0026 of Japanese Patent Application Laid-Open No. 2014-095007, paragraphs 0013 to 0047 of Japanese Patent Application Laid-Open No. 2014-80487, and paragraphs 0007 to 0028 of Japanese Patent Application Laid-Open No. 2013-227403, and the like, and the contents are incorporated into this specification.

[0410] 〔Polymerization inhibitor〕

[0411] The composition of the present invention may contain a polymerization inhibitor.

[0412] As the polymerization inhibitor, for example, a known polymerization inhibitor can be used. Examples of the polymerization inhibitor include phenol-based polymerization inhibitors (e.g., p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4-methoxynaphthol, etc.); hydroquinone-based polymerization inhibitors (e.g., hydroquinone, 2,6-di-tert-butylhydroquinone, etc.); quinone-based polymerization inhibitors (e.g., benzoquinone, etc.); free radicals (e.g., free radicals); radical)-based polymerization inhibitors (for example, 2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidinyl 1-oxyl free radical, etc.); nitrobenzene-based polymerization inhibitors (for example, nitrobenzene, 4-nitrotoluene, etc.); and phenothiazine-based polymerization inhibitors (for example, phenothiazine, 2-methoxyphenothiazine, etc.); etc.

[0413] Among them, phenol-based polymerization inhibitors or radical-based polymerization inhibitors are preferred from the viewpoint of providing a more excellent effect of the composition.

[0414] The content of the polymerization inhibitor is preferably 0.0001 to 0.5% by mass, more preferably 0.001 to 0.2% by mass, and even more preferably 0.008 to 0.05% by mass relative to the total solid content of the composition. One polymerization inhibitor may be used alone, or two or more polymerization inhibitors may be used simultaneously. When two or more polymerization inhibitors are used simultaneously, the total content is preferably within the above range.

[0415] The ratio of the content of the polymerization inhibitor to the content of the polymerizable compound in the composition (content of polymerization inhibitor / content of polymerizable compound (mass ratio)) is preferably 0.00005 to 0.02, and more preferably 0.0001 to 0.005.

[0416] [Organic solvent]

[0417] The composition of the present invention includes the organic solvent contained in the dispersion liquid, and may also contain an organic solvent other than the organic solvent contained in the composition by adding the dispersion liquid. Specific examples of such organic solvents are the same as those contained in the dispersion liquid, so their description will be omitted.

[0418] The content of the organic solvent (including the organic solvent contained in the dispersion) is preferably 10 to 97% by mass relative to the total mass of the composition. The lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, even more preferably 60% by mass or more, and particularly preferably 70% by mass or more. The upper limit is preferably 96% by mass or less, more preferably 95% by mass or less. The composition may contain only one organic solvent or two or more. When containing two or more, the total amount of these is preferably within the above range.

[0419] 〔Other optional ingredients〕

[0420] The composition may further contain any other components in addition to the above-mentioned components. For example, particulate components, ultraviolet absorbers, silane coupling agents, surfactants, sensitizers, co-sensitizers, crosslinking agents, curing accelerators, thermosetting accelerators, plasticizers, diluents and fat-sensitizing agents other than the above-mentioned components may be mentioned. In addition, known additives such as adhesion promoters and other auxiliary agents (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension adjusters and chain transfer agents) to the substrate surface may be added as needed.

[0421] For example, these components can be referred to in paragraphs 0183 to 0228 of Japanese Patent Application Publication No. 2012-003225 (paragraphs 0237 to 0309 of the corresponding U.S. Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0102, 0103 to 0104, and 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, and paragraphs 0159 to 0184 of Japanese Patent Application Publication No. 2013-195480, and these contents are incorporated into the description of the present application.

[0422] [Method for producing the composition]

[0423] The composition of the present invention can be prepared by mixing the above-mentioned components using a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, or the like).

[0424] Here, when the composition of the present invention contains a colorant, it is preferred to prepare the above-mentioned dispersion and the colorant dispersion in which the colorant is dispersed, and further mix these with other components to form a composition.

[0425] The colorant dispersion is preferably prepared by mixing a colorant, a resin (preferably a dispersant), and a solvent. Furthermore, it is also preferred that the colorant dispersion contain a polymerization inhibitor.

[0426] When preparing the composition, the components can be mixed all at once, or they can be dissolved or dispersed in a solvent and mixed sequentially. Furthermore, the order of addition and the operating conditions during mixing are not particularly limited.

[0427] The composition is preferably filtered through a filter for the purpose of removing foreign matter and reducing defects, etc. The filter is the same as that mentioned in the method for producing the dispersion, so its description will be omitted.

[0428] The composition preferably contains no impurities such as metals, halogen-containing metal salts, acids, and bases. The content of impurities contained in these materials is preferably 1 ppm by mass or less, more preferably 1 ppb by mass or less, further preferably 100 ppt by mass or less, particularly preferably 10 ppt by mass or less, and most preferably substantially free (below the detection limit of the measuring device).

[0429] The impurities can be measured using an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Inc., Agilent 7500cs model).

[0430] [cured film]

[0431] The cured film of the present invention is a film formed using the composition of the present invention. Specifically, the cured film of the present invention can be obtained by curing a composition layer formed using the composition of the present invention (including a patterned cured film).

[0432] The method for producing the cured film is not particularly limited, but preferably includes the following steps.

[0433] Composition layer forming step

[0434] Exposure process

[0435] Development process

[0436] Hereinafter, each step will be described.

[0437] [Composition layer forming step]

[0438] In the composition layer formation step, a layer of the composition (composition layer) is formed by applying the composition to a support or the like before exposure. As the support, for example, a solid-state imaging element substrate can be used, in which an imaging element (light-receiving element) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (e.g., a silicon substrate). Furthermore, a primer layer (undercoat layer) may be provided on the support as needed to improve adhesion to the upper layer, prevent diffusion of substances, and flatten the substrate surface.

[0439] As a method for applying the composition to the support, various coating methods such as slit coating, inkjet coating, spin coating, cast coating, roll coating, and screen printing can be applied. The film thickness of the composition layer is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.2 to 3 μm. The composition layer applied to the support is dried (prebaked) for 10 to 300 seconds at a temperature of 50 to 140° C. on a hot plate, in an oven, or the like.

[0440] Examples of the primer layer include films containing resins such as (meth)acrylic resins. Specific examples of methods for forming the primer layer include methods in which a composition containing a (meth)acrylate, a crosslinking agent, a surfactant, and a solvent is applied to a support using a coating method such as spin coating to obtain a coating film, followed by drying the coating film.

[0441] About undercoat layer, the contact angle preferably measured using diiodomethane is 20~70 degree, and the contact angle measured using water is 30~80 degree.If the contact angle is more than the lower limit of the above range, the wettability of the color filter is good, and if it is below the upper limit, the surface energy of the film can be controlled to have good coating properties to undercoat layer.As the method for the scope of the above-mentioned contact angle, methods such as adding a surfactant and controlling drying speed, spin coating, rotating speed can be enumerated.The contact angle of undercoat layer is based on the drop method and measured using a contact angle meter.

[0442] A commercially available product can be used as the primer layer, and an example thereof is CT-4000L manufactured by FUJIFILM Electronic Materials Co., Ltd.

[0443] [Exposure process]

[0444] In the exposure step, the composition layer formed in the composition layer forming step is exposed by irradiating it with active light or radiation, and the light-irradiated composition layer is cured.

[0445] As a method of light irradiation, it is preferable to perform light irradiation through a photomask having patterned openings.

[0446] Exposure is preferably performed by irradiation with radiation. The radiation that can be used for exposure is preferably ultraviolet rays such as g-rays, h-rays, or i-rays, and the light source is preferably a high-pressure mercury lamp. The irradiation intensity is preferably 5 to 1500 mJ / cm 2 , more preferably 10 to 1000 mJ / cm 2 .

[0447] When the composition contains a thermal polymerization initiator, the composition layer may be heated during the exposure step. The heating temperature is not particularly limited, but is preferably 80 to 250° C. The heating time is preferably 30 to 300 seconds.

[0448] In addition, in the exposure step, when the composition layer is heated, a post-heating step described below may be used simultaneously. In other words, in the exposure step, when the composition layer is heated, the method for producing a cured film may not include a post-heating step.

[0449] [Development process]

[0450] The development step is a step of developing the exposed composition layer to form a cured film. This step dissolves the portion of the composition layer not exposed to light during the exposure step, leaving only the photocured portion, thereby obtaining a patterned cured film.

[0451] The type of developer used in the development step is not particularly limited, but an alkaline developer that does not damage the imaging element and circuits on the substrate is preferred.

[0452] The development temperature is, for example, 20 to 30°C.

[0453] The development time is, for example, 20 to 90 seconds. In recent years, for better residue removal, it has sometimes been extended to 120 to 180 seconds. Furthermore, to further improve residue removal, the developer solution is sometimes discarded and then supplied in a repeated process of 60-second intervals.

[0454] The alkali developer is preferably an alkaline aqueous solution prepared by dissolving an alkaline compound in water so as to have a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass).

[0455] Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene (among them, organic bases are preferred).

[0456] When used as an alkaline developer, washing treatment with water is generally performed after development.

[0457] 〔Post-baking〕

[0458] A heat treatment (post-baking) is preferably performed after the exposure step. Post-baking is a post-development heat treatment to complete curing. The heating temperature is preferably 240°C or lower, more preferably 220°C or lower. The lower limit is not particularly limited, but considering efficiency and effective processing, it is preferably 50°C or higher, more preferably 100°C or higher.

[0459] Post-baking can be performed continuously or intermittently using a heating mechanism such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater.

[0460] The post-bake is preferably performed in an atmosphere with a low oxygen concentration. The oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, even more preferably 10% by volume or less, particularly preferably 7% by volume or less, and most preferably 3% by volume or less. The lower limit is not particularly limited, but is typically 10 ppm by volume or more.

[0461] Furthermore, it is possible to change to the post-baking based on the above-mentioned heating and complete the curing by UV (ultraviolet) irradiation.

[0462] In this case, the above-mentioned composition preferably further contains a UV curing agent. The UV curing agent is preferably a UV curing agent that can be cured at a wavelength shorter than the exposure wavelength of 365 nm, which is the wavelength of the polymerization initiator added for the usual i-ray exposure etching process. As a UV curing agent, for example, CIBS IRGACURE 2959 (product name) can be cited. In the case of UV irradiation, it is preferred that the composition layer is a material that is cured at a wavelength of 340 nm or less. The lower limit of the wavelength is not particularly limited, but is generally above 220 nm. In addition, the exposure amount of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and even more preferably 800 to 3500 mJ. In order to perform low-temperature curing more effectively, the UV curing process is preferably performed after the exposure process. An ozone-free mercury lamp is preferably used as the exposure light source.

[0463] [Physical properties, shape, and applications of cured films, etc.]

[0464] The film thickness of the cured film is preferably 0.1 to 4.0 μm, more preferably 1.0 to 2.5 μm. The cured film can be made thinner than this range or thicker depending on the application.

[0465] The reflectance of the cured film is preferably 10% or less, more preferably 5% or less, and even more preferably 3% or less. The lower limit is 0% or more.

[0466] The reflectivity referred to herein can be determined by using a VAR unit (V7200, a spectrometer manufactured by JASCO Corporation) to obtain a reflection spectrum by injecting light having a wavelength of 400 to 1100 nm at an incident angle of 5°. Specifically, the reflectivity of the cured film is determined by taking the reflectivity of light having a wavelength that exhibits the maximum reflectivity within the wavelength range of 400 to 1100 nm.

[0467] When the cured film is patterned, the size of one side of the pattern of the cured film is preferably 3 μm or less, more preferably 2 μm or less, and even more preferably 1.4 μm or less. The lower limit of the size of one side of the pattern of the cured film is not particularly limited, but is preferably 0.3 μm.

[0468] The pattern shape of the cured film is not particularly limited. However, when the cured film is a color filter used in a solid-state imaging element or the like, the pattern shape of the cured film is usually rectangular.

[0469] Furthermore, the above-mentioned cured film is suitable for portable devices such as personal computers, tablet computers, mobile phones, smartphones and digital cameras; OA (Office Automation) equipment such as printer multifunction machines and scanners; industrial equipment such as surveillance cameras, barcode readers, automated teller machines (ATMs), high-speed cameras and equipment with personal authentication functions using facial image authentication or biometric authentication; vehicle-mounted camera equipment; medical camera equipment such as endoscopes, capsule endoscopes and catheters; and space equipment such as living body sensors, biosensors, military reconnaissance cameras, stereo map cameras, meteorological and ocean observation cameras, land resource reconnaissance cameras and space astronomy and deep space target exploration cameras; and filters (for example, color filters) used in the light-shielding components and light-shielding films of modules, as well as anti-reflection components, i.e., anti-reflection films.

[0470] The cured film can also be used in applications such as micro-LEDs (Light Emitting Diodes) and micro-OLEDs (Organic Light Emitting Diodes). In addition to filters and optical films (e.g., color filters) used in micro-LEDs and micro-OLEDs, the cured film is also suitable for components that provide light-shielding or anti-reflection functions.

[0471] Examples of micro LEDs and micro OLEDs include those described in Japanese Unexamined Patent Application Publication No. 2015-500562 and Japanese Unexamined Patent Application Publication No. 2014-533890.

[0472] The cured film is also suitable as an optical filter or optical film (e.g., a color filter) used in quantum dot sensors and quantum dot solid-state imaging devices. Furthermore, it is suitable as a component that imparts light-shielding and anti-reflection functions. Examples of quantum dot sensors and quantum dot solid-state imaging devices include those described in U.S. Patent Application Publication No. 2012 / 37789 and International Publication No. 2008 / 131313.

[0473] [Light-shielding film, color filter, optical element, solid-state imaging element, and solid-state imaging device]

[0474] When the cured film of the present invention is formed using the composition of the present invention using a black colorant as a colorant, the cured film can also be preferably used as a so-called light-shielding film. Such a light-shielding film is also preferably used in a solid-state imaging element.

[0475] Furthermore, a light-shielding film is one of the preferred uses of the cured film of the present invention. The light-shielding film of the present invention can be produced in the same manner as described above as the method for producing the cured film.

[0476] When the cured film of the present invention is formed using the composition of the present invention using a colorant as a colorant, the cured film is preferably used as a so-called color filter. Such a color filter is also preferably used in a solid-state imaging device.

[0477] Furthermore, a color filter is one of the preferred applications of the cured film of the present invention. The color filter of the present invention can be produced in the same manner as the method further described above as the method for producing the cured film.

[0478] The present invention also includes the invention of an optical element. The optical element of the present invention is an optical element having the above-mentioned cured film. Examples of the optical element include optical elements used in optical equipment such as cameras, binoculars, microscopes, and semiconductor exposure equipment.

[0479] Among them, as the optical element, for example, a solid-state imaging element mounted in a camera or the like is preferable.

[0480] Furthermore, the solid-state imaging element of the present invention is a solid-state imaging element including the cured film of the present invention.

[0481] As an embodiment of the solid-state imaging element of the present invention containing a cured film, for example, a substrate is provided with a plurality of photodiodes constituting the light-receiving region of the solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) and a light-receiving element formed of polycrystalline silicon or the like, and a cured film is provided on the light-receiving element formation surface side of the support (for example, a portion other than the light-receiving portion and / or color adjustment pixels, etc.) or on the side opposite to the formation surface.

[0482] Furthermore, when the cured film is used as a light attenuating film, for example, if the light attenuating film is arranged so that a portion of light passes through the light attenuating film and enters a light receiving element, the dynamic range of the solid-state imaging element can be improved.

[0483] A solid-state imaging device includes the above-mentioned solid-state imaging element.

[0484] refer to Figures 1-2 , the configuration examples of the solid-state imaging device and the solid-state imaging element are described. Figures 1-2 In order to clarify each part, a portion is shown enlarged without regard to the ratio of thickness and / or width between them.

[0485] Figure 1 It is a schematic cross-sectional view showing a configuration example of a solid-state imaging device including the solid-state imaging element of the present invention.

[0486] like Figure 1 As shown, the solid-state imaging device 100 includes a rectangular solid-state imaging element 101 and a transparent cover glass 103 that is held above the solid-state imaging element 101 and seals the solid-state imaging element 101. Furthermore, a lens layer 111 is superimposed on the cover glass 103 via a spacer 104. The lens layer 111 is composed of a support 113 and a lens material 112. The lens layer 111 may also be a structure in which the support 113 and the lens material 112 are integrally formed. If stray light enters the peripheral area of ​​the lens layer 111, the light diffusion weakens the focusing effect of the lens material 112, and the light reaching the imaging unit 102 is reduced. In addition, noise caused by the stray light is generated. Therefore, a light-shielding film 114 is provided on the peripheral area of ​​the lens layer 111 to block light. The cured film of the present invention can also be used as the light-shielding film 114.

[0487] Solid-state imaging element 101 photoelectrically converts an optical image formed on its light-receiving surface, imaging section 102, and outputs the image as an image signal. Solid-state imaging element 101 includes a laminated substrate 105 formed by stacking two substrates. Laminated substrate 105 includes a rectangular chip substrate 106 and a circuit substrate 107 of equal size. Circuit substrate 107 is laminated on the back of chip substrate 106.

[0488] As a material of a substrate used as the chip substrate 106 , for example, a well-known material can be used.

[0489] An imaging unit 102 is provided in the center of the surface of the chip substrate 106. Furthermore, a light-shielding film 115 is provided in the peripheral region of the imaging unit 102. Light-shielding film 115 blocks stray light from entering the peripheral region, thereby preventing the generation of dark current (noise) from the circuits in the peripheral region. The cured film of the present invention can be used as light-shielding film 115.

[0490] A plurality of electrode pads 108 are provided on the edge of the surface of the chip substrate 106 . The electrode pads 108 are electrically connected to the imaging unit 102 via signal lines (which may be bonding wires) not shown and provided on the surface of the chip substrate 106 .

[0491] On the back surface of the circuit substrate 107, external connection terminals 109 are provided approximately below each electrode pad 108. Each external connection terminal 109 is connected to the electrode pad 108 via a through electrode 110 that vertically penetrates the multilayer substrate 105. Furthermore, each external connection terminal 109 is connected via wiring (not shown) to a control circuit that controls the driving of the solid-state imaging element 101 and an image processing circuit that performs image processing on the imaging signal output from the solid-state imaging element 101.

[0492] Figure 2 A schematic cross-sectional view of the imaging unit 102 is shown in FIG. Figure 2 As shown, the imaging unit 102 is composed of components such as a light-receiving element 201, a color filter 202, and a microlens 203, which are provided on a substrate 204. The color filter 202 includes a blue pixel 205b, a red pixel 205r, a green pixel 205g, and a black matrix 205bm. The cured film of the present invention can be used as the blue pixel 205b, the red pixel 205r, the green pixel 205g, and the black matrix 205bm.

[0493] As the material for the substrate 204, for example, the same material as the aforementioned chip substrate 106 can be used. A p-well layer 206 is formed on the surface of the substrate 204. Light-receiving elements 201 are arranged in a square lattice pattern within the p-well layer 206. The light-receiving elements 201 include an n-type layer and generate and accumulate signal charges through photoelectric conversion.

[0494] On one side of the light-receiving element 201, a vertical transfer path 208 comprising an n-type layer is formed via a readout gate portion 207 on the surface of the p-well layer 206. Furthermore, on the other side of the light-receiving element 201, a vertical transfer path 208 for an adjacent pixel is formed via an element isolation region 209 comprising a p-type layer. The readout gate portion 207 serves as a channel region for reading signal charge accumulated in the light-receiving element 201 to the vertical transfer path 208.

[0495] A gate insulating film 210 composed of an ONO (Oxide-Nitride-Oxide) film is formed on the surface of the substrate 204. A vertical transfer electrode 211 composed of polycrystalline silicon or amorphous silicon is formed on this gate insulating film 210, covering the vertical transfer path 208, the readout gate portion 207, and approximately directly above the element isolation region 209. The vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to transfer charge, and as a readout electrode that drives the readout gate portion 207 to read out signal charge. The signal charge is sequentially transferred from the vertical transfer path 208 to the horizontal transfer path and output portion (floating diffusion amplifier) ​​(not shown), where it is then output as a voltage signal.

[0496] A light shielding film 212 is formed on the vertical transfer electrode 211 to cover the surface thereof. The light shielding film 212 has an opening directly above the light receiving element 201 and shields the remaining area from light. The cured film of the present invention can be used as the light shielding film 212.

[0497] A transparent intermediate layer including an insulating film 213 made of BPSG (borophosphosilicate glass), an insulating film (passivation film) 214 made of P-SiN, and a planarizing film 215 made of a transparent resin or the like is provided on the light shielding film 212. The color filter 202 is formed on the intermediate layer.

[0498] [Image Display Device]

[0499] The image display device of the present invention includes the cured film of the present invention.

[0500] As an embodiment in which an image display device has a cured film, for example, a color filter formed using the cured film of the present invention is used in an image display device. The color filter may include a black matrix.

[0501] Next, a black matrix and a color filter including the black matrix will be described. Furthermore, a liquid crystal display device including such a color filter will be described as a specific example of an image display device.

[0502] Black Matrix

[0503] The cured film of the present invention is preferably also contained in a black matrix. A black matrix may be contained in image display devices such as color filters, solid-state imaging elements, and liquid crystal display devices.

[0504] Examples of the black matrix include the black matrix described above; a black edge portion provided at the periphery of an image display device such as a liquid crystal display; black grid-like and / or stripe-like portions between red, blue, and green pixels; and black dot-like and / or linear patterns used to shield TFTs (thin film field-effect transistors). The definition of the black matrix is ​​described, for example, in "Dictionary of Terms for Liquid Crystal Display Manufacturing Equipment," 2nd edition, by Taihei Kanno, Nikkan Kogyo Shimbun, Ltd., 1996, p. 64.

[0505] In order to improve the display contrast, and in the case of a liquid crystal display device using an active matrix drive method of thin film field effect transistors (TFT), to prevent the degradation of image quality caused by current leakage due to light, the black matrix preferably has a high light-shielding property (measured in optical density OD of 3 or more).

[0506] As a method for producing a black matrix, for example, it can be produced using the same method as the method for producing the above-mentioned cured film. Specifically, a composition layer can be formed by applying the composition on a substrate, and then exposing and developing it to produce a patterned cured film (black matrix). In addition, the film thickness of the cured film used as the black matrix is ​​preferably 0.1 to 4.0 μm.

[0507] The material of the substrate preferably has a transmittance of 80% or greater for visible light (wavelength 400-800 nm). Examples of such materials include glasses such as soda-lime glass, alkali-free glass, quartz glass, and borosilicate glass; and plastics such as polyester resins and polyolefin resins. From the perspective of chemical resistance and heat resistance, alkali-free glass and quartz glass are preferred.

[0508] Color Filters

[0509] The cured film of the present invention is also preferably included in a color filter.

[0510] Examples of color filters comprising a cured film include a color filter comprising a substrate and red, green, and blue colored pixels (cured film) formed on the substrate. Alternatively, the color filter may comprise a substrate, the black matrix, and red, green, and blue colored pixels formed in openings of the black matrix formed on the substrate.

[0511] The color filter including the black matrix can be manufactured by the following method, for example.

[0512] First, a coating film (composition layer) of a composition containing a coloring material corresponding to each colored pixel of a color filter is formed in the openings of a patterned black matrix formed on a substrate.

[0513] Next, the composition layer is exposed through a photomask having a pattern corresponding to the openings of the black matrix. After developing to remove the unexposed portions, the layer is baked to form colored pixels in the openings of the black matrix. For example, by performing this series of operations using a composition containing red, green, and blue pigments, a color filter having red, green, and blue pixels can be manufactured.

[0514] [Liquid Crystal Display Device]

[0515] The cured film of the present invention is also preferably included in a liquid crystal display device. As an embodiment in which a liquid crystal display device includes a cured film, an embodiment including the color filter described above can be given.

[0516] The liquid crystal display device of this embodiment may include, for example, a pair of opposing substrates and a liquid crystal compound sealed between the substrates. The substrates may be, for example, black matrix substrates as described above.

[0517] As a specific form of the above-mentioned liquid crystal display device, for example, a stacked body including, from the user side, a polarizer / substrate / color filter / transparent electrode layer / orientation film / liquid crystal layer / orientation film / transparent electrode layer / TFT (Thin Film Transistor: thin film field effect transistor) element / substrate / polarizer / backlight unit.

[0518] Examples of liquid crystal display devices include those described in "Electronic Display Devices (written by Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd. in 1990)" and "Display Devices (written by Junsho Ibuki, published by Sangyotosyo Inc. in 1989)." Furthermore, examples include those described in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd. in 1994)."

[0519] [Infrared sensor]

[0520] The cured film of the present invention is preferably also included in an infrared sensor.

[0521] use Figure 3 The infrared sensor of the above-mentioned embodiment will be described. Figure 3 It is a schematic cross-sectional view showing a configuration example of an infrared sensor including the cured film of the present invention. Figure 3 The infrared sensor 300 shown in FIG. 1 includes a solid-state imaging element 310 .

[0522] The imaging area provided on the solid-state imaging element 310 is formed by combining an infrared absorption filter 311 and a color filter 312 according to an embodiment of the present invention.

[0523] The infrared absorption filter 311 is a film that transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800 to 1300 nm, preferably light with a wavelength of 900 to 1200 nm, and more preferably light with a wavelength of 900 to 1000 nm). A cured film containing an infrared absorber (the form of the infrared absorber is as described above) can be used as a colorant.

[0524] The color filter 312 is a color filter formed with pixels that transmit and absorb specific wavelengths of light in the visible light region. For example, a color filter formed with red (R), green (G), and blue (B) pixels is used, and its form is as described above.

[0525] A resin film 314 (for example, a transparent resin film) capable of transmitting light having a wavelength that has passed through the infrared transmission filter 313 is disposed between the infrared transmission filter 313 and the solid-state imaging element 310 .

[0526] The infrared transmission filter 313 has visible light shielding properties and transmits infrared light of a specific wavelength. The cured film of the present invention containing a colorant that absorbs light in the visible light range (e.g., a perylene compound and / or a bisbenzofuranone compound) and an infrared absorber (e.g., a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, and a polymethine compound) can be used. For example, the infrared transmission filter 313 preferably blocks light with a wavelength of 400 to 830 nm while transmitting light with a wavelength of 900 to 1300 nm.

[0527] A microlens 315 is disposed on the incident light hν side of the color filter 312 and the infrared transmission filter 313. A planarization film 316 is formed so as to cover the microlens 315.

[0528] exist Figure 3 In the illustrated embodiment, the resin film 314 is provided, but the infrared transmission filter 313 may be formed instead of the resin film 314 . That is, the infrared transmission filter 313 may be formed on the solid-state imaging element 310 .

[0529] And, in Figure 3 In the illustrated embodiment, the film thickness of the color filter 312 and the film thickness of the infrared transmission filter 313 are the same, but the film thicknesses of the two may be different.

[0530] And, in Figure 3 In the form shown, the color filter 312 is arranged on the side closer to the incident light hν than the infrared absorption filter 311, but the order of the infrared absorption filter 311 and the color filter 312 can also be reversed, and the infrared absorption filter 311 can be arranged on the side closer to the incident light hν than the color filter 312.

[0531] And, in Figure 3 In the illustrated embodiment, the infrared absorption filter 311 and the color filter 312 are stacked adjacent to each other. However, the two filters do not necessarily need to be adjacent; another layer may be provided between them. The cured film of the present invention can be used as a light-shielding film on the ends and / or sides of the surface of the infrared absorption filter 311. Furthermore, when used on the inner walls of an infrared sensor device, it prevents internal reflection and / or unwanted light from entering the light-receiving portion, thereby improving sensitivity.

[0532] This infrared sensor simultaneously captures image information, enabling motion sensing, such as identifying the object being sensed. Furthermore, since it can acquire distance information, it can also capture images that include 3D information. Furthermore, this infrared sensor can be used as a biometric authentication sensor.

[0533] Next, a solid-state imaging device to which the above-described infrared sensor is applied will be described.

[0534] The solid-state imaging device includes a lens optical system, a solid-state imaging element, an infrared light-emitting diode, etc. For the configuration of the solid-state imaging device, reference can be made to paragraphs 0032 to 0036 of Japanese Patent Application Laid-Open No. 2011-233983, the contents of which are incorporated herein by reference.

[0535] [Headlamp unit]

[0536] The cured film of the present invention is also preferably incorporated as a light-shielding film into a headlamp unit for a vehicle such as an automobile. The cured film of the present invention incorporated as a light-shielding film into a headlamp unit is preferably formed into a pattern so as to shield at least a portion of light emitted from a light source.

[0537] use Figure 4 and Figure 5 The headlamp unit according to the above embodiment will be described. Figure 4 is a schematic diagram showing an example of the configuration of a headlamp unit. Figure 5 It is a schematic perspective view showing a configuration example of a light shielding portion of a headlight unit.

[0538] like Figure 4 As shown, the headlamp unit 10 includes a light source 12 , a light shielding portion 14 , and a lens 16 , which are arranged in this order.

[0539] like Figure 5 As shown, the light shielding portion 14 includes a base 20 and a light shielding film 22 .

[0540] Light-shielding film 22 is formed with openings 23 for illuminating light emitted from light source 12 in a specific pattern. The light distribution pattern emitted from lens 16 is determined by the shape of openings 23 in light-shielding film 22. Lens 16 projects light L from light source 12 that has passed through light-shielding portion 14. As long as a specific light distribution pattern can be emitted from light source 12, lens 16 is not essential. The lens 16 can be appropriately determined based on the irradiation distance and range of light L.

[0541] The structure of the base 20 is not particularly limited as long as it can hold the light shielding film 22 , but is preferably not deformed by heat from the light source 12 and is, for example, made of glass.

[0542] Figure 5 An example of a light distribution pattern is shown in FIG, but the present invention is not limited thereto.

[0543] Furthermore, the number of light sources 12 is not limited to one; for example, they may be arranged in a row or in a matrix. When multiple light sources are provided, for example, one light shielding portion 14 may be provided for each light source 12. In this case, the light shielding films 22 of the multiple light shielding portions 14 may all have the same pattern or different patterns.

[0544] The light distribution pattern based on the pattern of the light shielding film 22 will be described.

[0545] Figure 6 is a schematic diagram showing an example of a light distribution pattern by a headlamp unit. Figure 7 : is a schematic diagram showing another example of a light distribution pattern based on a headlamp unit. Figure 6 The light distribution pattern 30 shown in Figure 7 The light distribution patterns 32 shown in FIG. 3 all represent areas irradiated with light. Figure 6 The area 31 and Figure 7 In the case where the area 31 shown in FIG. 1 is not provided with the light shielding film 22, it indicates that the light source 12 (reference Figure 4 ) irradiated area.

[0546] By the pattern of the light shielding film 22, for example, Figure 6 As shown in the light distribution pattern 30 shown in FIG, the light intensity drops sharply at the edge 30a. Figure 6 The light distribution pattern 30 shown in FIG. 1 is a pattern in which light is not irradiated to oncoming vehicles when the vehicle is traveling on the left side, for example.

[0547] And, as Figure 7 As shown in the light distribution pattern 32, it is also possible to remove Figure 6 In this case, the light distribution pattern 30 is also a part of the pattern shown in FIG. Figure 6 Similar to the light distribution pattern 30 shown in FIG, the light intensity drops sharply at edge 32a, resulting in a pattern that prevents oncoming vehicles from receiving light when driving on the left. Furthermore, the light intensity also drops sharply at notch 33. Therefore, the area corresponding to notch 33 can display symbols indicating road conditions such as curves, uphill slopes, and downhill slopes. This improves nighttime driving safety.

[0548] The light shielding portion 14 is not limited to being fixedly disposed between the light source 12 and the lens 16 , but may be provided between the light source 12 and the lens 16 as needed by a driving mechanism (not shown) to obtain a specific light distribution pattern.

[0549] Furthermore, the light shielding portion 14 may be a light shielding member capable of shielding light from the light source 12. In this case, it may be provided between the light source 12 and the lens 16 as needed by a driving mechanism (not shown) to obtain a specific light distribution pattern.

[0550] The cured film of the present invention is also preferably used as a light-shielding film for fingerprint authentication. The light-shielding film preferably has a plurality of pores (holes) for transmitting light. The pores may be filled with a light-transmitting material.

[0551] Example

[0552] Below, based on embodiment, the present invention is further described in detail. The materials, usage amounts, ratios, processing contents and processing steps etc. shown in the following examples can be appropriately changed as long as they do not depart from the purpose of the present invention. Therefore, the scope of the present invention should not be interpreted restrictively by the examples shown below. In addition, the content in the table, as long as it is not particularly specified, represents a mass benchmark.

[0553] [Synthesis Example 1: Synthesis of polysiloxane compound (S-1)]

[0554] A mixed solution of 30 parts by mass of the silane coupling agent (A-1) listed in Table 1 and 70 parts by mass of ethanol was stirred at room temperature, and 15 parts by mass of a 0.1% by mass aqueous nitric acid solution was added thereto over 1 hour. The mixture was then stirred at 50°C for 24 hours. The reaction solution was concentrated under reduced pressure using an evaporator to obtain 27 parts by mass of a polysiloxane compound (S-1).

[0555] [Synthesis Examples 2 to 25: Synthesis of Polysiloxane Compounds (S-2) to (S-25)]

[0556] Polysiloxane compounds (S-2) to (S-25) were obtained by the same operation as in Synthesis Example 1 except that the silane coupling agents listed in Table 1 or Table 2 were used. Table 3 shows the physical properties.

[0557] <Silane coupling agent>

[0558] In Tables 1 and 2, * in the group shown in the column X represents the bonding position to * in the group shown in the column Y. Furthermore, Me represents a methyl group, and Et represents an ethyl group.

[0559] [Table 1]

[0560]

[0561] [Table 2]

[0562]

[0563] [Table 3]

[0564]

[0565] [Synthesis Example 27: Synthesis of Surface-Modified Particles (L-1)]

[0566] To a solution obtained by mixing 100 parts by mass of a dispersion (X-1) containing unmodified particles (aqueous dispersion of silica particles (manufactured by Nissan Chemical Industries, LTD., SNOWTEX ST-O-40, solid content concentration 40% by mass)), 100 parts by mass of ethanol and 2 parts by mass of a surface modifier (silane coupling agent (A-1)), 1% by mass of 1% aqueous ammonia was added, and the mixture was stirred at 25°C for 72 hours. The obtained solution was concentrated to 100 parts by mass. The solution was centrifuged (10,000 rotations per minute) and the supernatant was discarded. 1,000 parts by mass of 1-methoxy-2-propanol was added to the precipitate, centrifuged again, and the supernatant was removed. The obtained precipitate was dried under reduced pressure at 50°C for 24 hours to obtain 39 parts by mass of surface-modified particles (L-1).

[0567] (Analysis of Residual Amount of Surface Modifier and Its Condensate (Polysiloxane) in Surface Modified Particles)

[0568] 1 part by mass of the surface modified particles (L-1) obtained was added to 9 parts by mass of 1-methoxy-2-propanol and dispersed by ultrasonication for 1 hour. Then, a centrifugal separation operation was performed to concentrate the obtained supernatant. 29 Si NMR (Nuclear Magnetic Resonance) observation revealed that the peak value was below the detection limit (0.1 mass %).

[0569] [Synthesis Examples 27 to 60: Synthesis of Surface-Modified Particles (L-1) to (L-34)]

[0570] Surface-modified particles (L-1) to (L-34) were synthesized by the same procedures as in Synthesis Example 1, except that the dispersion and surface modifier (silane coupling agent) containing the unmodified particles listed in Table 4 were used. Furthermore, the residual amount of the surface modifier and its condensate (polysiloxane) in each surface-modified particle was analyzed in the same manner as for the surface-modified particle (L-1). The peak values ​​were all below the detection limit (0.1% by mass).

[0571] <Dispersion containing unmodified particles>

[0572] X-1: Aqueous dispersion of silica particles (manufactured by Nissan Chemical Industries, Ltd., SNOWTEX ST-O-40, solid content concentration 40% by mass) X-2: Isopropyl alcohol dispersion of silica particles (manufactured by Nissan Chemical Industries, Ltd., ORGANO SILICA SOL IPA-STL, solid content concentration 30% by mass) X-3: Methanol dispersion of titanium oxide particles obtained in the operation of Example 1 of International Publication No. 2016 / 136764 (solid content concentration 15% by mass) X-4: Aqueous dispersion of zirconium oxide particles obtained in the operation of Example 1 of JP-A-2010-150066 (solid content concentration 5% by mass)

[0573] [Table 4]

[0574]

[0575] [Synthesis Example 61: Synthesis of Unmodified Particles X-5 for Comparative Example]

[0576] The same operation was carried out as in Synthesis Example 27, except that the silane coupling agent (A-1) was not added, to obtain 38 parts by mass of unmodified particles X-5.

[0577] [Examples 1-1 to 1-43 and Comparative Examples 1-1 to 1-3: Preparation and Evaluation of Dispersions of Surface-Modified Particles]

[0578] 15 parts by mass of surface-modified particles (L-1), 100 parts by mass of dehydrated 1-methoxy-2-propanol, and polysiloxane (type and amount listed in Table 5) were added and ultrasonic dispersion was performed for 10 hours. The water content of the resulting dispersion was measured, and water was added to adjust the water content shown in Table 5.

[0579] In Table 5, the polysiloxane content (polysiloxane content) was calculated based on the following formula: The water content is the mass % of water relative to the total mass of the dispersion.

[0580] Polysiloxane content (%) = 100 × (amount of polysiloxane added) / {(amount of surface-modified particles or unmodified particles added) + (amount of polysiloxane added)}

[0581] <Evaluation of storage stability>

[0582] The storage stability of the obtained dispersion was confirmed by viscosity measurement after forced heating at 45°C for 60 days. The viscosity of the dispersion was measured using a viscometer (TV-22 viscometer, cone-plate type, manufactured by TOKI SANGYO CO., LTD.). The viscosity of the dispersion was measured while adjusting the temperature of the dispersion to 25°C.

[0583] A: The change rate of the dispersion viscosity is less than 2%.

[0584] B: The change rate of the viscosity of the dispersion is 2% or more and less than 5%.

[0585] C: The change rate of the viscosity of the dispersion is 5% or more and less than 8%.

[0586] D: The change rate of the viscosity of the dispersion liquid is 8% or more and less than 10%.

[0587] E: The change rate of the dispersion viscosity is 10% or more.

[0588] [Table 5]

[0589]

[0590] As shown in Table 5, the dispersions containing surface-modified particles and polysiloxane and having a polysiloxane content of 1 to 39% by mass in the present invention all exhibited excellent storage stability (Examples).

[0591] From the comparison between Example 1-16 and Examples 1-35 and 1-36, the groups contained in the modified portion of the surface-modified particles (i.e., R A1 Or R in formula A2 A2 ) and the functional groups contained in the units constituting the siloxane (ie, R B1 Or R in formula B2 B2 ) under the same conditions (Examples 1-16), it shows more excellent storage stability.

[0592] Comparison of Example 1-16 with Examples 1-37 and 1-38 shows that when the polysiloxane content is within the range of 1 to 25% by mass (Example 1-16), even better storage stability is demonstrated. Comparison of Example 1-39 with Example 1-41 and of Example 1-35 with Example 1-42 also confirms the same trend.

[0593] Comparison of Example 1-16 with Examples 1-39 and 1-40 shows that when the moisture content is within the range of 0.1 to 3 mass % (Example 1-16), even better storage stability is exhibited. A similar trend can also be observed in comparison of Example 1-42 with Example 1-43.

[0594] On the other hand, when the polysiloxane content was greater than 39% by mass (Comparative Example 1-1), when no polysiloxane was contained (Comparative Example 1-2), and when unmodified particles were used (Comparative Example 1-3), poor storage stability was exhibited.

[0595] [Examples 2-1 to 2-43 and Comparative Examples 2-1 to 2-3: Preparation of Curable Compositions]

[0596] A curable composition was prepared by mixing the following components. The components listed in Table 6 were used for the dispersion, polymerizable compound, and resin.

[0597] Dispersion liquid: 100 parts by mass

[0598] Polymerizable compound: 10 parts by mass

[0599] Resin: 5 parts by mass

[0600] Thermal polymerization initiator (tert-butyl perbenzoate): 1 part by mass

[0601] Surfactant W1 (structure shown below): 1 part by mass

[0602] <Resin>

[0603] b1: Resin with the following structure (the numerical value marked on the main chain is the molar ratio. Mw: 30000)

[0604] [Chemical Formula 13]

[0605]

[0606] b2: Resin with the following structure (the numerical value marked on the main chain is the molar ratio. Mw: 11000)

[0607] [Chemical Formula 14]

[0608]

[0609] b3: Resin with the following structure (the numerical value marked on the main chain is the molar ratio. Mw: 10000)

[0610] [Chemical Formula 15]

[0611]

[0612] (Polymerizable compound)

[0613] M-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

[0614] M-2: NK Ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0615] M-3: NK Ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0616] M-4: Succinic acid modified dipentaerythritol pentaacrylate

[0617] M-5: Dipentaerythritol hexaacrylate

[0618] (Surfactant)

[0619] Surfactant W1: 1 mass % PGMEA (propylene glycol monomethyl ether acetate) solution of the following compound (the ratio of the repeating units is expressed in mol %, Mw: 14000)

[0620] [Chemical Formula 16]

[0621]

[0622] <Evaluation of storage stability>

[0623] The storage stability of the curable composition was evaluated by the same procedure and evaluation criteria as those for the evaluation of storage stability using the above dispersion, except that the curable composition obtained as described above was used.

[0624] [Table 6]

[0625]

[0626] As shown in Table 6, it was confirmed that the evaluation results of the storage stability of the curable composition showed the same tendency as that of the above-mentioned dispersion.

[0627] <Evaluation of Cured Film>

[0628] A CT-4000L solution (manufactured by FUJIFILM Electronic Materials Co., Ltd.; clear primer) was applied to a 10 cm×10 cm glass substrate to a dry film thickness of 0.1 μm, dried to form a transparent film, and then heated at 220° C. for 5 minutes.

[0629] Next, the curable composition (E-1) was applied by spin coating so that the film thickness after pre-baking was 0.6 μm. Then, pre-baking was performed at 100° C. for 2 minutes and post-baking was performed at 200° C. for 3 minutes using a hot plate.

[0630] The surface morphology of the obtained cured film was good, with no haze observed. Furthermore, a peel test (evaluation was performed by applying a transparent tape (manufactured by NICHIBAN CO., LTD., a registered trademark) to the film and then peeling it off) revealed that no peeling or loss of the cured film was observed, and a tough film was formed.

[0631] Similar procedures and evaluations were performed using curable compositions (E-2) to (E-34), resulting in similarly strong films. In particular, the cured films of compositions (E-16) to (E-19), (E-25) to (E-29), (E-31), (E-33), and (E-34) containing fluoroalkyl or polysiloxane structures exhibited smooth and excellent surface morphology after tape removal.

[0632] On the other hand, when curable compositions (E-35) to (E-43) were used, cured films having good surface morphology were obtained, but in the peeling test, a portion of the cured film was lost or peeled off.

[0633] In addition, in the curable compositions (E-44) to (E-46) of the comparative examples, haze was observed on the coating surface morphology, and in the peel test, peeling and loss of the cured film were observed more frequently than when the curable compositions (E-35) to (E-43) were used.

[0634] [Examples 3-1 to 3-47 and Comparative Examples 3-1 to 3-3: Preparation of Coloring Compositions]

[0635] <Preparation of Pigment Dispersion>

[0636] A dispersion was prepared by mixing and dispersing the dispersion resins, pigments, pigment derivatives, and solvents of the types listed in Table 7 below at the ratios listed in Table 7 below for 3 hours using a bead mill (zirconium dioxide beads with a diameter of 0.3 mm). The dispersion was then prepared using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) equipped with a pressure reducing mechanism at 2000 kg / cm 3 The dispersion was carried out at a flow rate of 500 g / min under a pressure of 1000 rpm. This dispersion was repeated 10 times to obtain a pigment dispersion.

[0637] [Table 7]

[0638]

[0639] (Dispersion resin)

[0640] DPB-1: the following compound (solid content 30% by mass, PGMEA solution, Mw 16000)

[0641] DPB-2: the following compound (solid content 30% by mass, PGMEA solution, Mw 8000)

[0642] DPB-3: the following compound (solid content 30% by mass, PGMEA solution, Mw 15000)

[0643] In the following formulae, Me represents a methyl group, and Bu represents a butyl group.

[0644] [Chemical Formula 17]

[0645]

[0646] (Pigment derivatives)

[0647] The following compounds

[0648] [Chemical Formula 18]

[0649]

[0650] (Solvent)

[0651] PGMEA (propylene glycol monomethyl ether acetate)

[0652] Cyclopentanone

[0653] PGME (propylene glycol monomethyl ether)

[0654] <Preparation of Coloring Composition>

[0655] A colored composition was prepared by mixing the following components: The dispersion, pigment dispersion, resin, polymerizable compound, and photopolymerization initiator used the components listed in Table 8.

[0656] Dispersion liquid: 10 parts by mass

[0657] Pigment dispersion: 100 parts by mass

[0658] Resin: The amount listed in Table 8

[0659] Polymerizable compound: the amount listed in Table 8

[0660] Photopolymerization initiator: the amount listed in Table 8

[0661] Surfactant W1: 1 part by mass

[0662] p-Methoxyphenol: 0.01 parts by mass

[0663] (Photopolymerization initiator)

[0664] The following compounds (wherein Me represents a methyl group and Ph represents a phenyl group)

[0665] [Chemical Formula 19]

[0666]

[0667] <Evaluation of storage stability>

[0668] The storage stability of the curable composition was evaluated by the same procedure and evaluation criteria as those for the evaluation of the storage stability using the above dispersion, except that the colored composition obtained as described above was used.

[0669] [Table 8]

[0670]

[0671] As shown in Table 8, the evaluation results of the storage stability of the coloring composition showed the same tendency as the above-mentioned dispersion. In Example 3-16, even when the pigment was changed from titanium oxynitride to zirconium nitride, the same results as those of Example 3-16 were obtained.

[0672] <Evaluation of Patterned Cured Film>

[0673] A CT-4000L solution (manufactured by FUJIFILM Electronic Materials Co., Ltd.; clear primer) was applied to a silicon wafer to a dry film thickness of 0.1 μm, dried to form a transparent film, and then heated at 220° C. for 5 minutes.

[0674] Next, the coloring composition (F-1) was applied by spin coating so that the film thickness after prebaking would be 0.6 μm. Next, prebaking was performed at 100° C. for 2 minutes using a hot plate.

[0675] Next, the film was exposed at 500 mJ / cm using an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) through a mask pattern in which square pixels with a side of 2.0 μm were arranged in a 4 mm × 3 mm area on the substrate. 2 The exposed composition layer was then placed on a horizontal rotating table in a spin / spray developer (DW-30, manufactured by Chemitronics Co., Ltd.) and subjected to flood development at 23°C for 60 seconds using a CD-2000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.). The silicon wafer substrate was rotated at 50 rpm by a rotating device while being rinsed with pure water supplied in a shower from above the center of rotation through a spray nozzle. The resulting pattern was well-shaped and free of defects.

[0676] When the same evaluation was performed using compositions (F-2) to (F-50), compositions (F-2) to (F-34) and (F-39) to (F-47) obtained good patterns similar to (F-2).

[0677] On the other hand, in (F-35) to (F-38) and (F-48) to (F-50) using a non-oxime initiator as the photopolymerization initiator, a portion of the pattern was observed to be defective.

[0678] Furthermore, relatively more pattern defects were observed in (F-48) to (F-50) than in the cases where the colored compositions (F-35) to (F-38) were used, and the extent of these defects became problematic in practical use.

[0679] Among the colored compositions, compositions (F-16) to (F-19), (F-25) to (F-27), (F-31), (F-33), and (F-34) containing a group having a fluoroalkyl group or a polysiloxane structure and having unmodified particles of silica have particularly low reflectance compared to other cured films, and are found to be useful.

[0680] <Evaluation of transmittance and reflectance>

[0681] Black resist materials SK-9010 (product name) and SK-7000 (product name) manufactured by FUJIFILM Electronic Materials Co., Ltd. and dispersion D-25 of Examples 1 to 25 were mixed as shown in Table 9 to obtain Black Resist-1 to Black Resist-4.

[0682] [Table 9]

[0683]

[0684] Black resist-1 to black resist-4 were applied to a 10 cm × 10 cm glass substrate to the film thickness listed in Table 10 by adjusting the rotation speed and then heated for 120 seconds on a hot plate at 100°C (pre-baking). Subsequently, a UV irradiation exposure apparatus (UPE-1255ML) manufactured by USHIO LIGHTING, INC. was used at a rate of 1000 mJ / cm 2 The film was exposed to an exposure dose of 100 nm and then subjected to additional heat treatment (post-baking) using a hot plate at 220° C., thereby obtaining black resist films 1 to 6. The transmission spectra and reflection spectra of the obtained black resist films 1 to 6 were measured using a UV-visible near-infrared spectrophotometer V-7200 manufactured by JASCO Corporation. The results are shown in FIG. Figures 8 to 13 middle.

[0685] [Table 10]

[0686]

[0687] like Figures 8 to 10 As shown, it was confirmed that the black resist film formed using the black resist containing the dispersion liquid D-25 of Example 1-25 had high light-shielding properties, similarly to the black resist film formed without adding the dispersion liquid D-25.

[0688] And, as Figures 11 to 13 As shown, it was confirmed that the black resist film formed using the black resist containing the dispersion D-25 of Example 1-25 can reduce the reflectivity.

[0689] Optical fingerprint authentication applications I

[0690] On the fingerprint authentication device substrate, SW-7001 (product name) manufactured by FUJIFILM Electronic Materials Co., Ltd. was spin-coated to a film thickness of 3.5 μm. Using an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed through an appropriate mask. Next, development was performed using a developing device (Act-8 manufactured by Tokyo Electron Limited.). A 0.3% aqueous solution of tetramethylammonium hydroxide (TMAH) was used in the developer, and spin-capping immersion development was performed at 23°C for 60 seconds. Then, a pure water spin spray was used for rinsing, and post-baking was performed at 200°C for 5 minutes to produce a transparent columnar structure with a diameter of 3.5 μm.

[0691] Then, the black resist-1 was applied to a thickness of 1 μm. Then, exposure, development, and post-baking were performed appropriately to form a structure A (refer to FIG. 1 ) in which the uppermost portion of the transparent columnar structure was developed and the rest was coated with a black resist film. Figure 14 and Figure 15 ).like Figure 14 and Figure 15 As shown, a transparent columnar structure 403 and a black structure 410 (structure A) having a black resist film 405 are formed on a fingerprint authentication device substrate 401 .

[0692] By using the structure A as a light-shielding film for fingerprint authentication, the fingerprint authentication accuracy can be improved.

[0693] When black resists-2 to 4 are used instead of black resist-1, the fingerprint authentication accuracy can also be improved.

[0694] Optical fingerprint authentication applications II

[0695] In the same manner as in the above-mentioned "Application I for Optical Fingerprint Authentication", columnar structures with a diameter of 3.5 μm were manufactured on a fingerprint authentication device substrate. Then, in order to fill the spaces between the columnar structures, the above-mentioned black resist-1 was applied with a thickness of 3.7 μm. Then, exposure, development, and post-baking were performed as appropriate to form a structure B (refer to FIG. 1 ) in which transparent columnar structures were filled on the black resist film. Figure 16 and Figure 17 ).like Figure 16 and Figure 17 As shown, a black structure 510 (structure B) including a transparent columnar structure 503 and a black resist film 505 is formed on a fingerprint authentication device substrate 501 .

[0696] By using the structure B as a light-shielding film for fingerprint authentication, the fingerprint authentication accuracy can be improved.

[0697] When black resists-2 to 4 are used instead of black resist-1, the fingerprint authentication accuracy can also be improved.

[0698] Explanation of symbols

[0699] 10-headlamp unit, 12-light source, 14-light shielding portion, 16-lens, 20-base, 22-light shielding film, 23-opening portion, 30-light distribution pattern, 30a-edge, 31-area, 32-light distribution pattern, 32a-edge, 33-notch portion, 100-solid-state imaging device, 101-solid-state imaging element, 102-imaging portion, 103-cover glass, 104-spacer, 105-laminated substrate board, 106-chip substrate, 107-circuit substrate, 108-electrode pad, 109-external connection terminal, 110-through electrode, 111-lens layer, 112-lens material, 113-support, 114, 115-light shielding film, 201-light receiving element, 202-color filter, 203-microlens, 204-substrate, 205b-blue pixel, 205r-red pixel, 205g-green Pixel, 205bm-black matrix, 206-p-well layer, 207-readout gate portion, 208-vertical transfer path, 209-element isolation region, 210-gate insulating film, 211-vertical transfer electrode, 212-light shielding film, 213, 214-insulating film, 215-planarization film, 300-infrared sensor, 310-solid-state imaging element, 311-infrared absorption filter, 312-color filter, 313-infrared transmission filter, 314-resin film, 315-microlens, 316-planarization film, 401-fingerprint authentication device substrate, 403-transparent columnar structure, 405-black resist film, 410-black structure (structure A), 501-fingerprint authentication device substrate, 503-transparent columnar structure, 505-black resist film, 510-black structure (structure B).

Claims

1. A dispersion comprising: Inorganic oxide particles obtained by surface treatment with at least one compound selected from the group consisting of a compound represented by the following formula A1 and a compound represented by the following formula A2; A polysiloxane having at least one unit selected from the group consisting of a T unit represented by the following formula B1 and a D unit represented by the following formula B2; and organic solvents, The content of the polysiloxane is 0.5% by mass to 39% by mass relative to the total amount of the inorganic oxide particles and the polysiloxane. The refractive index of the inorganic oxide particles is 1.10 to 1.60, Formula A1 Si(R A1 )(X A1 )3 Formula A2 Si(R A2 )(R A20 )(X A2 )2 Formula B1 [R B1 SiO 3 / 2 ] Formula B2 [R B2 R B20 SiO] In the formula A1, R A1 represents a group containing at least one group selected from an aliphatic hydrocarbon group, an aryl group, an acryloyloxy group, a methacryloyloxy group, a fluoroalkyl group, a group having a polysiloxane structure, an epoxy group, an amino group, a quaternary ammonium group or a group having a salt thereof, a cyano group, a thiol group, and an oxetanyl group, X A1 represents a hydroxyl group or a monovalent hydrolyzable group, in the formula A1, the three X A1 Same or different from each other, In the formula A2, R A2 represents a group containing at least one group selected from an aliphatic hydrocarbon group, an aryl group, an acryloyloxy group, a methacryloyloxy group, a fluoroalkyl group, a group having a polysiloxane structure, an epoxy group, an amino group, a quaternary ammonium group or a group having a salt thereof, a cyano group, a thiol group, and an oxetanyl group, R A20 represents an alkyl or aryl group, X A2 represents a hydroxyl group or a monovalent hydrolyzable group, in the formula A2, two X A2 Same or different from each other, In the formula B1, R B1 represents a group containing at least one group selected from an aliphatic hydrocarbon group, an aryl group, an acryloyloxy group, a methacryloyloxy group, a fluoroalkyl group, a group having a polysiloxane structure, an epoxy group, an amino group, a quaternary ammonium group or a group having a salt thereof, a cyano group, a thiol group, and an oxetanyl group, In the formula B2, R B2 represents a group containing at least one group selected from an aliphatic hydrocarbon group, an aryl group, an acryloyloxy group, a methacryloyloxy group, a fluoroalkyl group, a group having a polysiloxane structure, an epoxy group, an amino group, a quaternary ammonium group or a group having a salt thereof, a cyano group, a thiol group, and an oxetanyl group, R B20 represents an alkyl group or an aryl group.

2. The dispersion according to claim 1, wherein The inorganic oxide particles are silica particles.

3. The dispersion according to claim 1 or 2, wherein The content of the polysiloxane is 1% by mass to 25% by mass based on the total amount of the inorganic oxide particles and the polysiloxane.

4. The dispersion according to claim 1 or 2, wherein The dispersion also contains water, The content of the water is 0.01% by mass to 5% by mass relative to the total mass of the dispersion.

5. The dispersion according to claim 4, wherein The content of the water is 0.1% by mass to 3% by mass relative to the total mass of the dispersion.

6. The dispersion according to claim 1 or 2, wherein R of the formula A1 A1 , R of the formula A2 A2 , R of the formula B1 B1 And R of the formula B2 B2 Each independently contains at least one group selected from a fluoroalkyl group and a group having a polysiloxane structure.

7. The dispersion according to claim 1 or 2, wherein When the inorganic oxide particles are surface-treated with the compound represented by the formula A1, and the polysiloxane contains the T unit represented by the formula B1, R of the formula A1 A1 With R of formula B1 B1 are the same group.

8. The dispersion according to claim 1 or 2, wherein When the inorganic oxide particles are surface-treated with the compound represented by the formula A2, and the polysiloxane contains the D unit represented by the formula B2, R of the formula A2 A2 With R of formula B2 B2 are the same group. 9 . A composition comprising the dispersion according to claim 1 and a polymerizable compound.

10. The composition according to claim 9, further comprising a resin.

11. The composition according to claim 9 or 10, further comprising a polymerization initiator.

12. The composition according to claim 9 or 10, further comprising a colorant. 13 . A cured film formed using the composition according to claim 9 . A color filter comprising the cured film according to claim 13 . A solid-state imaging element comprising the cured film according to claim 13 . 16 . An image display device comprising the cured film according to claim 13 .

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