TW201831528A - Light-shielding composition, light-shielding film, solid-state imaging device, color filter, and liquid crystal display device - Google Patents

Abstract

The present invention addresses the problem of providing a light-shielding composition capable of forming light-shielding films having excellent adhesion to the substrates and of forming light-shielding films having excellent heat resistance and an extremely low reflectance. Another problem is to provide a light-shielding film, a solid imaging element, a color filter, and a liquid-crystal display device. The light-shielding composition of the present invention comprises: particles including a nitride of a metal atom; and at least one ingredient selected from the group consisting of polymerizable compounds and resins. In the particles, the ratio of the number of metal atoms present in the particle surface to the number of silicon atoms present in the particle surface is 1.0 or less, the numbers being determined by an analysis by X-ray electron spectroscopy.

Description

Light-shielding composition, light-shielding film, solid-state photographic element, color filter and liquid crystal display device

The invention relates to a light-shielding composition, a light-shielding film, a solid-state imaging element, a color filter, and a liquid crystal display device.

Conventionally, as particles having light-shielding properties, particles of nitrides containing metal atoms (hereinafter, also referred to as "metal-containing nitride particles") are known, and light-shielding compositions containing the particles are known. For example, the light-shielding composition containing titanium nitride-containing particles is used for various purposes, for example, it has been used for the production of light-shielding films contained in liquid crystal display devices and solid-state imaging devices. More specifically, a light-shielding film called a black matrix is used on a glass substrate for color filters used in liquid crystal display devices and solid-state imaging devices to block light between colored pixels and improve contrast. In addition, the solid-state imaging element is provided with a light-shielding film in order to prevent noise and improve image quality. Currently, portable terminals for electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin camera modules. This type of camera module usually includes a solid-state imaging element such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor. A lens used to form a subject image on a solid-state imaging element.

As the light-shielding composition containing the metal-containing nitride particles as described above, for example, Patent Document 1 describes a black resin composition for display elements, which contains a predetermined titanium oxynitride and a curable binder, in oxygen nitrogen The surface of titanium oxide particles is coated with an inorganic compound and / or organic compound in the range of 0.01 to 30% by mass relative to titanium oxynitride. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-209102

The present inventors conducted a study on the black resin composition for display elements described in Patent Document 1 (hereinafter, referred to simply as "composition" in this paragraph.) As a result, it was found that there is no heat resistance required for the light-shielding composition And low reflectivity (indicating a state where the light reflectivity is low as described later). Furthermore, the light-shielding film obtained by applying and curing the above-mentioned composition on the substrate was studied, and as a result, it was found that there was no problem of adhesion to the substrate required for the light-shielding film. In addition, in this specification, heat resistance means that when a light-shielding composition layer formed using a light-shielding composition is heated, the light transmittance is not easily increased before and after heating (the rate of increase is low). Specifically, it means that Heat resistance measured by the method described in the examples.

An object of the present invention is to provide a light-shielding film capable of producing excellent adhesion to a substrate, and capable of forming a light-shielding film having excellent heat resistance and excellent low reflectance (hereinafter, also referred to as "having the effect of the present invention" ".) The shading composition. In addition, the subject of the present invention is to provide a light-shielding film, a solid-state imaging element, a color filter, and a liquid crystal display device.

The present inventors conducted intensive research in order to achieve the above-mentioned problems, and as a result, they found that the above-mentioned problems can be achieved by the following structure.

[1] A light-shielding composition comprising particles of a nitride containing a metal atom and at least one selected from the group consisting of a polymerizable compound and a resin, and the surface of the particles determined by X-ray photoelectron spectroscopy The content atom ratio of the content of metal atoms to the content of silicon atoms in the medium is 1.0 or less. [2] The light-shielding composition according to [1], which contains an atomic ratio of 0.7 or less. [3] The light-shielding composition according to [1] or [2], which further contains a polymerization initiator. [4] The light-shielding composition according to [3], wherein the polymerization initiator is a photopolymerization initiator. [5] The light-shielding composition according to [4], wherein the photopolymerization initiator is an oxime ester compound. [6] The light-shielding composition according to any one of [1] to [5], wherein the nitride of the metal atom is titanium nitride, and the particle-derived when CuKα rays are used as the X-ray source ( 200) The diffraction angle 2θ of the peak of the plane is 42.5 ° to 42.8 °. [7] A light-shielding film obtained by curing the light-shielding composition according to any one of [1] to [6]. [8] A solid-state imaging element including the light-shielding film described in [7]. [9] A color filter including the light-shielding film described in [7]. [10] A liquid crystal display device comprising the light-shielding film described in [7]. [Effect of the invention]

According to the present invention, it is possible to provide a light-shielding composition capable of producing a light-shielding film having excellent adhesion to a substrate, and capable of forming a light-shielding film having excellent heat resistance and excellent low reflectance. Moreover, according to the present invention, a light-shielding film, a solid-state imaging element, a color filter, and a liquid crystal display device can also be provided.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments. In addition, in this specification, the numerical range indicated by "-" indicates a range including the numerical values described before and after "-" as the lower limit and upper limit. In addition, in the description of the group (atomic group) in the present specification, the expressions that do not describe substitution and unsubstitution include those that do not contain a substituent and those that contain a substituent. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups), but also alkyl groups with substituted groups (substituted alkyl groups). In addition, in this specification, "actinic rays" or "radiation" means, for example, the bright line spectrum of a mercury lamp, excimer laser, far ultraviolet, extreme ultraviolet (EUV: Extreme ultraviolet), X-ray, and electron beam. In addition, in this specification, light means actinic rays or radiation. Unless otherwise specified, the "exposure" in this specification is not limited to exposure based on mercury lamps, excimer lasers, far ultraviolet, X-rays, and EUV light. The description based on particle beams such as electron beams and ion beams also includes In the exposure. In addition, in this specification, "(meth) acrylate" means acrylate and methacrylate. In addition, in this specification, "(meth) acrylic acid" means acrylic acid and methacrylic acid. In addition, in this specification, "(meth) acryloyl" means acryloyl and methacryloyl. In addition, in this specification, "(meth) acrylamide" means acrylamide and methacrylamide. In this specification, "monomer" and "monomer" have the same meaning. The monomer is different from the oligomer and polymer, and refers to a compound with a weight average molecular weight of 2,000 or less. In this specification, a polymerizable compound refers to a compound containing a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.

[Light-shielding composition] The light-shielding composition of the embodiment of the present invention includes the following components (1) and (2). (1) Particles of metal-containing nitrides (metal-containing nitride particles) (2) Polymerizable compounds and / or resins are one of the characteristic points of the above-mentioned light-shielding composition, and examples thereof include X-ray photoelectron spectroscopy. The content ratio of the content of metal atoms in the surface of the above-mentioned particles to the content of silicon atoms determined by analysis is 1.0 or less. In addition, in this specification, when referred to as a "metal atom", unless otherwise specified, it means a metal atom contained in the particles as a nitride.

In this specification, X-ray photoelectron spectroscopy (ESCA: Electron Spectroscopy for Chemical Analysis) is to irradiate the measurement object with X-rays and measure the inherent energy of the generated photoelectrons to analyze the measurement object (including metal nitride particles) The method of the content of each atom existing on the surface of the surface (the content based on the number of atoms of each atom: atomic%) means that it is performed under the following conditions.・ Device: ULVAC-PHI, INCORPORATED. Manufacture of Quantera-SXM (trade name) device ・ X-ray source: Monochromatic Al Kα rays (1486.6eV, 25W, 15kV, beam diameter 200 μmφ) ・ Measurement area: 200 μmφ ・ Measurement Conditions: Pass Energy = 140eV, step = 0.1eV, 4 to 8 times of accumulation times. Measurement method: The particles are punched by several punches to obtain thin granular test samples. This measurement sample was attached to the above-mentioned device, and the photoelectron extraction angle was measured at 10 degrees.

In addition, the particles can be separated from the light-shielding composition by the following method. First, an organic solvent containing chloroform is added to the light-shielding composition, and components other than the particles are dissolved to obtain a dissolved solution. The above-mentioned dissolution liquid was centrifuged to obtain a precipitate. Next, the precipitate is heated and concentrated to obtain particles.

According to the above X-ray photoelectron spectroscopy analysis, the content of silicon atoms relative to all atoms contained in the surface of the particle (unit: atomic%) and the content of metal atoms relative to all atoms contained in the surface of the particle can be obtained ( Unit: atomic%). The content atomic ratio of the content of metal atoms to the content of silicon atoms on the surface of the particles (hereinafter, also referred to as "metal atoms / silicon atoms") is calculated by the following formula. Formula: metal atom / silicon atom (containing atomic number ratio) = content of metal atom (unit: atom%) / content of silicon atom (unit: atom%) In addition, in this specification, the surface represents a depth of 2 nm from the outermost surface of the particle The area within.

The metal atoms / silicon atoms on the surface of the particles of the above embodiment are 1.0 or less, preferably 0.7 or less, more preferably 0.5 or less, and further preferably 0.3 or less. The lower limit value of the metal atom / silicon atom is not particularly limited, but usually 0 or more is preferable. In addition, in this specification, the state of a metal atom / silicon atom value of 0 means that the surface of the particle is completely coated with silicon atoms and / or a compound containing silicon atoms (silicon-containing compound), in other words, the entire surface of the particle is And / or the state where the silicon-containing compound is coated, the state where the entire surface of the particle is coated with the silicon-containing compound is preferable.

The mechanism by which the light-shielding composition containing metal nitride-containing particles in the surface of metal atoms / silicon atoms of 1.0 or less has the effect of the present invention is not clear, but the present inventors infer as follows. In addition, the scope of the present invention is not limited by the inference mechanism described below. In addition, it is also within the scope of the present invention that a mechanism other than the estimation mechanism described below can obtain the effects of the present invention.

In metal-containing nitride particles with a metal atom / silicon atom of 1.0 or less on the surface, most of the surface is coated with silicon atoms and / or silicon-containing compounds (that is, the coating rate is high.). The forms of the metal atom nitride and the silicon-containing compound will be described later. For example, when they are TiN (molecular weight 61.88) and SiO ₂ (molecular weight 60.01), the silicon-containing compound on the surface of the metal-containing nitride particles The content becomes 50% by mass or more in terms of mass conversion.

The inventors found that the surface of nitrides of metal atoms, especially those of metal atoms not containing oxygen atoms, which will be described later, is susceptible to oxidation. If the metal atom nitride is oxidized, the metal atom oxide and / or metal atom oxynitride may be generated on the surface. It is generally inferred that the oxide of metal atoms and the oxynitride of metal atoms are those having a higher transmittance of light with a wavelength of 400 to 700 nm than the nitride of metal atoms. Therefore, the light-shielding composition obtained by hardening the light-shielding composition containing particles of nitride containing metal atoms oxidized on the surface is generally poor in light-shielding property.

The manufacturing process of the color filter, solid-state imaging element, and liquid crystal display device containing the shading film obtained by curing the shading composition will be described later. In the manufacturing process, the shading formed by the shading composition may sometimes be heated The composition layer (for example, reflow soldering process, etc.). At this time, it is inferred that nitrides of metal atoms are particularly vulnerable to oxidation.

As described above, the metal-containing nitride particles contained in the light-shielding composition have a high coating rate. Therefore, the surface of the nitride that is susceptible to oxidation is coated with silicon atoms and / or silicon-containing compounds. It is presumed that it is not easy to be oxidized even after a heating process, and it is easy to maintain high light shielding (high heat resistance) .

In addition, the metal-containing nitride particles have a high coating rate, so silicon atoms and / or silicon-containing compounds on the surface and the substrate (as the substrate will be described later, for example, silicon substrates and alkali-free glass substrates, etc.) ) Interaction. Therefore, it is presumed that the light-shielding film obtained by curing the light-shielding composition has excellent adhesion to the substrate.

In addition, it is considered that the silicon-containing compound present on the surface of the metal-containing nitride particles forms a coating, and it is presumed that it functions as an anti-reflection layer. Therefore, it is presumed that the light-shielding film obtained by curing the light-shielding composition has excellent low reflectivity.

Hereinafter, each component contained in the light-shielding composition of the above embodiment will be described in detail.

[Particles] The particles are not particularly limited as long as they contain metal atom nitrides and have a predetermined surface state, and known metal-containing nitride particles can be used. The metal atom is not particularly limited, and known metal atoms can be used. Examples of metal atoms include transition metals. From the viewpoint of having a more excellent light-shielding property, a light-shielding film obtained by curing a light-shielding composition is preferably a group 3 to 11 transition metal, and Ti, Sc, and V , Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Re or Pt are better, Ti, Sc, V, Cr, Co, Cu, Y, Zr, Mo, Tc, Ru, Rh, Pd, Hf, Ta, W, Re or Pt are further preferred, Ti, V, Cr, Y, Zr, Nb, Hf, Ta, W or Re is particularly preferable, and Ti, V, Nb, Ta or Zr is the best.

The content of the metal atoms in the particles is not particularly limited, but it is preferably 20 to 80% by mass relative to the total mass of the particles. The content of metal atoms in the particles can be analyzed by ICP (Inductively Coupled Plasma) emission spectrometry. In addition, one kind of metal atom may be used alone, or two or more kinds may be used. When two or more kinds of metal atoms are used, the total content is preferably within the above range.

The particles contain nitrides of metal atoms. When synthesizing nitrides of metal atoms, oxygen is sometimes mixed. The content of oxygen atoms in the metal atom nitride relative to the total mass of the metal atom nitride is preferably 0.001 to 40% by mass, more preferably 0.001 to 35% by mass, and even more preferably 0.001 to 30% by mass. The content of oxygen atoms can be analyzed by inert gas fusion infrared absorption method. In addition, regarding the nitride of the metal atom, it is actually preferable that the light-shielding film obtained by hardening the light-shielding composition has a more excellent light-shielding property without containing oxygen atoms. The fact that it does not contain oxygen atoms means that no oxygen atoms can be detected by the above measurement method.

<Titanium nitride> One of the preferable aspects of the nitride of the metal atom includes titanium nitride. The titanium nitride is not particularly limited, and known titanium nitride can be used.

Examples of titanium nitride include low-order titanium oxide represented by TiN, TiO ₂ , and Ti _n O _2n-1 ( ₁ ≦ _n ≦ 20) and TiN _x O _y (0 <x <2.0, 0.1 <Y <2.0) indicates the state of titanium oxynitride. Among the above titanium nitrides, the diffraction angle 2θ derived from the peak of the (200) plane when CuKα rays are used as the X-ray source is preferably 42.5 ° or more and 43.5 ° or less.

When CuKα rays were used as the X-ray source to measure the X-ray diffraction spectrum of titanium nitride, the peak with the strongest intensity was observed. For TiN, a peak derived from the (200) plane was observed around 2θ = 42.5 °, and for TiO, at 2θ = 43.4 ° A peak from the (200) plane was observed. On the other hand, although not the strongest peak intensity, but on anatase type TiO _2, in the vicinity of 2θ = 48.1 ° derived from the observed (200) plane peak of _2, in the vicinity of 2θ = 39.2 ° observer on the rutile type TiO To the peak from the (200) plane. As a result, the more titanium nitride contains a large amount of oxygen atoms, the more the peak position shifts to the higher angle side with respect to 42.5 °.

The diffraction angle 2θ of the peak derived from the (200) plane of titanium nitride is preferably 42.5 ° or more and 43.5 ° or less, and more preferably 42.5 ° or more and 42.8 ° or less. If the diffraction angle 2θ of the peak derived from the (200) plane of titanium nitride is 42.5 ° or more and 42.8 ° or less, the light-shielding composition has more excellent effects of the present invention. When titanium nitride contains titanium oxide TiO ₂ , as the strongest peak, a peak derived from anatase TiO ₂ (101) is observed around 2θ = 25.3 °, and rutile is observed around 2θ = 27.4 °. Type TiO ₂ (110) peak. However, because TiO ₂ is white, it is the main reason for reducing the light-shielding property of the light-shielding film obtained by hardening the light-shielding composition, so it is preferable to reduce it to the point where it is not observed as a peak.

The size of crystallites constituting titanium nitride can be obtained from the half-value width of the peak obtained by the measurement of the X-ray diffraction spectrum described above. The calculation of the crystallite size can be performed using Scherrer's formula.

The size of the crystallites constituting titanium nitride is preferably 50 nm or less, preferably 20 nm or more, and more preferably 20 to 50 nm. If the crystallite size is 20 to 50 nm, the ultraviolet (especially i-ray (365 nm)) transmittance of the light-shielding film formed by the light-shielding composition tends to become higher, and a light-shielding composition with higher sensitivity can be obtained.

The specific surface area of titanium nitride is not particularly limited, and can be obtained by the BET (Brunauer, Emmett, Teller) method. The specific surface area of titanium nitride is preferably 5.0 to 100 m ² / g, and more preferably 10 to 60 m ² / g.

When the particles contain titanium nitride, the diffraction angle 2θ derived from the (200) peak of the particles is preferably 42.5 ° or more and 43.5 ° or less, and more preferably 42.5 ° or more and 42.8 ° or less. If the diffraction angle 2θ of the particle derived from the peak of the (200) plane is 42.5 ° or more and 42.8 ° or less, the light-shielding composition has more excellent effects of the present invention. The above particles contain silicon atoms. If the diffraction angle 2θ of the particles from the peak of the (200) plane is 42.5 ° to 42.8 °, the content of titanium nitride in the central part of the particles is more, and the silicon atoms in the outer periphery The content is higher. That is, particles with a 2θ within the above range easily become core-shell particles in which titanium nitride is coated with a silicon-containing compound.

(Method for producing metal atom nitride) The method for producing metal atom nitride is not particularly limited, and a known method can be used. As a method for producing a nitride of a metal atom, for example, a gas phase reaction method may be mentioned. Examples of the gas-phase reaction method include an electric furnace method and a thermal plasma method. The thermal plasma method is preferable from the viewpoint of low impurity mixing, easy particle size uniformity, and high productivity. In the thermal plasma method, the method of generating thermal plasma is not particularly limited, and direct current arc discharge, multi-layer arc discharge, high frequency (RF) plasma, and hybrid plasma, etc. Less high-frequency plasma is better. The specific manufacturing method of the metal atom nitride based on the thermal plasma method is not particularly limited. For example, as a manufacturing method of titanium nitride, titanium tetrachloride and ammonia gas are reacted in a plasma flame Method (Japanese Patent Laid-Open No. 2-22110); a method of synthesizing nitrogen powder by evaporating titanium powder by high-frequency thermal plasma and introducing nitrogen as a carrier gas during cooling (Japanese Patent Laid-Open No. 61- 11140 Gazette); and the method of blowing ammonia gas into the periphery of the plasma (Japanese Patent Laid-Open No. 63-85007), etc. However, the method for producing a metal atom nitride is not limited to the above, and the method is not limited as long as a metal atom nitride having desired physical properties can be obtained.

The particles contain nitrides of the above-mentioned metal atoms, and the content atom ratio of the content of metal atoms to the content of silicon atoms in the surface of the particles determined by X-ray photoelectron spectroscopy is 1.0 or less. That is, a predetermined amount of silicon atoms and / or silicon-containing compounds exist on the surface of the particles. Among them, the presence of silicon-containing compounds on the surface of the particles is preferred. The presence of a silicon-containing compound on the surface of the particles is not particularly limited. For example, a state in which a metal atom nitride is provided with a silicon compound-containing coating on the surface, in other words, the metal atom nitride is contained The appearance of silicon compound coating (core-shell particles), etc. In addition, in this specification, the nitride of a metal atom is coated with a silicon-containing compound, which means that when the surface of the particles is analyzed by ESCA, the state of atoms (specifically, silicon atoms) derived from the silicon-containing compound can be detected.

<Silicon-containing compound> The silicon-containing compound used for coating metal atom nitrides is not particularly limited as long as it contains silicon atoms, and a known silicon-containing compound can be used. Examples of the silicon-containing compound include silicon dioxide, silane compounds, and siloxane resins.

Examples of the silane compound include the compounds described in paragraph 0029 of Japanese Patent Laid-Open No. 2004-219978, and the above contents are incorporated in this specification.

Examples of the siloxane resin include at least one kind of hydrolyzed and condensed resin selected from the group consisting of alkoxysilane compounds represented by the following formulas (1) to (3).

Formula (1): (R ¹ ) _a Si (OR ² ) _4-a

In formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group is an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, more preferably 1 to 3), and an alkenyl group (preferably having 2 to 12 carbon atoms, preferably 2 to 6) ), An alkynyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6), an aryl group (preferably having 6 to 22 carbon atoms, preferably 6 to 14 and more preferably 6 to 10) ), Aralkyl (preferably having 7 to 23 carbon atoms, more preferably 7 to 15, more preferably 7 to 11) is preferred, and alkyl, aryl or alkenyl is more preferred. a is 0, 1, or 2.

Formula (2): R ³ Si (R ⁴ ) _c (OR ⁵ ) _3-c

In formula (2), R ³ is a functional group-containing group. As the functional group, a group containing a hetero atom (S, O, N, P, Si, etc.) in the structure is preferable. Alternatively, it is preferable to contain a polymerizable group, an acid group or a basic group. (Meth) acryloyloxy, thiol (Sulfanyl group), epoxy, oxetanyl, glycidyl, glycidoxy, hydroxyl, phenolic hydroxyl, carboxyl Acid group, phosphoric acid group, sulfonic acid group, phosphonic acid group, amino group, isocyanate group, urea group or group having these substituents. When R ³ is bonded to silicon via a linking group, examples of the linking group include the linking group L described in paragraph 0105 of Japanese Patent Laid-Open No. 2016-74870, and the above content is incorporated in this specification. Among these, as the linking group, a hydrocarbon linking group is preferred. The carboxylic acid group, sulfonic acid group, phosphoric acid group, and phosphonic acid group can form salts or esters, and anhydrous substances thereof. Amino groups can also form salts. R ⁴ and R ⁵ are each independently a group having the same meaning as R ¹ . In addition, c is 0 or 1.

Formula (3): R ⁶ ₃ Si-X- (SiR ⁷ ₃ ) _d

In formula (3), R ⁶ and R ⁷ are each independently a group or alkoxy group having the same meaning as R ¹ (the number of carbon atoms is preferably from 1 to 12, preferably from 1 to 6, more preferably from 1 to 3) Particularly preferred), alkenyloxy (preferably having 2 to 12 carbon atoms, more preferably 2 to 6), alkynyloxy (preferably having 2 to 12 carbon atoms, more preferably 2 to 6), Aryloxy (C 6 to 22 is more preferred, 6 to 14 is more preferred, 6 to 10 is more preferred) or aralkoxy (C 7 to 23 is more preferred, 7 to 15 is more preferred) Good, especially 7 ～ 11). Among the plurality of R ⁶ and R ⁷ , 1 to 4 groups may be R ³ . X is a linking group of 2 or more valences. When X is a divalent linking group, the example of the linking group L mentioned above may be mentioned. Specific examples thereof include S, O, CO, NR ^N and polysulfide groups (S 2 to 6) or the like. When X is a trivalent linking group, for example, an isocyanuric acid skeleton can be mentioned. d is an integer of 1-4, and 1 or 2 is preferable. R ¹ to R ⁷ may each independently have an arbitrary substituent T. In addition, within the scope of exerting the effects of the present invention, the silicon atom may be bonded via the linking group L. Alternatively, adjacent ones may be bonded or condensed to form a ring.

Examples of the compound represented by formula (1) include methyltrimethoxysilane and phenyltrimethoxysilane. As specific examples of the other compounds represented by formula (1), the compounds described in paragraph 0025 of Japanese Patent Application Laid-Open No. 2016-74870 can be cited, and the above contents are incorporated in this specification. In addition, as a specific example of the compound represented by the formula (2), the compound described in paragraph 0026 of Japanese Patent Laid-Open No. 2016-74870 can be given, and as a specific example of the compound represented by the formula (3), there can be given The compound described in paragraph 0027 of Japanese Patent Laid-Open No. 2016-74870 is incorporated into this specification.

The siloxane resin can be obtained through the hydrolysis reaction and the condensation reaction using the above-mentioned alkoxysilane compound. As the hydrolysis condensation reaction, a well-known method can be used, and if necessary, a catalyst such as an acid or an alkali can be used. The catalyst is not particularly limited as long as the pH is changed. Specifically, examples of the acid (organic acid, inorganic acid) include nitric acid, phosphoric acid, oxalic acid, acetic acid, formic acid, and hydrochloric acid. Examples of the base include ammonia, triethylamine, and ethylenediamine.

(Method of coating by silicon-containing compound) As a method of coating a nitride of a metal atom by a silicon-containing compound, there is no particular limitation, and a known coating method can be used. As a method of coating a metal atom nitride with a silicon-containing compound, for example, the method described in Japanese Patent Laid-Open No. 53-33228, page 2 lower right to page 4 upper right (instead of titanium oxide, metal is used Atomic nitride), the method described in paragraphs 0015 to 0043 of Japanese Patent Laid-Open No. 2008-69193 (instead of fine-grained titanium dioxide, a metal atom nitride is used), paragraph 0020 and 0124 to 0138 of Japanese Patent Laid-Open No. 2016-74870 The method described in the paragraph (instead of metal oxide particles, using a nitride of metal atoms), the above content is incorporated in this specification.

When the nitride of the metal atom is coated with the silicon-containing compound, the thickness of the coating film based on the silicon compound is not particularly limited, but 1 to 10 nm is preferable. In addition, the thickness of the coating film based on the silicon-containing compound can be measured by embedding the particles in a resin, using an ultra-thin microtome, cutting the particles according to the resin, and using a transmission electron microscope (TEM: Transmission Electron Microscope) Observe the cutting profile, perform element mapping based on an energy dispersive X-ray analysis device, and analyze the coating state based on the silicon-containing compound.

The average primary particle diameter of the particles is not particularly limited. From the viewpoint of the light-shielding composition layer having more excellent flatness and the particles in the light-shielding composition being less likely to settle, the average primary particle diameter is 5 to 70 nm. good. In addition, in this specification, the average primary particle diameter means the average primary particle diameter of the particles measured by the following method. In the measurement of the average primary particle diameter, it can be measured using a transmission electron microscope (Transmission Electron Microscope, TEM). As a transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used. Measure the maximum length of the particle image obtained by the transmission electron microscope (Dmax: the maximum length at 2 points on the outline of the particle image) and the maximum length vertical length (DV-max: by two parallel to the maximum length When the image is sandwiched by a straight line, the shortest length between the two straight lines is vertically connected), and the average value (Dmax × DV-max) 1/2 is used as the particle size. The particle size of 100 particles was measured by this method, and the arithmetic average value was used as the average primary particle size of the particles. The "average primary particle diameter" in the examples of the present specification is also the same as the above-mentioned arithmetic average.

[Polymerizable compound and / or resin] The light-shielding composition contains a polymerizable compound and / or resin.

<Polymerizable compound> The polymerizable compound is not particularly limited as long as it contains a polymerizable group, and a known polymerizable compound can be used. The content of the polymerizable compound is preferably 5 to 30% by mass relative to the total solid content of the light-shielding composition. One type of polymerizable compound may be used alone, or two or more types may be used. When two or more polymerizable compounds are used, the total content is preferably within the above range.

The polymerizable compound preferably contains one or more compounds containing ethylenically unsaturated bonds, more preferably contains two or more compounds, more preferably contains three or more compounds, and more preferably contains five or more compounds. The upper limit is, for example, 15 or less. Examples of the group containing an ethylenically unsaturated bond include vinyl, (meth) allyl, (meth) acryloyl and the like.

As the polymerizable compound, for example, the compounds described in paragraph 0050 of Japanese Patent Laid-Open No. 2008-260927 and paragraph 0040 of Japanese Patent Laid-Open No. 2015-68893 can be used, and the above contents are incorporated in this specification.

The polymerizable compound may be, for example, any of chemical forms such as monomers, prepolymers, oligomers, and mixtures thereof, and polymers thereof. The polymerizable compound is preferably a 3 to 15-functional (meth) acrylate compound, and more preferably a 3 to 6-functional (meth) acrylate compound.

The polymerizable compound is preferably a compound containing one or more groups containing ethylenic unsaturated bonds and having a boiling point of 100 ° C. or higher under normal pressure. For example, the compounds described in paragraph 0227 of JP-A-2013-29760 and paragraphs 0254-0257 of JP-A-2008-292970 can be referred to, and this content is incorporated in this specification.

As the polymerizable compound, dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku) can also be used. Co., Ltd.), dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a city Products, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and these (meth) acryloyl groups via ethylene glycol residues, propylene glycol residues The basic structure (for example, SR454 and SR499 commercially available from Sartomer company Inc.) is preferred. These types of oligomers can also be used. Also, NK ester A-TMMT (Pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), etc. can be used. The preferred polymerizable compounds are shown below.

The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. As the polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and a non-aromatic carboxylic anhydride and an unreacted hydroxyl group of an aliphatic polyhydroxy compound are reacted to have an acid group The polymerizable compound is more preferable. Among the esters, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include ARONIX TO-2349, M-305, M-510, and M-520 manufactured by TOAGOSEI CO., LTD.

The acid value of the polymerizable compound containing an acid group is preferably 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in manufacturing and / or handling. Moreover, the photopolymerization performance is good and the curability is excellent.

Regarding the polymerizable compound, a compound containing a caprolactone structure is also preferable. The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule, and examples include trimethylolethane, ditrimethylolethane, and trihydroxy. Polyols such as methylpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin, trimethylolmelamine, etc. are obtained by esterification with (meth) acrylic acid and ε-caprolactone , Ε-caprolactone modified polyfunctional (meth) acrylate. Among them, compounds having a caprolactone structure represented by the following formula (Z-1) are preferred.

[Chemical Formula 1]

In formula (Z-1), all 6 Rs are groups represented by the following formula (Z-2), or 1 to 5 of the 6 Rs are groups represented by the following formula (Z-2), The remainder is a group represented by the following formula (Z-3).

[Chemical Formula 2]

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 system-bonded bond.

[Chemical Formula 3]

In the formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond.

Polymerizable compounds containing a caprolactone structure are commercially available as KAYARAD DPCA series from Nippon Kayaku CO., LTD., For example, DPCA-20 (in the above formulas (Z-1) to (Z-3), m = 1, the number of groups represented by the formula (Z-2) = 2, the compound where R ^{1 is} all hydrogen atoms), DPCA-30 (same formula, m = 1, the group represented by the formula (Z-2) The number of = 3, all compounds of R ¹ are hydrogen atoms, DPCA-60 (same formula, m = 1, the number of groups represented by formula (Z-2) = 6, the compound of all R ¹ is hydrogen atoms ), DPCA-120 (in the same formula, m = 2, the number of groups represented by formula (Z-2) = 6, the compound in which R ^{1 is} all hydrogen atoms), etc.

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

[Chemical Formula 4]

In formulas (Z-4) and (Z-5), E independently represents-((CH ₂ ) _y CH ₂ O)-or ((CH ₂ ) _y CH (CH ₃ ) O)-, y is independently Represents an integer of 0 to 10, and X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group. In formula (Z-4), the total number of (meth) acryloyl groups is 3 or 4, m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. In formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

In formula (Z-4), m is preferably an integer of 0 to 6, and an integer of 0 to 4 is more preferable. Moreover, the total of each m is preferably an integer of 2 to 40, an integer of 2 to 16 is more preferable, and an integer of 4 to 8 is even more preferable. In formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. In addition, the total of each n is preferably an integer of 3 to 60, an integer of 3 to 24 is more preferable, and an integer of 6 to 12 is even more preferable. In addition,-((CH ₂ ) _y CH ₂ O)-or ((CH ₂ ) _y CH (CH ₃ ) O)-in the formula (Z-4) or formula (Z-5) is the terminal on the oxygen atom side The form bonded to X is preferable.

The compound represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, the six Xs in the formula (Z-5) are all in the form of acryloyl groups, and the compound in which the six Xs in the formula (Z-5) are all in acryloyl groups and at least one of the six Xs is The state of the mixture of hydrogen atom compounds is preferred. With such a structure, the developability can be further improved.

In addition, as the total content of the compound represented by formula (Z-4) or formula (Z-5) in the polymerizable compound, 20% by mass or more is preferable, and 50% by mass or more is more preferable. Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferred.

Furthermore, the polymerizable compound may have a cardo skeleton. As the polymerizable compound containing a cardo skeleton, a polymerizable compound having a 9,9-diaryl fluorene skeleton is preferred. The polymerizable compound containing a cardo skeleton is not limited, and examples thereof include Oncoat EX series (manufactured by NAGASE & CO., LTD) and Ogsol (manufactured by Osaka Gas Chemicals Co., Ltd.).

<Resin> The resin is not particularly limited, and known resins can be used. The content of the resin is preferably 2 to 30% by mass relative to the total solid content of the light-shielding composition. One type of resin may be used alone, or two or more types may be used. When two or more resins are used, the total amount is preferably within the above range.

Examples of the resin include epoxy resin, acrylic resin, siloxane resin, and polyimide resin. The resin may be photosensitive or non-photosensitive.

As the resin, in order to realize water development or weak alkali water development, a resin soluble or swellable in water or weak alkali water is preferable. Among them, as the resin, an alkali-soluble resin (a resin containing a group that promotes alkali solubility (alkali-soluble group)) is more preferable. Examples of the alkali-soluble resin include resins containing at least one alkali-soluble group in the molecule, for example, polyhydroxystyrene-based resins, polysiloxane-based resins, (meth) acrylic resins, and Base) acrylamide resin, (meth) acrylic acid / (meth) acrylamide copolymer resin, epoxy resin and polyimide resin.

The alkali-soluble group is not particularly limited, and examples thereof include a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. The alkali-soluble group may be only one kind, or two or more kinds.

Specific examples of the alkali-soluble resin include, for example, polyamide. Generally, polyamic acid is obtained by subjecting a compound having an acid anhydride group and a diamine compound to an addition polymerization reaction at 40 to 100 ° C, and a repeating unit containing the following formula (4) is preferred.

[Chemical Formula 5]

In the above formula (4), R ₁ is an organic group having a carbon number of 2 to 22 or more, and R ₂ is an organic group having a carbon number of 1 to 22, and n is an integer of 1 or more.

As the above-mentioned polyamic acid, for example, those obtained by reacting a tetracarboxylic dianhydride and an aromatic diamine compound in a polar solvent are preferred. Examples of the tetracarboxylic dianhydride include compounds described in paragraphs 0041 and 0043 of Japanese Patent Laid-Open No. 2008-260927, and the above contents are incorporated in this specification. Examples of the aromatic diamine compound include compounds described in paragraphs 0040 and 0043 of Japanese Patent Laid-Open No. 2008-260927, and the above contents are incorporated in this specification. The method for synthesizing polyamide is not particularly limited, and a known method can be used. As a method of synthesizing polyamide, for example, the method described in paragraph 0044 of Japanese Patent Laid-Open No. 2008-260927 can be used, and the above contents are incorporated in this specification.

As another aspect of the alkali-soluble resin, a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound may be mentioned. The unsaturated carboxylic acid is not particularly limited, and examples thereof include monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and vinyl acetate; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, or Its anhydride; phthalic acid mono (2- (meth) acryloyloxyethyl) and other polycarboxylic acid monoesters; etc.

Examples of the copolymerizable ethylenically unsaturated compound include methyl (meth) acrylate. In addition, the compounds described in paragraphs 0027 of Japanese Patent Application Laid-Open No. 2010-97210 and paragraphs 0036 to 0037 of Japanese Patent Application Laid-Open No. 201568893 can also be used, and the above contents are incorporated in this specification.

Furthermore, it is also possible to use in combination with a copolymerizable ethylenically unsaturated compound and a compound containing an ethylenically unsaturated group in the side chain. As the ethylenically unsaturated group, (meth) acrylic acid is preferred. For example, it is possible to obtain an acrylic resin having an ethylenically unsaturated group in the side chain, that is, to add an ethylenically unsaturated compound containing a shrinking group or an alicyclic epoxy group to a carboxylic acid group of an acrylic resin containing a carboxylic acid group成 反应。 In response.

As the alkali-soluble resin, for example, Japanese Patent Publication No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Publication No. 54-92723 No., Japanese Patent Laid-Open No. 59-53836 and Japanese Patent Laid-Open No. 59-71048 describe radical polymers containing carboxylic acid groups in the side chain; European Patent No. 993966, European Patent No. 1204000 and Japanese Patent Laid-Open Acetal-modified polyvinyl alcohol-based binder resin containing alkali-soluble groups described in various publications such as 2001-318463; polyvinylpyrrolidone; polyethylene oxide; alcohol-soluble nylon and 2,2-bis- (4-hydroxyl The reaction product of phenyl) -propane and epichlorohydrin is also polyether; the polyimide resin described in International Publication No. 2008/123097; etc.

As the alkali-soluble resin, for example, the compounds described in paragraphs 0225 to 0245 of Japanese Patent Laid-Open No. 2016-75845 can also be used, and the above contents are incorporated in this specification.

[Arbitrary components] The light-shielding composition may contain other components. Examples of other components include dispersants, polymerization initiators, solvents, surfactants, and viscosity modifiers. Hereinafter, each aspect will be described in detail.

<Dispersant> The light-shielding composition preferably contains a dispersant. The dispersant helps to improve the dispersibility of the colorant (particles and pigments described later). In this specification, the resin and the dispersant are different components.

When the light-shielding composition contains a dispersant, the content of the dispersant is preferably 5 to 30% by mass relative to the total solid content of the light-shielding composition. One kind of dispersant may be used alone, or two or more kinds may be used. When two or more dispersants are used, the total amount is preferably within the above range.

As the dispersant, for example, a known dispersant can be appropriately selected and used. Among them, polymer compounds are preferred. Examples of the dispersant include polymer dispersants [for example, polyamidoamine and its salts, polycarboxylic acid and its salts, high molecular weight unsaturated acid esters, modified polyurethane, modified polyester, and modified poly (A Group) acrylate, (meth) acrylic copolymer, formalin condensate of naphthalene sulfonate], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine and pigment derivatives.

(High-molecular compound) The high-molecular compound is adsorbed on the surface of the colorant to be dispersed, and plays a role of preventing the re-agglomeration of the dispersion. Therefore, terminal modified polymers, grafted polymers, block polymers and the like that contain fixed portions on the surface of the pigment are preferred.

It is preferable that the polymer compound contains a structural unit containing a graft chain. In addition, in this specification, "structural unit" has the same meaning as "repeating unit". The polymer compound including the structural unit containing such a graft chain has an affinity with a solvent due to the graft chain, so the dispersibility of the colorant and the dispersion stability after time (time stability) are excellent. In addition, due to the presence of the graft chain, the polymer compound including the structural unit containing the graft chain has affinity with the polymerizable compound or other applicable resins. As a result, residues are not easily generated during alkali development. If the graft chain becomes longer, the three-dimensional repulsion effect is improved and the dispersibility of the coloring agent is improved. On the other hand, if the graft chain is too long, the adsorption force to the colorant decreases, and the dispersibility of the colorant tends to decrease. Therefore, the number of atoms other than hydrogen atoms in the graft chain is preferably 40 to 10,000, the number of atoms other than hydrogen atoms is more preferably 50 to 2000, and the number of atoms other than hydrogen atoms is 60 to 500. good. Among them, the graft chain represents the root of the main chain of the copolymer (the atom bonded to the main chain from the branched group of the main chain) to the end of the group branched from the main chain.

The graft chain preferably contains a polymer structure. Examples of such a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, and a polymer. Urea structure, polyamide structure and polyether structure, etc. In order to improve the interaction between the graft chain and the solvent and thereby improve the dispersibility of the colorant, the graft chain contains at least one selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure One type of graft chain is preferable, and a graft chain containing at least one of a polyester structure or a polyether structure is more preferable.

The macromonomer containing such a graft chain is not particularly limited, and a macromonomer containing a reactive double bond group can be appropriately used. Corresponding to the structural unit containing the graft chain included in the polymer compound, as a commercially available macromonomer suitable for the synthesis of the polymer compound, the compounds described in paragraph 0040 of Japanese Patent Laid-Open No. 2015-034983 can be cited.

As specific examples of the structural unit containing a graft chain included in the polymer compound, for example, the structural units described in paragraphs 0041 to 0058 of Japanese Patent Laid-Open No. 2015-034983 are cited, and these contents are incorporated in this specification. In addition, the dispersant may include various structural units described in paragraphs 0059 to 0088 of JP 2015-034983.

In addition, as the dispersant, in addition to the above-mentioned polymer compound, a graft copolymer of paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 of US2011 / 0124824) of Japanese Patent Application Publication No. 2010-106268 can be used. These contents can be invoked and incorporated into this manual. Furthermore, in addition to the above, paragraphs 0028 to 0084 of Japanese Patent Laid-Open No. 2011-153283 (corresponding columns of paragraphs 0075 to 0133 of the corresponding US2011 / 0279759) can also be used which contains an acidic group bonded via a linking group The polymer compounds constituting the side chain structure, which can be used for reference, are incorporated in this specification.

<Polymerization initiator> When the light-shielding composition contains a polymerizable compound, the light-shielding composition preferably contains a polymerization initiator. The polymerization initiator is not particularly limited, and a known polymerization initiator can be used. Examples of the polymerization initiator include photopolymerization initiators and thermal polymerization initiators, and photopolymerization initiators are preferred. The initiator is preferably selected from those without coloring properties and those with high fading properties. In addition, as the polymerization initiator, a so-called radical polymerization initiator is preferred. The content of the polymerization initiator is preferably 2 to 20% by mass relative to the total solid content of the light-shielding composition. One type of polymerization initiator may be used alone, or two or more types may be used. When two or more polymerization initiators are used, the total content is preferably within the above range.

As a thermal polymerization initiator, for example, 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalononitrile, dimethyl- (2,2 ')-azo Azo compounds such as bis (2-methylpropionate) [V-601] and organic peroxides such as benzoyl peroxide, lauryl peroxide and potassium persulfate. Specific examples of the polymerization initiator include, for example, the polymerization initiators described in pages 65 to 148 of Kato Kiyosaka "Ultraviolet Curing System" (published by the Comprehensive Technology Center Co., Ltd .: Heisei Year 1).

(Photopolymerization initiator) The light-shielding composition preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can initiate the polymerization of the polymerizable compound, and a known photopolymerization initiator can be used. As the photopolymerization initiator, for example, those having photosensitivity in the ultraviolet region to the visible light region are preferred. Moreover, the photopolymerization initiator may be an active agent that produces some action with the photosensitizer excited by light and generates active radicals, or it may be an initiator that initiates cationic polymerization according to the type of polymerizable compound. Furthermore, it is preferred that the photopolymerization initiator contains at least one compound having an absorption coefficient of at least about 50 moles in the range of about 300 nm to 800 nm (330 nm to 500 nm is more preferable.).

The content of the photopolymerization initiator is preferably 2 to 20% by mass relative to the total solid content of the light-shielding composition. One type of photopolymerization initiator may be used alone, or two or more types may be used. When two or more kinds of photopolymerization initiators are used, the total amount thereof is preferably within the above range.

Examples of the photopolymerization initiator include alkyl benzophenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and oxime ester-based photopolymerization initiators (oxime ester compounds). Among them, it is preferable to contain an oxime ester compound from the viewpoint that the light-shielding composition has more excellent effects of the present invention.

As photopolymerization initiators, more specifically, halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton, those containing an oxadiazole skeleton, etc.), acetylphosphine compounds such as acetylphosphine oxide, and hexaaryl Oxime compounds such as biimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, etc.

In particular, when applying the above-mentioned light-shielding composition to the production of a light-shielding film, it is necessary to form a fine pattern in a sharp shape, so it is important to develop the residue in the unexposed portion together with curability without residue. From this viewpoint, it is particularly preferable to use an oxime ester compound as a photopolymerization initiator. In particular, when forming a fine pattern, step exposure is used in the exposure for curing, but this exposure machine may be damaged by halogen, and it is necessary to suppress the addition amount of the photopolymerization initiator to be low. Therefore, considering these aspects, when forming a fine pattern, it is particularly preferable to use an oxime ester compound as a photopolymerization initiator. As a specific example of the photopolymerization initiator, for example, it is possible to refer to paragraphs 0265 to 0268 of JP-A-2013-29760, the contents of which are incorporated in this specification.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acetylphosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Laid-Open No. 10-291969 and an acylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used. As the hydroxyacetophenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone compound, IRGACURE-907, IRGACURE-369, or IRGACURE-379EG (trade names: all manufactured by BASF) can be used as a commercially available product. As the aminoacetophenone compound, a compound described in Japanese Patent Laid-Open No. 2009-191179 whose absorption wavelength matches a long-wavelength light source such as 365 nm or 405 nm can also be used. As the acetylphosphine compound, IRGACURE-819 or IRGACURE-TPO (trade names: all manufactured by BASF) can be used as a commercially available product.

・ Oxime ester compound As a photopolymerization initiator, an oxime ester compound (oxime compound) is more preferable. The oxime compound has high sensitivity and high polymerization efficiency, can harden the light-shielding composition layer regardless of the concentration of the coloring agent, and it is easy to set the concentration of the coloring agent high. As specific examples of the oxime compound, the compounds described in Japanese Patent Laid-Open No. 2001-233842, the compounds described in Japanese Patent Laid-Open No. 2000-80068, or the compounds described in Japanese Patent Laid-Open No. 2006-342166 can be used. Examples of the oxime compound include 3-benzyloxyiminobutane-2-one, 3-ethoxyiminobutane-2-one, and 3-propionyloxyimide. Butane-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxy Imino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one and 2-ethoxycarbonyloxyimino-1- Phenylpropane-1-one, etc. Also, JCS Perkin II (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, Japanese special The compounds described in Japanese Patent Laid-Open No. 2000-66385, Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2004-534797 and Japanese Patent Laid-Open No. 2006-342166, etc. Among commercially available products, IRGACURE-OXE01 (made by BASF), IRGACURE-OXE02 (made by BASF), IRGACURE-OXE03 (made by BASF), or IRGACURE-OXE04 (made by BASF) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka Arkls NCI-831 and Adeka Arkls NCI-930 (manufactured by ADEKA CORPORATION), and N-1919 (containing carbazole · oxime ester skeleton light) can also be used Starter (made by ADEKA CORPORATION), NCI-730 (made by ADEKA CORPORATION), etc.

In addition, as oxime compounds other than those described above, the compounds described in Japanese Patent Publication No. 2009-519904 having an oxime linked to the N-position of carbazole can be used; US Patent No. The compound described in Japanese Patent No. 7626957; the compound described in Japanese Patent Laid-Open No. 2010-15025 and U.S. Patent Publication No. 2009-292039 with a nitro group introduced into the pigment portion; the ketone described in International Patent Publication No. 2009-131189 An oxime compound; a compound described in US Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule; described in Japanese Patent Laid-Open No. 2009-221114 having a maximum absorption at 405 nm and good sensitivity to a g-ray light source Compounds; etc. For example, it is possible to refer to paragraphs 0274 to 0275 of Japanese Patent Laid-Open No. 2013-29760, which are incorporated in this specification. Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferred. In addition, the N-O bond of the oxime compound may be an oxime compound of the (E) form, an oxime compound of the (Z) form, or a mixture of the (E) form and the (Z) form.

[Chemical Formula 6]

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. As the monovalent substituent represented by R in formula (OX-1), a monovalent non-metallic atomic group is preferred. Examples of monovalent non-metallic atomic groups include alkyl groups, aryl groups, acetyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heterocyclic groups, alkylthiocarbonyl groups, and arylthiocarbonyl groups. Furthermore, these groups may have one or more substituents. Furthermore, the aforementioned substituents may be further substituted with other substituents. Examples of the substituent include halogen atom, aryloxy group, alkoxycarbonyl group or aryloxycarbonyl group, acetyloxy group, acetyl group, alkyl group, aryl group and the like. As the monovalent substituent represented by B in the formula (OX-1), an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group is preferred. These groups may have more than one substituent. As the substituent, the aforementioned substituent may be exemplified. As the divalent organic group represented by A in the formula (OX-1), an alkylene group, a cycloalkylene group or an alkynyl group having 1 to 12 carbon atoms is preferred. These groups may have more than one substituent. As the substituent, the aforementioned substituent may be exemplified.

As the photopolymerization initiator, an oxime compound containing a fluorine atom can also be used. Specific examples of the oxime compound containing a fluorine atom include compounds described in Japanese Patent Application Laid-Open No. 2010-262028; compounds 24, 36-40 of Japanese Patent Application No. 2014-500852; and Japanese Patent Application 2013 -Compound No. 164471 (C-3); etc. This content is incorporated into this manual.

As the photopolymerization initiator, compounds represented by the following general formulas (1) to (4) can also be used.

[Chemical Formula 7]

[Chemical Formula 8]

In formula (1), R ¹ and R ² independently represent an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or the number of carbon atoms 7-30 arylalkyl groups, when R ¹ and R ² are phenyl groups, phenyl groups may be bonded to each other to form a fluorenyl group, and R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms Group, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

^{(2), R 1, R 2, 1} , R 2, R ³ and the same formula the meanings of R ⁴ in the formula R (1) in R ³ and R ^4, R ⁵ represents -R ^6, -OR ^6, -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, halogen atom or Hydroxy, R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents Direct bonding or carbonyl, a represents an integer from 0 to 4.

In formula (3), R ¹ represents a C 1-20 alkyl group, a C 4-20 alicyclic hydrocarbon group, a C 6-30 aryl group or a C 7-30 aryl group Alkyl, R ³ and R ⁴ independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or the number of carbon atoms Heterocyclic group of 4-20, X represents a direct bond or a carbonyl group.

Formula (4), R ^1, R ³ and R ⁴ defined for the formula (3) in R ^1, the same as R ³ and R ^4, R ⁵ represents ^{-R 6, -OR 6, -SR 6} , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, halogen atom or hydroxyl group, R ⁶ represents carbon An alkyl group having 1 to 20 atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, X represents a direct bond or a carbonyl group, a represents an integer of 0-4.

In the above formula (1) and formula (2), it is preferred that R ¹ and R ² are independently methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl, respectively. R ³ is preferably methyl, ethyl, phenyl, tolyl or xylyl. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond. In addition, in the above formulas (3) and (4), it is preferable that R ^{1 is} independently methyl, ethyl, n-propyl, isopropyl, cyclohexyl, or phenyl, respectively. R ³ is preferably methyl, ethyl, phenyl, tolyl or xylyl. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a direct bond. As specific examples of the compounds represented by formula (1) and formula (2), for example, the compounds described in paragraph numbers 0076 to 0079 of JP-A-2014-137466 can be given. This content is incorporated into this manual.

Specific examples of oxime compounds that can be suitably applied to the above-mentioned light-shielding composition are shown below. In addition, as the oxime compound, the compound described in Table 1 of International Publication No. 2015/036910 can also be used, and the above content is incorporated in this specification.

[Chemical Formula 9]

The oxime compound has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, and a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm is more preferable, and a higher absorbance at 365 nm and 405 nm is more preferable. Regarding the molar absorption coefficient of the oxime compound at 365 nm or 405 nm, from the viewpoint of sensitivity, 1,000 to 300,000 is preferable, 2,000 to 300,000 is more preferable, and 5,000 to 200,000 is even more preferable. The molar absorption coefficient of the compound can be measured by a well-known method, for example, with an ultraviolet-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian Corporation) using an ethyl acetate solvent at a concentration of 0.01 g / L. A photopolymerization initiator can be used in combination of 2 or more types as needed.

Furthermore, as the photopolymerization initiator, compounds described in paragraphs 0052 of JP-A-2008-260927, paragraphs 0033-0037 of JP-A 201097210, and paragraphs 0044 of JP-A 201568893 can also be used. The above contents are incorporated in this manual.

As the photopolymerization initiator, bifunctional or trifunctional compounds can also be used. Specific examples of such compounds include paragraphs 0417 to 0412 of Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Publication No. 2016-532675 , The dimer of the oxime compound described in paragraphs 0039 to 0055 of International Publication No. 2017/033680, the compounds (E) and (G) described in Japanese Patent Publication No. 2013-522445, and International Publication No. 2016/034963 Cmpd1 ~ 7 etc. described in the number.

<Solvent> The light-shielding composition preferably contains a solvent. Examples of the solvent include water and organic solvents. Among them, the light-shielding composition preferably contains an organic solvent. When the light-shielding composition contains a solvent, the solid content of the light-shielding composition is preferably 10 to 40% by mass. If the solid content of the light-shielding composition is equal to or higher than the lower limit, the viscosity is low and the coatability is optimized. Furthermore, the concentration of the more reactive compound becomes lower, so the stability over time is optimized. In addition, if the solid content of the light-shielding composition is equal to or less than the upper limit, the viscosity is kept appropriate, and the coating property is optimized. Moreover, the coloring agent with heavier specific gravity becomes less prone to settling and the stability over time is optimized.

(Organic solvent) When the light-shielding composition contains an organic solvent, the content of the organic solvent is preferably 60 to 90% by mass relative to the total mass of the light-shielding composition. In addition, one type of organic solvent may be used alone, or two or more types may be used. When two or more organic solvents are used, the total amount is preferably within the above range.

The organic solvent is not particularly limited, and examples thereof include acetone, methyl ethyl ketone, cyclohexane, dichloroethane, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl ether. , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetone acetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl Ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether , Diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide , Γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate, N-methyl-2-pyrrolidone and ethyl lactate.

When it contains two or more organic solvents, it is selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethylene glycol Dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol Two or more types of monomethyl ether and propylene glycol monomethyl ether acetate are preferred.

(Water) The light-shielding composition may contain water. Water may be intentionally added, or it may be inevitably included in the light-shielding composition by adding each component contained in the light-shielding composition. The content of water is preferably 0.01 to 1% by mass relative to the total mass of the light-shielding composition. When the content of water is within the above range, the formation of pores is suppressed when the light-shielding film is produced, and the moisture resistance of the light-shielding film is improved.

<Surfactant> The light-shielding composition preferably contains a surfactant. The surfactant contributes to improving the coatability of the light-shielding composition.

When the light-shielding composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass relative to the total mass of the light-shielding composition. One type of surfactant may be used alone, or two or more types may be used. When two or more surfactants are used, the total amount is preferably within the above range.

Examples of the surfactant include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.

For example, when the light-shielding composition contains a fluorine-based surfactant, the liquid characteristics (particularly, fluidity) of the light-shielding composition are further improved. That is, when a film is formed using a light-shielding composition containing a fluorine-based surfactant, by reducing the interfacial tension between the coated surface and the coating liquid, the wettability to the coated surface is improved, and the coating The coatability of the surface is improved. Therefore, even when a thin film having a thickness of several μm is formed with a small amount of liquid, it is more appropriate to form a film with a small thickness unevenness and a uniform thickness, which is effective in this regard.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass. Fluorine-based surfactants having a fluorine content in this range are effective in the uniformity and / or liquid-saving properties of the thickness of the coating film, and the solubility in the light-shielding composition is also good.

Examples of fluorine-based surfactants include MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177, MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F479, MEGAFACE F475, MEGAFACE F475 , MEGAFACE F482, MEGAFACE F554, MEGAFACE F780 (above, manufactured by DIC CORPORATION), Fluorado FC430, Fluorado FC431, Fluorado FC171 (above, manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S-393, Surflon KH-40 (above, manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA SOLUTIONS INC.), Etc.

Specific examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and these ethoxylates and propoxylates (for example, glycerol propoxylates) , Glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene Glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, TETRONIC 304, 701, 704, manufactured by BASF) 901, 904, 150R1), SOLSPERSE 20000 (The Lubrizol corporatin), etc. Moreover, Pionin D-6112-W manufactured by TAKEMOTO OIL & FAT CO., LTD, NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by MORISHITA & CO., LTD.), And organosiloxane polymer KP341 (Shin-Etsu Chemical Co. , Ltd.), (meth) acrylic (co) polymer Polyflow No.75, No.90, No.95 (manufactured by KYOEISHA CHEMICAL CO., LTD), W001 (manufactured by Yusho Co Ltd), etc.

Specific examples of the anionic surfactants include W004, W005, and W017 (manufactured by Yusho Co Ltd).

Examples of silicone-based surfactants include "Toray Silicone DC3PA", "Toray Silicone SH7PA", "Toray Silicone DC11PA", "Toray Silicone SH21PA", and "Toray Silicone SH28PA" manufactured by Dow Corning Toray CO., LTD. "," Toray Silicone SH29PA "," Toray Silicone SH30PA "," Toray Silicone SH8400 "," TSF-4440 "," TSF-4300 "," TSF-4445 "," TSF-4460 "manufactured by Momentive Performance Materials Inc., "TSF-4452", Shin-Etsu Chemical Co., Ltd. manufactures "KP341", "KF6001", "KF6002", BYK Additives & Instruments manufactures "BYK307", "BYK323", "BYK330", "BYK333", etc.

<Other coloring materials> The light-shielding composition may contain coloring materials other than the above-mentioned particles. As other coloring materials, various known pigments (coloring pigments) and dyes (coloring dyes) can be used. When the light-shielding composition contains other coloring materials, its content can be determined according to the optical characteristics of the light-shielding film obtained by hardening. In addition, other coloring materials may be used alone, or two or more types may be used.

As the color pigment, for example, when used in the manufacture of color filters, color pigments (color pigments) such as R (red), G (green), and B (blue) that form the color pixels of the color filter can be used. Black pigments (black pigments) for black matrix formation or shading film formation. As a coloring dye, for example, when used in the manufacture of color filters, in addition to color-based dyes (color dyes) such as R (red), G (green), and B (blue) that form the color pixels of the color filter, The coloring agent described in paragraphs 0027 to 0200 of JP 2014-42375 is used. In addition, a black-based dye (black dye) generally used for black matrix formation or light-shielding film formation can be used.

In addition, as other coloring materials, the coloring materials described in paragraphs 0031 of Japanese Patent Laid-Open No. 2008-260927 and paragraphs 0015 to 0025 of Japanese Patent Laid-Open No. 2015-68893 can be used. The above content is incorporated in this specification.

<Viscosity modifier> The light-shielding composition may contain a silane coupling agent as a viscosity modifier. Examples of the silane coupling agent include 3-glycidyl ether propyl trimethoxy silane, 3-glycidyl ether propyl triethoxy silane, 3-glycidyl ether propyl methyl dimethoxy silane , 3-glycidyl ether propyl methyl diethoxy silane, vinyl trimethoxy silane and vinyl triethoxy silane, etc. The content of the viscosity modifier is not particularly limited, but it is preferably 0.02 to 20% by mass relative to the total solid content of the light-shielding composition.

[Production method of light-shielding composition] The light-shielding composition can be mixed with the above-mentioned various components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, or a wet disperser) To prepare. When preparing the light-shielding composition, the components constituting the light-shielding composition may be collectively blended, or they may be blended sequentially after dissolving or dispersing the components in a solvent. In addition, there is no particular restriction on the order of input and working conditions at the time of blending.

In order to remove foreign substances or reduce defects, it is preferable to filter the light-shielding composition with a filter. As a filter, as long as it is used for filtering purposes, it can be used without particular limitation. For example, it can be formed by materials such as fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high density and ultrahigh molecular weight) such as polyethylene and polypropylene (PP). Filter. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred. The pore size of the filter is preferably about 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. By setting it as this range, it is possible to suppress filtration clogging of the pigment, and it is possible to reliably remove fine foreign substances such as impurities and aggregates contained in the pigment.

When using filters, different filters can be combined. At this time, the filtration by the first filter may be performed only once, or may be performed twice or more. When combining different filters to perform two or more filtrations, the pore size after the second filtration is preferably the same or larger than the pore diameter of the first filtration. Furthermore, the first filters having different pore sizes within the above range may be combined. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it is possible to select from various filters provided by NIHON PALL LTD., Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (formerly Mykrolis Corpration), or KITZ MICROFILTER CORPORATION. The second filter can be formed of the same material as the first filter described above. 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. The light-shielding composition of the present invention preferably does not contain impurities such as metals, metal salts containing halogens, acids and alkalis. The content of impurities contained in the filter material is preferably 1 ppm or less, more preferably 1 ppb or less, further preferably 100 ppt or less, particularly preferably 10 ppt or less, and actually does not contain (below the detection limit of the measuring device) the good. In addition, the above impurities can be measured by an inductively coupled plasma mass analyzer (manufactured by Yokogawa Analytical Systems Inc., Agilent 7500cs type).

[Light-shielding film and manufacturing method thereof] The light-shielding film can be formed by using a light-shielding composition. The thickness of the light-shielding film is not particularly limited, and 0.2 to 25 μm is preferable. The above-mentioned thickness is an average thickness, which is a value obtained by measuring the thickness of any 5 points or more of the light-shielding film and arithmetically averaging these.

The manufacturing method of the light-shielding film is not particularly limited, and a method of manufacturing the light-shielding film by applying the above-mentioned light-shielding composition on a substrate to form a coating film and subjecting the coating film to a curing treatment. The method of hardening treatment is not particularly limited, and photo-hardening treatment or thermal hardening treatment may be mentioned. From the viewpoint of easier pattern formation, photo-hardening treatment (especially, hardening treatment by irradiation with actinic rays or radiation) is preferred .

As a preferred aspect when manufacturing a pattern-shaped light-shielding film, a method having a process of applying a light-shielding composition on a substrate to form a light-shielding composition layer (hereinafter, abbreviated as "light-shielding" as appropriate) may be mentioned. Process of forming a layer of a sexual composition ".); A process of exposure by irradiating actinic rays or radiation to a layer of a light-shielding composition (hereinafter, appropriately referred to as" exposure process ".); And the composition of light-shielding after exposure The process of developing the object layer to form a light-shielding film (hereinafter, abbreviated as "development process"). Specifically, the light-shielding composition is coated on the substrate directly or via another layer to form a light-shielding composition layer (light-shielding composition layer forming process), and actinic rays or radiation is irradiated through a predetermined mask pattern to shield the light-shielding composition layer The composition layer is exposed, and only the light-shielding composition layer irradiated with light is cured (exposure process) and developed with a developing solution (development process), whereby a pattern-shaped light-shielding film can be manufactured. Hereinafter, each process in the above-mentioned state will be described.

<Light-shielding composition layer formation process> In the light-shielding composition layer formation process, a light-shielding composition is coated on a substrate to form a light-shielding composition layer. The type of the substrate is not particularly limited. When used as a solid-state imaging element, for example, a silicon substrate is used, and when used as a color filter, a glass substrate is used. As a method of applying the light-shielding composition to the substrate, spin coating, slit coating, inkjet method, spray coating, spin coating, cast coating, roll coating, screen printing method, etc. can be applied Various coating methods. The light-shielding composition layer coated on the substrate is preferably dried at 70 to 110 ° C. for 2 to 4 minutes.

<Exposure process> In the exposure process, the light-shielding composition layer formed in the light-shielding composition layer formation process is irradiated with actinic rays or radiation through a mask to perform exposure. The exposure is preferably performed by irradiation of radiation. As radiation that can be used during exposure, ultraviolet rays such as g-rays, h-rays, and i-rays are particularly preferred. As a light source, a high-pressure mercury lamp is preferred. The irradiation intensity is preferably ⁵ mJ / cm ² or more and 1500 mJ / cm ² or less.

<Development process> The exposure process is followed by a development process (development process) to dissolve unexposed portions of the exposure process into the developer solution. By this, only the photohardened part remains. As the developer, an alkaline developer can be used. In this case, it is preferable to use an organic alkali developer. The development temperature is usually 20 ° C. or more and 30 ° C. or less, and the development time is 20 seconds or more and 90 seconds or less. As the alkaline aqueous solution (alkaline developing solution), for example, as the inorganic-based developing solution, alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate are dissolved. The concentration is 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass of alkaline aqueous solution. In addition, examples of the organic alkali developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrahydroxide. Basic compounds such as butylammonium, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine and 1,8-diazabicyclo- [5,4,0] -7-undecene, etc. The concentration is 0.001 to 10% by mass, preferably 0.005 to 0.5% by mass of alkaline aqueous solution. To the alkaline aqueous solution, for example, a suitable amount of water-soluble organic solvents such as methanol and ethanol and / or surfactants can also be added. In addition, when using a developer containing such an alkaline aqueous solution, the light-shielding film is usually washed (rinsed) with pure water after development.

In addition, the manufacturing method of the light-shielding film may have other processes. As for other processes, there is no particular limitation, and it can be appropriately selected according to needs. As other processes, for example, a surface treatment process of the substrate, a pre-heating process (pre-baking process), a post-heating process (post-baking process), etc. may be mentioned. After the light-shielding composition layer forming process, the exposure process, and the development process, a hardening process (post-baking process) that hardens by heating and / or exposing the patterned light-shielding film that has been formed can be performed as needed.

<Pre-heating process and post-heating process> The heating temperature of the aforementioned pre-heating process and post-heating process is preferably 80 to 250 ° C. The upper limit is more preferably 200 ° C or lower, and further preferably 150 ° C or lower. The lower limit is preferably 90 ° C or higher. The heating time of the pre-heating process and the post-heating process is preferably 30 to 300 seconds. The upper limit is preferably 240 seconds, and more preferably 180 seconds or less. The lower limit is preferably 60 seconds or more.

In addition, when the light-shielding composition contains a non-photosensitive resin, a photoresist coating film may be formed thereon, followed by exposure and development to set a desired pattern. Thereafter, after removing the photoresist or the oxygen barrier film as necessary, heating and hardening it to obtain a pattern-shaped light-shielding film. The thermosetting conditions vary depending on the resin. For example, when a light-shielding composition containing polyamide is used to obtain a light-shielding film, the light-shielding composition layer (containing polyamide) is usually heated at 200 to 350 ° C. ～ 120 minutes to obtain polyimide (equivalent to shading film).

[Solid-state imaging element] The solid-state imaging element according to the embodiment of the present invention includes the light-shielding film. The solid-state imaging element includes a light-shielding film, and is not particularly limited. For example, the following structure may be mentioned: a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) constituting the solid-state imaging element is provided on the substrate A plurality of light-receiving elements including photodiodes, polysilicon, etc. are provided on the light-receiving element forming surface side of the support (for example, a portion other than the light-receiving portion or a pixel for color adjustment, etc.) or on the opposite side of the forming surface Invented shading film.

1 to 2, an example of the structure of a solid-state imaging device will be described. In addition, in FIGS. 1-2, in order to clarify each part, a part of the enlargement and display are disregarded regardless of the ratio of the thickness and the width of each other. As shown in FIG. 1, the solid-state imaging device 100 includes a rectangular solid-state imaging element 101 and a transparent cover glass 103 which is held above the solid-state imaging element 101 and seals the solid-state imaging element 101. In addition, a lens layer 111 is provided 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 be a structure in which the support 113 and the lens material 112 are integrally formed. When stray light enters the peripheral region of the lens layer 111, the effect of light gathering by the lens material 112 is weakened due to light diffusion, and the light reaching the imaging unit 102 is reduced. Also, noise caused by stray light is generated. Therefore, a light shielding film 114 is provided in the peripheral area of the lens layer 111 to shield light. The light-shielding film of the embodiment of the present invention can also be used as the light-shielding film 114 described above.

The solid-state imaging element 101 photoelectrically converts the optical image formed by the imaging unit 102 serving as its light-receiving surface and outputs it as an image signal. The solid-state imaging element 101 includes a laminated substrate 105 in which two substrates are laminated. The laminated substrate 105 includes a rectangular wafer substrate 106 and a circuit substrate 107 of the same size, and the circuit substrate 107 is laminated on the back surface of the wafer substrate 106.

The material used as the substrate of the wafer substrate 106 is not particularly limited, and known materials can be used.

An imaging unit 102 is provided at the center of the surface of the wafer substrate 106. In addition, if stray light enters the peripheral region of the imaging unit 102, dark current (noise) is generated from the circuits in the peripheral region. Therefore, the peripheral region is provided with a light shielding film 115 to shield the light. The light-shielding film of the above embodiment can also be used as the light-shielding film 115.

A plurality of electrode pads 108 are provided on the surface edge of the wafer substrate 106. The electrode pad 108 is electrically connected to the imaging unit 102 via a signal line (a bonding wire) not shown provided on the surface of the wafer substrate 106.

On the back surface of the circuit board 107, external connection terminals 109 are provided at positions substantially below the electrode pads 108, respectively. Each external connection terminal 109 is connected to the electrode pad 108 via a penetration electrode 110 that vertically penetrates the laminated substrate 105. In addition, each external connection terminal 109 is connected to a control circuit that controls driving of the solid-state imaging element 101 and an image processing circuit that performs image processing on an imaging signal output from the solid-state imaging element 101 via wiring not shown.

As shown in FIG. 2, the imaging unit 102 is composed of various parts provided on the substrate 204 such as the light receiving element 201, the color filter 202, and the microlens 203. The color filter 202 has a blue pixel 205b, a red pixel 205r, a green pixel 205g, and a black matrix 205bm. The light-shielding film of the above embodiment can also be used as the black matrix 205bm.

As the material of the substrate 204, the same material as the aforementioned wafer substrate 106 can be used. A p-well layer 206 is formed on the surface layer of the substrate 204. In the p-well layer 206, a light-receiving element 201 including an n-type layer and generating and accumulating signal charges by photoelectric conversion is formed in a square lattice.

On one side of the light receiving element 201, a vertical transfer path 208 including an n-type layer is formed via the read gate portion 207 of the surface layer of the p-well layer 206. In addition, on the other side of the light receiving element 201, a vertical transfer path 208 belonging to an adjacent pixel is formed via an element separation region 209 including a p-type layer. The read gate portion 207 is used to read the signal charge accumulated in the light receiving element 201 to the channel area of the vertical transfer path 208.

On the surface of the substrate 204, a gate insulating film 210 including an ONO (Oxide-Nitride-Oxide) film is formed. On this gate insulating film 210, a vertical transfer electrode 211 including polysilicon or amorphous silicon is formed so as to cover substantially directly above the vertical transfer path 208, the read gate portion 207, and the element isolation region 209. The vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to transfer charges and a read electrode that drives the read gate portion 207 to read signal charges. The signal charges are sequentially transferred from the vertical transfer path 208 to a horizontal transfer path and an output unit (floating diffusion amplifier) not shown, and then output as a voltage signal.

On the vertical transfer electrode 211, a light-shielding film 212 is formed so as to cover the surface thereof. The light-shielding film 212 has an opening at a position directly above the light-receiving element 201, and shields other areas. The light-shielding film of the above embodiment can also be used as the light-shielding film 212. On the light-shielding film 212, a transparent intermediate layer including: an insulating film 213 including BPSG (borophospho silicate glass), an insulating film (passivation film) 214 including P-SiN, and a planarizing film 215 including transparent resin or the like . The color filter 202 is formed on the intermediate layer.

[Black Matrix] The black matrix includes the above-mentioned light-shielding film. The black matrix is sometimes included in color filters, solid-state imaging devices, and liquid crystal display devices. Examples of the black matrix include: those described above; black edges provided on the peripheral portion of a display device such as a liquid crystal display device; grid-shaped and / or striped black portions between red, blue, and green pixels; Dot-shaped and / or line-shaped black patterns used for TFT (thin film transistor) shading. The definition of this black matrix is described in, for example, Taihe Kanno, "Glossary of Liquid Crystal Display Manufacturing Devices", Second Edition, NIKKAN KOGYO SHIMBUN, LTD., 1996, p.64. The black matrix improves the display contrast, and in the case of an active matrix drive type liquid crystal display device using a thin film transistor (TFT), it prevents the deterioration of the image quality caused by the leakage of light current, so it has a high light blocking property (optical density OD 3 or more) is preferred.

The manufacturing method of the black matrix is not particularly limited, and can be manufactured by the same method as the manufacturing method of the above-mentioned light-shielding film. Specifically, a light-shielding composition can be applied to a substrate to form a light-shielding composition layer, and exposed and developed to produce a pattern-shaped light-shielding film (black matrix). In addition, the thickness of the light-shielding film used as the black matrix is preferably 0.1 to 4.0 μm.

The material of the substrate is not particularly limited, and preferably has a transmittance of 80% or more with respect to visible light (wavelength: 400 to 800 nm). Specific examples of such materials include soda-lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester resins and polyolefin silicon resins; etc. From the viewpoints of properties and heat resistance, alkali-free glass, quartz glass, etc. are preferred.

[Color filter] The color filter according to the embodiment of the present invention includes a light-shielding film. The form in which the color filter contains a light-shielding film is not particularly limited, and a color filter provided with a substrate and a black matrix can be mentioned. That is, a color filter including red, green, and blue colored pixels formed in an opening of a black matrix formed in a substrate shape can be exemplified.

The color filter containing a black matrix (light-shielding film) can be manufactured by the following method, for example. First, a coating film (resin composition layer) of each color resin composition containing a pigment corresponding to each colored pixel of a color filter is formed in an opening of a black matrix formed in a substrate-like pattern. In addition, the resin composition for each color is not particularly limited, and a known resin composition can be used. In the light-shielding composition, it is preferable to use a resin composition using the pigment for each colored pixel instead of particles. Next, the resin composition layer is exposed through a photomask having a pattern corresponding to the opening of the black matrix. Then, after removing the unexposed portion by development processing, baking is performed, whereby colored pixels can be formed in the opening of the black matrix. For example, a series of operations can be performed using the resin composition containing each color of red, green, and blue pigments, whereby a color filter having red, green, and blue pixels can be manufactured.

[Liquid Crystal Display Device] The liquid crystal display device of the embodiment of the present invention includes a light-shielding film. As the liquid crystal display device includes a light-shielding film, it is not particularly limited, and examples thereof include a color filter including a black matrix (light-shielding film).

As the liquid crystal display device of this embodiment, for example, a pair of substrates disposed opposite to each other and a liquid crystal compound enclosed between the substrates can be mentioned. As the above-mentioned substrate, there has been described as a substrate for a black matrix. Specific examples of the liquid crystal display device include, for example, a polarizer / substrate / color filter / transparent electrode layer / orientation film / liquid crystal layer / orientation film / transparent electrode layer / TFT (Thin (Thin Film Transistor) laminated body of element / substrate / polarizer / backlight unit.

In addition, the liquid crystal display device according to the embodiment of the present invention is not limited to the above, and examples thereof include "electronic display device (Showa Sasaki, Kogyo Chosakai Publishing Co., Ltd. issued in 1990)" and "display Devices (Ibuki Shunzhang, Industrial Books Co., Ltd., published in the first year of Heisei) and other liquid crystal display devices. Also, for example, a liquid crystal display device described in "Second Generation Liquid Crystal Display Technology (Edited by Uchida Ryoo, Kogyo Chosakai Publishing Co., Ltd., 1994)". [Example]

Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the examples shown below. In addition, in the description of this embodiment, unless otherwise specified, "parts" and "%" are quality standards.

<Synthesis Example 1: Synthesis of a dispersion sol (A-1) containing a nitride of a metal (Ti) atom coated with a silicone resin> As a nitride of a metal atom, titanium nitride (Wako Pure Chemical Industries) was prepared , Ltd., trade name "TiN 50nm", average particle diameter 50nm). The above 0.2 parts by mass of titanium nitride was dispersed in 0.2 parts by mass of pure water, and 0.16 parts by mass of 28.6% by mass tartaric acid aqueous solution and 0.06 parts by mass of 50% by mass KOH aqueous solution were added and stirred. Next, alumina beads (manufactured by TAIMEI CHEMICALS CO., LTD., High-purity alumina beads) with a particle size of 0.1 mm were added, and this was supplied to a wet pulverizer (manufactured by Kansai Paint Co., Ltd.). Machine) for 360 minutes of crushing and dispersion. Then, after removing the alumina beads with a stainless steel filter with a mesh of 44 μm, 1.4 parts by mass of pure water was further added to the obtained solution and stirred to obtain an aqueous dispersion of titanium nitride with a solid content of 11% by mass. Copies. Next, after washing the aqueous dispersion of titanium nitride with ion exchange water using an ultrafiltration membrane, 0.06 parts by mass of an anion exchange resin (manufactured by Mitsubishi Chemical Co., Ltd .: SANUPC) was added to perform deionization treatment. After that, the obtained solution was supplied to a centrifuge (CR-21 manufactured by Hitachi Koki Co., Ltd.) and treated at 12,000 rpm for 1 hour, and ion-exchanged water was added to the obtained precipitate, thereby An aqueous dispersion sol of titanium nitride with a solid content concentration of 10% by mass was prepared. After adding 9.6 parts by mass of the cation exchange resin to 0.6 parts by mass of the above-mentioned titanium nitride aqueous dispersion sol while stirring, the cation exchange resin was separated to prepare a deionized titanium nitride aqueous dispersion sol. Next, using an ultrafiltration membrane device (filter membrane manufactured by Asahi Kasei Corporation, SIP-1013), the dispersion medium of the water-dispersed sol was replaced with methanol from water and concentrated, thereby obtaining a methanol-dispersed sol of titanium nitride ( a-1) 0.3 parts by mass. The solid content concentration of this titanium nitride methanol-dispersed sol was 30% by mass.

Put 25 parts by mass of methyltrimethoxysilane, 75 parts by mass of phenyltrimethoxysilane, 1050 parts by mass of (a-1) titanium nitride methanol dispersion sol, and 100 parts by mass of γ-butyrolactone into the reaction vessel To prepare a solution. After the reaction vessel was installed in a temperature-adjustable water bath, while stirring, 30 parts by mass of water and 1.0 part by mass of phosphoric acid were added dropwise to the solution so that the reaction temperature did not exceed 40 ° C. After the dropwise addition, 500 parts by mass of γ-butyrolactone was added to the solution, the water bath temperature was set to 105 ° C., and the solution was stirred for 2.5 hours while removing methanol from the solution. Then, 1000 parts by mass of γ-butyrolactone was further added to the solution, the bath temperature was set at 130 ° C., and heated for 2 hours, thereby obtaining 1.9 parts by mass of a nitride containing metal atoms coated with a silicone resin ( Titanium nitride) dispersion sol (A-1). The solid content concentration of this dispersion sol was 20% by mass. The solvent removed part of the dispersed sol. ESCA measured the obtained solid. As a result, the metal atom (Ti) / Si atom was 0.1.

<Synthesis Examples 2-9 and Comparative Synthesis Example 1: Synthesis of dispersion sols (A-2) to (A-9) and (B-1) containing nitrides of metal atoms coated with silicone resins> The type of nitride of the metal atom, the amount of addition of methyltrimethoxysilane, and the amount of addition of phenyltrimethoxysilane were changed as described in Table 1, except that the same operation as in Synthesis Example 1 was performed to obtain Dispersion sols (A-2) to (A-9) and (B-1) containing nitrides of metal atoms coated with silicone resin. In addition, Table 1 summarizes the metal atoms / Si atoms of each particle measured by ESCA.

[Table 1]

<Comparative Synthesis Example 2: Synthesis of a dispersion sol (B-2) containing a nitride of a metal atom coated with silicon oxide> The same operation as in Production Example 1 of Japanese Patent Laid-Open No. 2006-209102 was performed to obtain a Titanium oxynitride coated with silicon oxide. ESCA measurement was performed, and as a result, the metal atom (Ti) / Si atom was 2.2. 30 parts by mass of titanium oxynitride coated with silicon oxide, 45 parts by mass of BYK2001 (manufactured by BYK Chemie Co., Ltd., 20% by mass solution), and 125 parts by mass of γ-butyrolactone were mixed to obtain a mixed solution. Next, using a circulation type dispersing device (bead mill, manufactured by Shinmaru Enterprises Corporation, trade name "NPM") and zirconia beads (φ0.05 mm), the mixed liquid was dispersed to obtain nitrogen containing metal atoms coated with silicon oxide Dispersed sol (B-2) of compound (titanium oxynitride).

<Comparative Synthesis Example 3: Synthesis of Dispersion Sol (B-3) containing metal atom nitride> Instead of titanium oxynitride coated with silicon oxide, titanium nitride (Wako Pure Chemical Industries, Ltd., A trade name "TiN 50nm"), except for this, a dispersion sol (B-3) of a nitride (titanium nitride) containing metal atoms was obtained in the same manner as in Comparative Synthesis Example 2.

[Preparation of light-shielding composition 1] The following components were mixed to obtain a light-shielding composition 1. • 1000 parts by mass of dispersion sol (A-1) • 25 parts by mass of polymerizable compound (T1) • 12 parts by mass of alkali-soluble resin (J1) • Photopolymerization initiator: NCI-831 (made by ADEKA CORPORATION, equivalent to oxime ester) Compound.) 12 parts by mass Surfactant: BYK333 (PGMEA (propylene glycol 1-monomethyl ether 2-acetate) 10% by mass solution) 10 parts by mass

In the above, the polymerizable compound (T1) and the alkali-soluble resin (J1) are compounds represented by the following formulas. [Chemical Formula 10] [Chemical Formula 11]

[Preparation of light-shielding compositions 2 to 13 and comparative light-shielding compositions 1 to 3] The components described in Table 2 were mixed to obtain light-shielding compositions 2 to 13 and comparative light-shielding compositions 1 to 3.

[Table 2]

The abbreviations of the photopolymerization initiator in Table 2 are as follows.・ OXE01 (manufactured by BASF, trade name “Irgacure OXE01”, equivalent to oxime ester compound.) • OXE02 (manufactured by BASF company, trade name “Irgacure OXE02”, equivalent to oxime ester compound.) • PI-03 (in the following formula The indicated compound is equivalent to the oxime ester compound.)

[Chemical Formula 12]

・ PI-04 (The compound represented by the following formula corresponds to the oxime ester compound.)

[Chemical Formula 13]

・ Irg369 (made by BASF, trade name “Irgacure 369”, equivalent to alkyl benzophenone photopolymerization initiator.) • TPO (made by BASF company, trade name “Irgacure TPO”, equivalent to acylphosphine oxide-based light Polymerization initiator.) LC951 (manufactured by Kusumoto Chemicals, Ltd., trade name "Dispalon LC-951")

The polymerizable compounds (T2) and (T3) in Table 2 are compounds represented by the following formulas. In addition, n in the polymerizable compound (T2) is 2. [Chemical Formula 14]

The alkali-soluble resins (J2) and (J3) in Table 2 are compounds represented by the following formulas.・ Alkali soluble resin (J2) [Chemical formula 15]

・ Alkali-soluble resin (J3) (equivalent to polyamide) [Chemical formula 16]

[Examples 1 to 13 and Comparative Examples 1 to 3: Evaluation of each light-shielding composition] The following tests of Evaluations 1 to 3 were performed on each light-shielding composition. Hereinafter, each evaluation method and result will be described.

[Evaluation 1: Adhesion of light-shielding film to silicon substrate] Each light-shielding composition of Examples and Comparative Examples was applied to an 8-inch silicon wafer by spin coating so that the dry film thickness became 1.5 μm (Silicon substrate), thereby obtaining a light-shielding composition layer. After that, for each wafer, the light-shielding composition layer was heated on a hot plate (heating condition: 100 ° C, 2 minutes). The light-shielding composition layer after heating was subjected to an exposure amount of 1000 mJ / cm ² using an i-ray step exposure device FPA-3000i5 + (manufactured by Canon Co., Ltd.) via a 10 μm line and a space mask. Exposure. After that, the silicon wafer was placed on a horizontal rotary table of a rotary / spray developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.). Next, the light-shielding composition layer subjected to the exposure process placed on the silicon wafer of the rotary / spray developing machine was processed at 23 ° C. using CD-2000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) After 60 seconds of spin immersion development, a pattern-shaped light-shielding film was obtained. The obtained pattern-shaped light-shielding film was dried at 200 ° C. for 5 minutes. In the obtained pattern-shaped light-shielding film, an arbitrary area of 100 μm × 100 μm was observed with a scanning electron microscope (SEM, Scanning Electron Microscope) (magnification of 10,000 times), and the portion where the pattern was missing was counted. The smaller the number of missing patterns, the better. The results are shown in Table 3.

[Evaluation 2: Heat resistance of light-shielding film] Each light-shielding composition of Examples and Comparative Examples was coated on a silicon wafer (silicon substrate) so as to have a dry film thickness of 1.5 μm to obtain a composition with light-shielding Layer of silicon wafer. The silicon wafer provided with the above-mentioned light-shielding composition layer was placed on a 100 ° C hot plate so as to be in contact with the substrate surface (the surface on the opposite side of the light-shielding composition layer), and heated for 2 minutes. A light-shielding film was obtained by exposing the heated light-shielding composition layer with an exposure amount of 1000 mJ / cm ² using an i-ray step exposure device FPA-3000i5 + (manufactured by Canon Co., Ltd.). The heat resistance of the light-shielding film was evaluated by the following method. First, the light-shielding film was peeled from the silicon wafer, and the highest transmittance T ₁ (%) at a wavelength of 400 to 700 nm was measured using a spectrophotometer. Next, for each silicon wafer, the light-shielding film produced by the same method as above is placed on a 300 ° C hot plate and heated for 1 hour. The light-shielding film was peeled from the silicon wafer and heated for 1 hour, and the highest transmittance T ₂ (%) was measured in the same manner as described above. Next, from T ₁ and T ₂ , the increase rate (%) of the highest transmittance was obtained by the following formula. The smaller the increase rate, the better the heat resistance, and the better. The results are shown in Table 3. Formula: Increase rate (%) = (T ₂ -T ₁ ) / T ₁ × 100

[Evaluation 3: Light reflectance of the light-shielding film] On the silicon wafer, each light-shielding composition of Examples and Comparative Examples was coated so that the dry film thickness became 1.5 μm, and silicon with a light-shielding composition layer was obtained Wafer. The silicon wafer provided with the above-mentioned light-shielding composition layer was placed on a 100 ° C hot plate so as to be in contact with the substrate surface (the surface on the opposite side of the light-shielding composition layer), and heated for 2 minutes. A light-shielding film was obtained by exposing the heated light-shielding composition layer with an exposure amount of 1000 mJ / cm ² using an i-ray step exposure device FPA-3000i5 + (manufactured by Canon Co., Ltd.). The low reflectivity of the light-shielding film was evaluated by the following method. From the light-shielding film side, 400-700 nm light was incident on the silicon wafer at an incidence angle of 5 degrees, and the highest reflectance (unit:%) was measured using a spectroscope UV4100 manufactured by Hitachi High-Technologies Corporation. The smaller the value of the highest reflectance, the lower the reflectivity of the light-shielding film, which is preferable. The results are shown in Table 3.

[table 3]

From the results shown in Table 3, it can be seen that the light-shielding composition used in each example can produce a light-shielding film having excellent adhesion to a silicon substrate, and has excellent heat resistance and excellent low reflectance. The light-shielding film obtained by curing the light-shielding composition of the embodiment of the present invention is suitable as a light-shielding film for solid-state imaging elements. Furthermore, comparing the light-shielding compositions 1 to 3 does not have the effect of the present invention, and the obtained light-shielding film is also outside the practical range.

[Example 1B: Fabrication of solid-state imaging element] A color filter of a silicon wafer having a color filter (1 cm square) with a pixel size of 2.0 μm and a film thickness of 1.5 μm, a microlens, metal wiring, and a photodiode In the peripheral portion, using the light-shielding composition 1, a light-shielding film having a width of 10 μm and a film thickness of 1.5 μm was formed by photolithography. Using the obtained silicon wafer, a solid-state photographic element was fabricated. The obtained solid-state photographic element has high resolution and excellent color separation.

[Examples 2B to 13B] Instead of the light-shielding composition 1, the light-shielding compositions 2 to 13 were used, except that the solid-state imaging element was produced by the same method as in Example 1B. As a result, the produced solid-state imaging The element is the same as Example 1B and has excellent performance.

[Examples 14 to 26 and Comparative Examples 4 to 6: Evaluation of each light-shielding composition] In the tests of Evaluations 1 to 3 above, instead of a silicon wafer (silicon substrate), an alkali-free glass substrate was used. Each test was carried out in the same way. The results are shown in Table 4.

[Table 4]

From the results shown in Table 4, it can be seen that the light-shielding composition used in each example can produce a light-shielding film having excellent adhesion to an alkali-free glass substrate, and has excellent heat resistance and excellent low reflectance. The light-shielding film obtained by curing the light-shielding composition of the embodiment of the present invention is suitable as a light-shielding film for color filters, liquid crystal display devices, and solid-state imaging devices. On the other hand, the comparative light-shielding compositions 1 to 3 do not have the effect of the present invention, and the obtained light-shielding film is also outside the practical range.

[Example 14B: Fabrication and evaluation of color filter] Instead of using a silicon wafer (silicon substrate), an alkali-free glass substrate was used, and it was prepared by "Evaluation 1: Adhesion of light-shielding film to silicon substrate" In the same method, a light-shielding film (black matrix) was formed using a light-shielding composition 1 on an alkali-free glass substrate. In addition, a mask having a linear pattern of 20 μm was used for exposure. Next, in the opening of the light-shielding film, a red (R) having a linear pattern of 100 μm was formed in the same manner as the black matrix prepared above by using the resin composition R-1 for red (R) described below Coloring pattern. In the same way, the following green (G) resin composition G-1 is used to form a green (G) coloring pattern, and the blue (B) resin composition B-1 is used to form a blue (B) coloring pattern. Pattern, thereby producing a color filter containing a black matrix. The manufactured color filter was processed with ITO (Indium Tin Oxide) transparent electrode, alignment film, etc., and a liquid crystal display device was installed. The picture quality of the obtained display device is good.

[Examples 15B to 26B] Instead of the light-shielding composition 1, the light-shielding compositions 2 to 13 were used. A black matrix was produced by the same method as in Example 14B, and a color filter containing the black matrix was further produced. As a result, the manufactured color filter is the same as Example 14B and has excellent performance.

<Preparation of resin composition for red (R), resin composition for green (G), and resin composition for blue (B)> Instead of particles, the following pigments were used, in addition to the light-shielding composition 1 In the same way, the resin composition R-1 for red (R), the resin composition G-1 for green (G), and the resin composition B-1 for blue (B) were produced. • Pigment for red (R): CI Pigment Red 254 • Pigment for green (G): 30/70 [mass ratio] mixture of CI Pigment Green 36 and CI Pigment Yellow 219 • Pigment for Blue (B): CI Pigment Blue Color 15: 30/70 [mass ratio] mixture of CI Pigment Violet 23

[Example 27] The following components were mixed to obtain a light-shielding composition 14. • 1000 parts by mass of dispersing sol (A-1) • 49 parts by mass of alkali-soluble resin (J3) • Surfactant: BYK333 (10% by mass solution of PGMEA) 10 parts by mass

On the silicon wafer (silicon substrate), the light-shielding composition 14 was coated so that the dry film thickness became 1.5 μm, and a light-shielding composition layer was formed. Next, the light-shielding composition layer was baked at 100 ° C for 2 minutes. Thereafter, the light-shielding composition layer was further heated at 140 ° C for 20 minutes. Next, a positive photoresist "FHi622BC" (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was coated on the light-shielding composition layer, and pre-baking was performed to form a film with a thickness of 0.8 μm on the light-shielding composition layer. Photoresist layer. Next, using an i-ray stepper (manufactured by Canon Co., Ltd.), the photoresist layer was pattern-exposed at an exposure amount of 350 mJ / cm ² through a 20 μm line and space mask. Then, by developing the photoresist layer after exposure with a tetramethylammonium hydroxide aqueous solution to obtain a patterned resist film, the light-shielding composition layer is etched to form a light-shielding composition layer Formed a pattern. After that, using a photoresist stripping solution "MS230C" (manufactured by FUJIFILM Electronic Materials Co., Ltd.), the stripping time was set to 120 seconds, the patterned resist film was removed, and further cleaning with pure water and spin drying were performed. , A pattern-like light-shielding composition layer was obtained. Thereafter, the pattern-shaped light-shielding composition layer was subjected to dehydration and baking treatment at 100 ° C for 2 minutes, and further baked at 300 ° C for 120 minutes to obtain a pattern-shaped light-shielding film.

The adhesion of the obtained light-shielding film to the silicon wafer (silicon substrate) was evaluated by the same method as described above. As a result, no pattern loss was observed.

Furthermore, a light-shielding composition 14 was coated on a silicon wafer (silicon substrate) so that the dry film thickness was 1.5 μm, and a silicon wafer having a light-shielding composition layer was obtained. Next, the silicon wafer provided with the above-mentioned light-shielding composition layer was placed on a 300 ° C hot plate and heated for 120 minutes so that the substrate surfaces (the surface opposite to the light-shielding composition layer) were in contact Shading film. The light-shielding film obtained from the silicon wafer was peeled, and the highest transmittance T ₁ (%) at a wavelength of 400 to 700 nm was measured with a spectrophotometer. Next, for each silicon wafer, the light-shielding film produced by the same method as above is placed on a 300 ° C hot plate and heated for 1 hour. The light-shielding film was peeled from the silicon wafer and heated for 1 hour, and the highest transmittance T ₂ (%) was measured by the same method as described above. Next, from T ₁ and T ₂ , the increase rate (%) of the highest transmittance was obtained by the following formula. As a result, it was 0%.

Furthermore, the light-shielding composition 14 was coated on the silicon wafer so that the dry film thickness became 1.5 μm, and a silicon wafer having the light-shielding composition layer was obtained. Next, the silicon wafer provided with the above-mentioned light-shielding composition layer was placed on a 300 ° C hot plate and heated for 120 minutes so that the substrate surfaces (the surface opposite to the light-shielding composition layer) were in contact with each other. Shading film. From the light-shielding film side, 400-700 nm light was incident on the silicon wafer at an incidence angle of 5 degrees, and the highest reflectance (unit:%) was measured by a spectroscope UV4100 manufactured by Hitachi High-Technologies Corporation. As a result, the light reflectance is 3%.

[Comparative Example 7] A comparative light-shielding composition 4 was prepared and evaluated in the same manner as in Example 27 except that the dispersion sol (A-1) was changed to (B-1). As a result, there were 10 missing patterns, the increase rate of the highest transmittance was 11%, and the light reflectance was 8%, which was outside the practical range as a light-shielding film.

(Titanium nitride particles TiN-1) As Ti particles, titanium nitride particles TiN-1 (equivalent to titanium nitride) were produced using TC-200 (manufactured by TOHO TECHNICAL SERVICE CO., LTD., Average primary particle diameter 20 nm). ). First, the Ti particles were subjected to plasma treatment in Ar gas, whereby Ti nanoparticles were formed. After the Ar gas atmosphere, the O ₂ concentration of 50ppm or less, at 30 ℃ will Ti nanoparticles after the plasma treatment for 24 hours, the concentration of O ₂ in the embodiment becomes 100ppm O ₂ is introduced into the Ar gas atmosphere In a gas state, let stand at 30 ° C for 24 hours (pretreatment of Ti particles). After that, the "TTSP separator (trade name)" manufactured by Hosokawa Micron was used to classify the obtained Ti nanoparticles under the condition that the yield became 10% to obtain a powder of Ti nanoparticles. The average primary particle diameter of the obtained powder was observed by TEM (transmission electron microscope), and the average particle diameter of 100 particles was obtained by arithmetic average. As a result, it was 120 nm. Titanium nitride particles TiN-1 were manufactured using the apparatus for manufacturing black composite fine particles described in FIG. 1 of International Publication No. 2010/147098. Specifically, in the device for manufacturing black composite particles, a high-frequency voltage of about 4 MHz and about 80 kVA is applied to the high-frequency oscillation coil of the plasma torch, and 50 L / argon gas is supplied as the plasma gas from the plasma gas supply source The mixed gas of min and 50L / min of nitrogen makes the argon-nitrogen thermal plasma flame in the plasma torch. Then, a carrier gas of 10 L / min is supplied from the spray gas supply source of the material supply device. Then, the titanium particles obtained as described above are supplied into the hot plasma flame in the plasma torch together with argon gas as a carrier gas, and are evaporated in the hot plasma flame to be highly dispersed in a gas phase state. In addition, nitrogen was used as the gas supplied into the chamber by the gas supply device. The flow velocity in the chamber at this time was 5 m / sec, and the supply amount was 1000 L / min. In addition, the pressure in the cyclone was set to 50 kPa, and the speed at which each raw material was supplied from the chamber to the cyclone was set to 11 m / s (average value). In this way, titanium nitride particles TiN-1 were obtained.

X-ray diffraction measurement of titanium nitride particles TiN-1 was performed. For the measurement, the powder sample was placed in an aluminum standard sample holder, and the measurement was performed by wide-angle X-ray diffractometry (manufactured by Rigaku Corporation, trade name "RU-200R"). As measurement conditions, the X-ray source is CuKα rays, the output is 50kV / 200mA, the slit system is 1 ° -1 ° -0.15mm-0.45mm, the measurement step (2θ) is 0.02 °, and the scanning speed is set. 2 ° / min. In addition, the diffraction angle derived from the peak of the TiN (200) plane observed near the diffraction angle 2θ (42.6 °) was measured. As a result, the peak diffraction angle derived from the TiN (200) plane was 42.64 °.

[Preparation and evaluation of light-shielding composition TiN-1] In Synthesis Example 1, nitride was used instead of titanium nitride (manufactured by Wako Pure Chemical Industries, Ltd., trade name "titanium nitride 50 nm", average particle diameter 50 nm) Titanium particles TiN-1 were synthesized in the same way as a dispersed sol (TiN-1) containing nitrides of metal (Ti) atoms coated with silicone resin. Next, in the preparation of the light-shielding composition 1, the light-shielding composition TiN-1 was prepared in the same manner except that the dispersion sol (TiN-1) was used instead of the dispersion sol (A-1). Using the light-shielding composition TiN-1, the same evaluation as in Example 1 was performed, and as a result, the same results as in Example 1 were obtained.

(Titanium nitride particles TiN-2) It was manufactured in the same way as the titanium nitride particles TiN-1 except that the speed of supplying each raw material from the chamber to the cyclone was changed to 8 m / s (average value) Titanium nitride particles TiN-2. X-ray diffraction measurement was performed in the same manner as TiN-1. As a result, the peak diffraction angle derived from the TiN (200) plane was 42.61 °.

[Preparation and evaluation of light-shielding composition TiN-2] In Synthesis Example 1, nitride was used instead of titanium nitride (manufactured by Wako Pure Chemical Industries, Ltd., trade name "titanium nitride 50 nm", average particle diameter 50 nm) In addition to the titanium particles TiN-2, a dispersion sol (TiN-2) containing a nitride of metal (Ti) atoms coated with a silicone resin was synthesized in the same manner. Next, in the preparation of the light-shielding composition 1, the light-shielding composition TiN-2 was prepared in the same manner except that the dispersion sol (TiN-2) was used instead of the dispersion sol (A-1). Using the light-shielding composition TiN-2, the same evaluation as in Example 1 was performed, and as a result, the same results as in Example 1 were obtained.

(Titanium nitride particles TiN-3) It was manufactured in the same way as titanium nitride particles TiN-1 except that the speed of supplying each raw material from the chamber to the cyclone was changed to 13 m / s (average value) Titanium nitride particles TiN-3. X-ray diffraction measurement was performed in the same manner as TiN-1. As a result, the peak diffraction angle derived from the TiN (200) plane was 42.78 °.

[Preparation and evaluation of light-shielding composition TiN-3] In Synthesis Example 1, nitride was used instead of titanium nitride (manufactured by Wako Pure Chemical Industries, Ltd., trade name "titanium nitride 50 nm", average particle diameter 50 nm) In addition to the titanium particles TiN-3, a dispersion sol (TiN-3) containing nitrides of metal (Ti) atoms coated with silicone resin was synthesized in the same manner. Next, in the preparation of the light-shielding composition 1, the light-shielding composition TiN-3 was prepared in the same manner except that the dispersion sol (TiN-3) was used instead of the dispersion sol (A-1). Using the light-shielding composition TiN-3, the same evaluation as in Example 1 was performed, and as a result, the same results as in Example 1 were obtained.

(Titanium nitride particles TiN-4) It was manufactured in the same manner as titanium nitride particles TiN-1 except that the speed of supplying each raw material from the chamber to the cyclone was changed to 14.5 m / s (average value) Titanium nitride particles TiN-4. The X-ray diffraction measurement was performed in the same manner as TiN-1. As a result, the peak diffraction angle derived from the TiN (200) plane was 42.85 °.

[Preparation and evaluation of light-shielding composition TiN-4] In Synthesis Example 1, nitride was used instead of titanium nitride (manufactured by Wako Pure Chemical Industries, Ltd., trade name "titanium nitride 50 nm", average particle diameter 50 nm) In addition to the titanium particles TiN-4, a dispersion sol (TiN-4) containing nitrides of metal (Ti) atoms coated with silicone resin was synthesized in the same manner. Next, in the preparation of the light-shielding composition 1, the light-shielding composition TiN-4 was prepared in the same manner except that the dispersion sol (TiN-4) was used instead of the dispersion sol (A-1). Using the light-shielding composition TiN-4, the same evaluation as in Example 1 was performed. As a result, the adhesion of the obtained light-shielding film to the silicon substrate and the glass substrate was the same as in Example 1. On the other hand, regarding the heat resistance of the light-shielding film, a result worse than that of Example 1 was obtained, but it was at a level where there was no problem in practical use. In addition, the light reflectance of the light-shielding film is 4%.

(Titanium nitride particles TiN-5) It was manufactured in the same way as the titanium nitride particles TiN-1 except that the speed of supplying each raw material from the chamber to the cyclone was changed to 20 m / s (average value) Titanium nitride particles TiN-5. X-ray diffraction measurement was performed in the same manner as TiN-1. As a result, the peak diffraction angle derived from the TiN (200) plane was 43.5 °.

[Preparation and evaluation of light-shielding composition TiN-5] In Synthesis Example 1, nitride was used instead of titanium nitride (manufactured by Wako Pure Chemical Industries, Ltd., trade name "titanium nitride 50 nm", average particle diameter 50 nm) In addition to the titanium particles TiN-5, a dispersion sol (TiN-5) containing nitrides of metal (Ti) atoms coated with silicone resin was synthesized in the same manner. Next, in the preparation of the light-shielding composition 1, the light-shielding composition TiN-5 was prepared by the same method except that the dispersion sol (TiN-5) was used instead of the dispersion sol (A-1). Using the light-shielding composition TiN-5, the same evaluation as in Example 1 was carried out. As a result, the adhesion (number of missing patterns) of the obtained light-shielding film to the silicon substrate and the glass substrate was 2. In addition, regarding the heat resistance of the light-shielding film, a result worse than that of the light-shielding composition TiN-4 was obtained, but it was at a level where there was no problem in practical use. In addition, the light reflectance of the light-shielding film is 4%.

[Example (X-1)] In the light-shielding composition 1, TO138OSE manufactured by TOAGOSEI CO., LTD. Was used instead of the polymerizable compound (T1), and the following 6 masses were used instead of 12 parts by mass of the alkali-soluble resin (J1). Part (solid content conversion) of resin A and 6 parts by mass (solid content conversion) of resin B mixture, and instead of dispersion sol (A-1) used dispersion sol (X-1), except that the same The method adjusted the light-shielding composition (X-1). In addition, the dispersion sol (X-1) is a sol: In the synthesis of the dispersion sol (A-1), when γ-butyrolactone is added for the second time, 1000 parts by mass of γ-butyrolactone is changed to γ- 700 parts by mass of butyrolactone and 300 parts by mass of N-methyl-2-pyrrolidone. The above-mentioned light-shielding composition (X-1) was evaluated in the same manner as in Example 1. As a result, the same evaluation results as in Example 1 were obtained.

・ Synthesis of Resin A is filled with 95.1g of 4,4'-diaminodiphenyl ether, 6.2g of bis (3-aminopropyl) tetramethyldisilaxane, 525g of γ-butyrolactone, 220g Of N-methyl-2-pyrrolidone, add 144.1g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and make it react at 70 ℃ for 3 hours, then add 3.0g of o Phthalic anhydride was further reacted at 70 ° C for 2 hours to obtain a 25% by weight polyamic acid solution (Resin A solution).

・ Synthesis of Resin B is filled with 176.7g of 3'-diaminodiphenylbenzene, 18.6g of bis (3-aminopropyl) tetramethyldisilaxane, 2667g of γ-butyrolactone, and 527g of N Methyl-2-pyrrolidone, add 439.1g of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and make it react at 70 ℃ for 3 hours, then add 2.2g of phthalic anhydride, This was further reacted at 70 ° C. for 2 hours to obtain a 20% by weight polyamic acid solution (Resin B solution).

[Example (X-2)] In the light-shielding composition 1, as the polymerizable compound, a polymerizable compound (TR-1) having the following structure and a polymerizable compound (T1) were used, and the mixing ratio was set to 50. Except for the mass% / 50 mass% mixture, a light-shielding composition (X-2) was produced in the same manner as the light-shielding composition 1. The above-mentioned light-shielding composition (X-2) was evaluated in the same manner as in Example 1. As a result, the same evaluation results as in Example 1 were obtained. In addition, the manufacturing method of a polymerizable compound (TR-1) is referred to Japanese Unexamined Patent Publication No. 2009-169049. [Chemical Formula 17]

100‧‧‧Solid-state camera

101‧‧‧Solid photography element

102‧‧‧Camera Department

103‧‧‧ Cover glass

104‧‧‧ spacer

105‧‧‧Laminated substrate

106‧‧‧ Wafer substrate

107‧‧‧ circuit board

108‧‧‧electrode pad

109‧‧‧External connection terminal

110‧‧‧through electrode

111‧‧‧Lens layer

112‧‧‧Lens material

113‧‧‧Support

114, 115‧‧‧ shading film

201‧‧‧Receiving element

202‧‧‧ color filter

203‧‧‧Microlens

204‧‧‧ substrate

205b‧‧‧blue pixels

205r‧‧‧Red pixel

205g‧‧‧green pixels

205bm‧‧‧Black Matrix

206‧‧‧p well

207‧‧‧Read gate

208‧‧‧Vertical transfer path

209‧‧‧Component separation area

210‧‧‧Gate insulating film

211‧‧‧Vertical transfer electrode

212‧‧‧shading film

213、214‧‧‧Insulating film

215‧‧‧ Flattening film

FIG. 1 is a schematic cross-sectional view showing a configuration example of a solid-state imaging device. FIG. 2 is an enlarged schematic cross-sectional view of the imaging unit of FIG. 1.

Claims (10)

A light-shielding composition comprising: particles of a nitride containing metal atoms; and at least one kind selected from the group consisting of a polymerizable compound and a resin, and the surface of the particles determined by X-ray photoelectron spectroscopy The content atom ratio of the aforementioned metal atom content to the silicon atom content is 1.0 or less. The light-shielding composition as described in item 1 of the scope of patent application, wherein the content atomic ratio is 0.7 or less. The light-shielding composition as described in item 1 or 2 of the scope of patent application further contains a polymerization initiator. The light-shielding composition as described in item 3 of the patent application range, wherein the polymerization initiator is a photopolymerization initiator. The light-shielding composition as described in item 4 of the patent application, wherein the photopolymerization initiator is an oxime ester compound. The light-shielding composition as described in item 1 of the patent application range, wherein the nitride of the metal atom is titanium nitride, and the diffraction from the peak of the (200) plane of the particle when CuKα rays are used as the X-ray source The angle 2θ is 42.5 ° to 42.8 °. A light-shielding film obtained by hardening the light-shielding composition described in any one of claims 1 to 6. A solid-state photographic element containing the light-shielding film described in item 7 of the patent application scope. A color filter containing the light-shielding film as described in item 7 of the patent scope. A liquid crystal display device comprising a light-shielding film as described in item 7 of the patent application.