TW201806853A - Composition, cured film, color filter, light-blocking film, solid-state imaging element and image display device - Google Patents

Abstract

Provided is a composition which is capable of forming a cured film that has excellent patterning properties, while exhibiting excellent anti-corrosion properties for electrodes. Also provided are a cured film, a color filter, a light-blocking film, a solid-state imaging element and an image display device. This composition contains titanium nitride-containing particles, which contain chlorine atoms; and the content of the chlorine atoms in the titanium nitride-containing particles is 0.001-0.3% by mass.

Description

Composition, cured film, color filter, light-shielding film, solid-state photographic element, and image display device

The invention relates to a composition, a cured film, a color filter, a light-shielding film, a solid-state photographic element, and an image display device.

A solid-state imaging device includes a photographic lens, a solid-state imaging element such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal Oxide Semiconductor) disposed behind the photographic lens (hereinafter, the solid-state imaging element is also referred to as "image sensing "." And a circuit board on which the solid-state imaging element is mounted. This solid-state imaging device is mounted on a digital camera, a camera-equipped mobile phone, a smartphone, and the like. In a solid-state imaging device, noise caused by reflection of visible light is sometimes generated. Accordingly, in order to suppress the generation of noise, a predetermined light-shielding film is provided in the solid-state imaging device. As a composition for forming a light-shielding film, a black composition containing a black pigment such as titanium black is used.

On the other hand, it is disposed in a color filter such as a solid-state imaging element, a liquid crystal image device, and the like. In order to prevent mixing of light between colored pixels to improve contrast, etc., R (red), G (green), and B may be used. A black matrix is formed between the (blue) pixels. In addition, in the color filter, in order to prevent light leakage from the light receiving portion of the solid-state imaging element, a light shielding film (frame light shielding film) around the image sensor is formed in a frame region thereof. A black composition containing a black pigment such as titanium black is also used in the composition for forming the black matrix. For example, Patent Document 1 discloses "a black resin composition for a resin black matrix, which contains at least a light-shielding material, a resin, and a solvent, and contains at least titanium nitride particles as a light-shielding material, and wherein CuKα rays are used as the X-ray source. The diffraction angle 2θ of the above-mentioned titanium nitride particles originating from the peak of the (200) plane is 42.5 ° or more and 42.8 ° or less. "(The first patent application range). [Prior Art Literature] [Patent Literature]

[Patent Document 1]: Japanese Patent No. 5136139

The hardened film of the black composition containing the titanium nitride particles (containing titanium nitride particles) as described above is, for example, a black matrix of a light-shielding film or a color filter used as a constituent member of a solid-state imaging device or a periphery of an image sensor. When a light-shielding film is used, it may be laminated on a substrate on which electrodes such as an electrode pattern are arranged. The present inventors produced a black composition containing titanium nitride particles (containing titanium nitride particles) described in Patent Document 1, and used this to form a hardened film on the substrate on which the electrodes were arranged so as to cover the electrodes, and implemented Its evaluation. As a result, it was found that, depending on the type of the titanium nitride particles (containing titanium nitride particles), rust or the like is generated in a region in contact with the light-shielding film of the electrode, that is, the electrode may be corroded in some cases. In the same manner, it was found that when a pattern-shaped cured film is formed using the black composition, the resolution (patternability) of the pattern does not satisfy the desired requirements.

An object of the present invention is to provide a composition capable of producing a cured film having excellent corrosion resistance and excellent pattern formation of an electrode. Another object of the present invention is to provide a cured film, a color filter, a light-shielding film, a solid-state imaging element, and an image display device.

The present inventors have conducted intensive studies on the above problems, and as a result, found that the above problems can be solved by adjusting the content of the chlorine atom in the titanium nitride-containing particles to a predetermined numerical range, and have completed the present invention. That is, it was found that the above-mentioned object can be achieved by the following structure.

(1) A composition containing titanium nitride-containing particles containing chlorine atoms, and a content of the chlorine atom in the titanium nitride-containing particles is 0.001 to 0.3% by mass. (2) The composition according to (1), wherein when CuKα rays are used as the X-ray source, the diffraction angle 2θ of the peak originating from the (200) plane of the titanium nitride-containing particles is more than 42.8 ° and 43.5 ° or less. (3) The composition according to (1) or (2), wherein the specific surface area of the titanium nitride-containing particles obtained by the BET method is 40 to 60 m ² / g. (4) The composition according to any one of (1) to (3), wherein the average primary particle diameter of the titanium nitride-containing particles is 10 to 30 nm. (5) The composition according to any one of (1) to (4), in which a photo observation of the primary particle image of the titanium nitride-containing particles using a transmission electron microscope is performed on 100 observation objects More than 60 are spherical. (6) The composition according to any one of (1) to (5), further comprising two or more solvents. (7) The composition according to any one of (1) to (6), further comprising a dispersant. (8) The composition according to (7), wherein a content ratio of the dispersant to the titanium nitride-containing particles is 0.3 or less by mass ratio. (9) The composition according to any one of (1) to (8), further comprising a polymerizable compound. (10) The composition according to any one of (1) to (9), further comprising a polymerization initiator. (11) The composition according to any one of (1) to (10), wherein the solid content in the composition is 10 to 40% by mass. (12) The composition according to any one of (1) to (11), wherein the content of the titanium nitride-containing particles is 30 to 70% by mass based on the total solid content of the composition. (13) The composition according to any one of (1) to (12), further comprising water, and the content of the water is 0.1 to 1% by mass relative to the total mass of the composition. (14) The composition according to any one of (1) to (13), further comprising a dispersant selected from the group consisting of polycaprolactone, polyvalerolactone, polymethyl acrylate, and polymethyl methacrylate At least one structure of the group consisting of methyl methacrylate. (15) A cured film obtained using the composition according to any one of (1) to (14). (16) A color filter having the cured film according to (15). (17) A light-shielding film having the cured film according to (15). (18) A solid-state imaging element having the cured film according to (15). (19) An image display device having the cured film according to (15). [Inventive effect]

According to the present invention, it is possible to provide a composition capable of producing a cured film having excellent corrosion resistance and excellent pattern formation of an electrode. Furthermore, the present invention can provide a cured film, a color filter, a light-shielding film, a solid-state imaging element, and an image display device.

Hereinafter, the present invention will be described. In the present specification, a numerical range expressed using "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value. In the description of the group (atomic group) in the present specification, the expressions that do not describe substitution and unsubstitution include those that have a substituent together with those that do not have a substituent. For example, "alkyl" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent. In the present specification, "active light" or "radiation" means, for example, a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. In the present invention, light means active light or radiation. Regarding "exposure" in this specification, unless otherwise specified, it is not limited to exposure based on the bright line spectrum of a mercury lamp, far-ultraviolet rays, X-rays, and EUV light represented by excimer lasers, and electron beam and ion beams. The depiction of the particle beam is also included in the exposure. In this specification, "(meth) acrylate" means acrylate and methacrylate, "(meth) acrylic" means acrylic and methacrylic, and "(meth) acryl" refers to acryl and methyl Acrylic amidino, "(meth) acrylamide" means acrylamide and methacrylamide. In addition, in this specification, "monomer" and "monomer" have the same meaning. The monomer in the present invention is different from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound refers to a compound having a polymerizable group, and may be a monomer or a polymer. A polymerizable group refers to a group that participates in a polymerization reaction. [Composition] The composition of the present invention contains titanium nitride-containing particles containing chlorine atoms, and the content of the chlorine atom in the titanium nitride-containing particles is 0.001 to 0.3% by mass. According to the composition of the present invention, a cured film having excellent electrode corrosion resistance and excellent pattern formation properties can be produced. The present inventors conducted intensive studies, and as a result, it was confirmed that a black composition using titanium nitride-containing particles having a chlorine atom content of more than 0.3% by mass as a pigment component was used to dispose the electrode. When a light-shielding film is formed on a substrate, the above-mentioned chlorine atom reacts with moisture in the air and the like to generate hydrochloric acid depending on the use environment conditions, which may cause deterioration of the electrode member. On the other hand, it was found that when a titanium nitride-containing particle containing a chlorine atom content of less than 0.001% by mass is used as a pigment component, the optical density (OD) of the obtained coating film becomes high, and the pattern forming property tends to decrease. . From the viewpoints described above, by setting the content of the chlorine atom in the titanium nitride-containing particles contained in the composition to 0.001 to 0.3% by mass, a cured film having excellent electrode corrosion resistance and excellent pattern formation properties can be formed.

<Titanium Nitride-Containing Particles Containing Chlorine Atoms> In the production of titanium nitride-containing particles, a gas-phase reaction method is generally used, and specific examples thereof include an electric furnace method and a thermal plasma method. Among these manufacturing methods, the thermal plasma method is preferred from the viewpoints of the less mixing of impurities, the easy-to-match particle size, and the higher productivity. Examples of the method for generating thermal plasma include direct current arc discharge, multi-phase arc discharge, high-frequency (RF) plasma, and hybrid plasma. The high-frequency plasma that contains less impurities from the electrode is more suitable. good. As a specific manufacturing method of titanium nitride-containing particles based on the thermal plasma method, for example, titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced into the device as a carrier gas, and titanium is cooled by a cooling process. Method for nitriding powder to synthesize titanium nitride-containing particles and the like. The thermal plasma method is not limited to the above. In addition, by using the thermal plasma method to obtain titanium nitride-containing particles, it is easy to adjust the diffraction angle 2θ (the details will be described later) originating from the peak of the (200) plane when CuKα rays are used as the X-ray source. It is more than 42.8 ° and less than 43.5 °.

Among them, the method for making the titanium nitride-containing particles contain a chlorine atom is not particularly limited. As an example, a method of synthesizing titanium nitride-containing particles containing a chlorine atom by using titanium tetrachloride together with titanium powder and circulating ammonia gas as a carrier gas in the above thermal plasma method is mentioned. In addition, when the content of the chlorine atom in the titanium nitride-containing particles is a predetermined amount or more, for example, the particles are heat-treated at 100 to 300 ° C (120 to 280 ° C, more preferably 120 to 250 ° C) for 5 minutes. ～ 72 hours (3 to 48 hours is more preferable, and 3 to 36 hours is more preferable). By the heat treatment, the content of the chlorine atoms contained in the titanium nitride-containing particles can be adjusted to a predetermined amount.

Titanium powder materials (titanium particles) and titanium tetrachloride-based high purity used in the production of titanium nitride-containing particles are preferred. The titanium powder material and titanium tetrachloride are not particularly limited, and those with a titanium element purity of 99.99% or more are preferably used, and those with a purity of 99.999% or more are more preferable.

The titanium powder material (titanium particles) and titanium tetrachloride used in the production of titanium nitride-containing particles may contain atoms other than titanium atoms. Examples of other atoms that can be contained in the titanium powder material include Fe atoms and Si atoms. When the titanium powder material and titanium tetrachloride contain Fe atoms, the content of Fe atoms is preferably more than 0.001% by mass relative to the total mass of the titanium powder material and titanium tetrachloride. Thereby, the pattern formation property of a cured film is more excellent. When the titanium powder material and titanium tetrachloride contain Fe atoms, the content of Fe atoms is preferably less than 0.4% by mass relative to the total amount of the titanium powder material and titanium tetrachloride. Thereby, the corrosion resistance of the electrode based on the cured film is further improved (the corrosion of the electrode by the cured film can be more suppressed). That is, the titanium powder material used in the production of titanium nitride-containing particles and the Fe atoms contained in titanium tetrachloride are in the above range (more than 0.001% by mass and less than 0.4% by mass), and the present invention can be obtained more significantly. Effect of the invention. When the titanium powder material and titanium tetrachloride contain Si atoms, the content of Si atoms is more than 0.002 mass% and less than 0.3 mass% with respect to the total mass of the titanium powder material, more preferably 0.01-0.15 mass%, and 0.02-0.1 The mass% is more preferable. When the content of Si atoms exceeds 0.002% by mass, the pattern formability of the cured film is further improved. In addition, it is considered that when the content of Si atoms is less than 0.3% by mass, the polarity of the outermost layer of the titanium nitride-containing particles obtained is stable, and the dispersant when dispersing the titanium nitride-containing particles is adsorbed to the titanium nitride-containing particles is obtained. The improvement is that the amount of undispersed titanium nitride-containing particles is reduced, thereby suppressing the generation of particles. That is, when the titanium powder material used in the production of titanium nitride-containing particles and the Si atoms contained in titanium tetrachloride are within the above-mentioned ranges, the effect of the present invention can be more significantly obtained. In addition, the moisture content of the titanium powder material (titanium particles) and titanium tetrachloride used in the production of titanium nitride-containing particles is preferably less than 1% by mass, and more preferably less than 0.1% by mass. It is better that it is not substantially included. When the titanium powder material used in the production of the titanium nitride-containing particles and the moisture in the titanium tetrachloride are within the above range, the effect of the present invention can be more significantly obtained.

The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 50 to 85% by mass, more preferably 50 to 80% by mass, and 50 to 75% by mass relative to the total mass of the titanium nitride-containing particles. Is even better. The content of Ti atoms in titanium nitride-containing particles can be analyzed by ICP (High Frequency Inductively Coupled Plasma) emission spectrometry. The content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 20 to 50% by mass, more preferably 20 to 45% by mass, and 20 to 40% by mass relative to the total mass of the titanium nitride-containing particles. Is even better. The nitrogen atom content can be analyzed by an inert gas fusion thermal conductivity method. The content of oxygen atoms in the titanium nitride-containing particles is preferably 12% by mass or less, and more preferably 8% by mass or less, based on the total mass of the titanium nitride-containing particles. The content of oxygen atoms can be analyzed by an inert gas melting infrared absorption method.

The content of the chlorine atom in the titanium nitride-containing particles is 0.001 to 0.3% by mass based on the total mass of the titanium nitride-containing particles. Among them, 0.005 to 0.3% by mass is preferred, 0.01 to 0.3% by mass is even more preferred, 0.1 to 0.3% by mass is even more preferred, and 0.1 to 0.15% by mass is particularly preferred. When the content of the chlorine atom is 0.001% by mass or more, the pattern forming property of the cured film is excellent. When the content of the chlorine atom is 0.3% by mass or less, the pattern forming property of the cured film is excellent, and the electrode based on the cured film is excellent in corrosion resistance. The content of chlorine atoms in the titanium nitride-containing particles was measured by ICP emission spectrometry.

When CuKα ray is used as the X-ray source to measure the X-ray diffraction spectrum, the diffraction angle 2θ of the peak originating from the (200) plane of the titanium nitride-containing particles is more than 42.8 ° and less than 43.5 °. An OD value of a cured film (for example, a black matrix, etc.) obtained by using a composition containing titanium nitride-containing particles having such characteristics becomes an appropriate value, and pattern formation (resolution) is more excellent.

As described above, the diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particles is preferably more than 42.8 ° and less than 43.5 °, more preferably 42.85-43.3 °, and even more preferably 42.9-43.2 °. Titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and usually become significant when oxygen is mixed during the synthesis and the particle size is small, but some oxygen can be contained by oxidation of the particle surface, etc. atom. Among them, it is preferable to obtain a higher OD value (optical concentration) when the amount of oxygen contained in the titanium nitride-containing particles is small. It is preferable that the titanium nitride-containing particles do not contain TiO ₂ as a subcomponent. When titanium nitride-containing particles contain titanium oxide TiO ₂ as a sub-component, the peak derived from anatase TiO ₂ (101) as the strongest peak appears at around 2θ = 25.3 ° and originates from rutile TiO ₂ ( 110) The peak appears around 2θ = 27.4 °. However, since TiO ₂ is white, it is a factor that reduces the light-shielding property of the black matrix. Therefore, it is preferable to reduce it to such an extent that it cannot be observed as a peak.

The crystallite size of the titanium nitride-containing particles can be determined from the half-value amplitude of the X-ray diffraction peaks, and calculated using the Scherrer formula.

The crystallite size is preferably 20 nm or more, and more preferably 20 to 50 nm. When a black matrix is formed by using titanium nitride-containing particles having a crystallite size of 20 nm or more, the transmitted light of the cured film is blue to blue-violet as its peak wavelength is 475 nm or less, which can achieve both high light shielding and ultraviolet sensitivity. Black matrix.

Titanium nitride-containing particles capable of specific surface area determined by BET method, 40 ~ 60m ² / g is preferred, 40 ~ 58m ² / g is more preferably, 42 ~ 55m ² / g is further preferred. By setting the specific surface area of the titanium nitride-containing particles to 40 to 60 m ² / g, the OD (optical concentration) value of the obtained cured film becomes a more appropriate range, the pattern formation property (resolution) is superior, and the composition It also has excellent filterability.

The average primary particle diameter of the titanium nitride-containing particles is preferably 10 to 30 nm, more preferably 10 to 28 nm, even more preferably 10 to 25 nm, and even more preferably 10 to 20 nm. By setting the average primary particle diameter of the titanium nitride-containing particles to 10 to 30 nm, the OD (optical density) value of the obtained cured film becomes an appropriate range. In addition, from the viewpoint of the stability of the viscosity of the composition over time, the average primary particle diameter of the titanium nitride-containing particles is preferably 10 nm or more. In addition, in the present invention, the average primary particle diameter of the titanium nitride-containing particles means that the particles can be observed by a transmission electron microscope (for example, a device of JEM-2100F field emission transmission electron microscope manufactured by JEOL Ltd.), The number average particle diameter of the primary particles was obtained from the obtained photos. Specifically, a dispersion liquid containing titanium nitride-containing particles was prepared by the method described in the examples, and the solid content of the dispersion liquid was reduced to about 1% by mass. The dispersion was added dropwise, and a transmission electron microscope image of titanium nitride-containing particles present on the carbon foil after drying was observed. The projected area of the primary particles containing titanium nitride particles was determined by the above-mentioned device, and thereby the circular equivalent diameter was determined. The arithmetic mean of the obtained circle-equivalent diameters is taken as the primary particle diameter. More specifically, after measuring the primary particle size of 100 particles randomly selected to obtain an average primary particle size, the arithmetic average of the primary particle sizes of 80 particles excluding the largest 10 and smallest 10 particles was calculated. Equivalent circle diameter. In the photo observation of a particle image using the transmission electron microscope described above, it is preferable that 60 or more of the 100 observation objects (in other words, 60% or more) are spherical. When 60% or more of the titanium nitride-containing particles used are spherical, the OD (optical density) value of the obtained cured film is in an appropriate range, and the pattern formability (resolution) is more excellent. In addition, since more than 60% of the titanium nitride-containing particles used are spherical, the composition has excellent filterability and viscosity stability over time. In the present invention, the term "spherical" means that the particles do not necessarily have to be spherical. For example, the particles may be approximately spherical (the ratio of the short / long diameter in the two-dimensional figure at the time of projection is about 0.7 to 1), and the rotating ellipse. body.

The content of the titanium nitride-containing particles is preferably 30 to 70% by mass, more preferably 40 to 68% by mass, and even more preferably 42 to 65% by mass with respect to the total solid content of the composition. When the content of the titanium nitride-containing particles is within the above-mentioned numerical range, the spectroscopic property (good OD value) is excellent, and the pattern forming property (resolution) and the corrosion resistance of the electrode are also excellent. In addition, in this specification, a solid content means a component which comprises the hardened film formed from a composition, and does not contain a solvent. For example, since the polymerizable compound described later is a component constituting a cured film, it is included in a solid component even if it is a liquid (liquid).

<Dispersant> The composition of the present invention preferably contains a dispersant. The dispersant helps improve the dispersibility of the pigments such as the titanium nitride-containing particles. In this invention, a dispersing agent is a component different from the binder resin mentioned later. As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Among them, a polymer compound is preferred. Examples of the dispersant include polymer dispersants [for example, polyamidoamine and its salts, polycarboxylic acids and their salts, high molecular weight unsaturated esters, modified polyurethanes, modified polyesters, modified poly (methyl Group) acrylate, (meth) acrylic copolymer, formalin naphthalenesulfonate], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, and pigment derivatives. Polymer compounds can be further classified into linear polymers, terminally modified polymers, graft polymers, and block polymers according to their structure.

The polymer compound is adsorbed on the surface of the dispersion such as titanium nitride-containing particles and pigments as needed, and plays a role of preventing re-aggregation of the dispersion. Therefore, it is preferable to have a terminal modified polymer, a graft polymer, and a block polymer that are fixed to the pigment surface. On the other hand, by modifying the surface of the titanium nitride-containing particles, it is also possible to promote the adsorptivity of polymer compounds to this.

The polymer compound preferably has a structural unit having a graft chain. In addition, in this specification, a "structural unit" has the same meaning as a "repeating unit." A polymer compound having a structural unit having such a graft chain has excellent dispersibility of pigments such as titanium nitride particles and dispersion stability over time because the graft chain has an affinity with a solvent. In addition, with the presence of the graft chain, the polymer compound having a structural unit having the graft chain has affinity with a polymerizable compound or another resin that can be used. As a result, residues are less likely to be generated during alkali development. When the graft chain becomes longer, the steric repulsion effect increases and the dispersibility of pigments and the like improves. On the other hand, if the graft chain is too long, the adsorption force to pigments such as titanium nitride-containing particles decreases, and the dispersibility of the pigments and the like 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 2,000, and the number of atoms other than hydrogen atoms is more preferably 60 to 500. good. Herein, the graft chain represents the root of the main chain of the copolymer (the atom bonded to the main chain from the main chain branched group) to the end of the main chain branched group.

The graft chain preferably has a polymer structure. Examples of the polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, and a poly (meth) acrylate structure. Urea structure, polyamine structure and polyether structure. In order to improve the interaction between the graft chain and the solvent and thereby improve the dispersibility, the graft chain system has at least one selected from the group consisting of a polyester structure, a polyether structure, and a poly (meth) acrylate structure. The graft chain of the seed is more preferable, and the graft chain having at least one of a polyester structure and a polyether structure is more preferable.

The macromonomer having such a graft chain is not particularly limited, and a macromonomer having a reactive double bond group can be appropriately used.

Corresponding to the structural unit with a graft chain in the polymer compound, AA-6 (trade name, manufactured by TOAGOSEI CO., LTD.) Can be used as a commercially available macromonomer suitable for the synthesis of the polymer compound, AA-10 (trade name, manufactured by TOAGOSEI CO., LTD.), AB-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AS-6 (trade name, TOAGOSEI CO., LTD.), AN-6 (Trade name, manufactured by TOAGOSEI CO., LTD.), AW-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AA-714 (trade name, manufactured by TOAGOSEI CO., LTD.), AY-707 (product Name, manufactured by TOAGOSEI CO., LTD.), AY-714 (trade name, manufactured by TOAGOSEI CO., LTD.), AK-5 (trade name, manufactured by TOAGOSEI CO., LTD.), AK-30 (trade name, (Manufactured by TOAGOSEI CO., LTD.), AK-32 (trade name, manufactured by TOAGOSEI CO., LTD.), Blemmer PP-100 (trade name, manufactured by NOF CORPORATION.), Blemmer PP-500 (trade name, NOF CORPORATION. (Manufactured), Blemmer PP-800 (trade name, manufactured by NOF CORPORATION.), Blemmer PP-1000 (trade name, manufactured by NOF CORPORATION.), Blemmer 55-PET-800 (trade name, NOF CORPORATION.), Blemmer PME-4000 (trade name, manufactured by NOF CORPORATION.), Blemmer PSE-400 (trade name, manufactured by NOF CORPORATION.), Blemmer PSE-1300 (trade name, manufactured by NOF CORPORATION.), Blemmer 43PAPE -600B (trade name, manufactured by NOF CORPORATION.), Etc. Among them, AA-6 (trade name, manufactured by Toagosei. Company, Limited.), AA-10 (trade name, manufactured by TOAGOSEI CO., LTD.), And AB-6 (trade name, manufactured by TOAGOSEI CO., LTD.) Are used. , AS-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AN-6 (trade name, manufactured by TOAGOSEI CO., LTD.), Blemmer PME-4000 (trade name, manufactured by NOF CORPORATION.), Etc. are preferred .

The dispersant preferably has at least one structure selected from the group consisting of polycaprolactone, polyvalerolactone, polymethyl acrylate, and polymethyl methacrylate. It is more preferable to use two or more of these structures. Here, the polycaprolactone structure means a structure having a ring-opening of ε-caprolactone as a repeating unit. The polyvalerolactone structure means a structure having a ring-opening of δ-valerolactone as a repeating unit. Specific examples of the dispersant having a polycaprolactone structure include those in which j and k in the following formula (1) and the following formula (2) are five. In addition, specific examples of the dispersant having a polyvalerolactone structure include those in which j and k in the following formula (1) and the following formula (2) are four. Specific examples of the dispersant having a polymethyl acrylate structure include those in which X ⁵ in the following formula (4) is a hydrogen atom and R ⁴ is a methyl group. Further, as specific examples of the dispersant having a polymethyl methacrylate structure, those in which X ⁵ is a methyl group and R ⁴ is a methyl group in the following formula (4) can be mentioned.

The polymer compound as a structural unit having a graft chain preferably includes a structural unit represented by any one of the following formulae (1) to (4), and includes the following formula (1A), the following formula (2A), The structural unit represented by any one of the following formula (3A), (3B), and (4) is more preferable.

[Chemical Formula 1]

In Formulae (1) to (4), W ¹ , W ² , W ^3, and W ⁴ each independently represent an oxygen atom or NH. It is preferable that W ¹ , W ² , W ³ and W ⁴ are oxygen atoms. In the formulae (1) to (4), X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. As X ¹ , X ² , X ³ , X ^4, and X ⁵ , from the viewpoint of synthetic limitation, alkyl groups each independently having a hydrogen atom or a carbon number (number of carbon atoms) of 1 to 12 are preferred. Preferably, each independently is a hydrogen atom or a methyl group, and a methyl group is more preferable.

In the formulae (1) to (4), Y ¹ , Y ² , Y ^3, and Y ⁴ each independently represent a divalent linking group, and the structure of the linking group is not particularly limited. Specific examples of the divalent linking group represented by Y ¹ , Y ² , Y ³ and Y ⁴ include the following linking groups (Y-1) to (Y-21). In the structure shown below, A and B each represent a bonding site with the left terminal group and the right terminal group in Formulas (1) to (4), respectively. Among the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of simplicity of synthesis.

[Chemical Formula 2]

In Formulas (1) to (4), Z ¹ , Z ² , Z ^3, and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, and specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group. And amine groups. Among these, as the organic group represented by Z ¹ , Z ² , Z ^3, and Z ⁴ , especially from the viewpoint of improving dispersibility, those having a steric repulsive effect are preferred, and each independently has 5 to 6 carbon atoms. An alkyl or alkoxy group of 24 is preferred, wherein each is independently a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms. Kew is better. The alkyl group contained in the alkoxy group may be any of linear, branched, and cyclic groups.

In Formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500. In the formulas (1) and (2), j and k each independently represent an integer of 2 to 8. From the viewpoint of the dispersion stability and developability of the composition, j and k in the formulae (1) and (2) are preferably integers of 4 to 6, and 5 is more preferred.

In the formula (3), R ³ represents a branched or linear alkylene group, an alkylene group having 1 to 10 carbon atoms is preferred, and an alkylene group having 2 or 3 carbon atoms is more preferred. When p is 2 to 500, a plurality of R ³ may be the same as each other or different from each other. In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. Examples of R ⁴ include a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and a hydrogen atom or an alkyl group is more preferable. When R ⁴ is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. A linear alkyl group having 1 to 20 carbon atoms is more preferred, and a linear alkyl group having 1 to 6 carbon atoms is more preferred. In formula (4), when q is 2 to 500, a plurality of X ⁵ and R ^{4 in the} graft copolymer may be the same as each other or different from each other.

In addition, the polymer compound may have two or more different structural units and a structural unit having a graft chain. That is, the molecules of the polymer compound may include structural units represented by formulas (1) to (4), which are different from each other. In formulas (1) to (4), n, m, p, and When q represents an integer of 2 or more, in the formulae (1) and (2), the side chains may include structures in which j and k are different from each other. In the formulae (3) and (4), there are plural numbers in the molecule Each of R ³ , R ⁴ and X ⁵ may be the same as each other or different from each other.

As the structural unit represented by the formula (1), a structural unit represented by the following formula (1A) is more preferable from the viewpoint of the dispersion stability and developability of the composition. In addition, as the structural unit represented by the formula (2), a structural unit represented by the following formula (2A) is more preferable from the viewpoint of the dispersion stability and developability of the composition.

[Chemical Formula 3]

In the formula ^{(1A), X 1, X} Y 1, Z 1 and n are as defined in the formula (1) is ^1, Y ^1, Z ¹ and n, respectively, preferred ranges are also the same. In formula ^{(2A), X 2, Y} 2, Z 2 and m are as defined for the formula X (2) is ^2, Y ^2, Z ² and the same as m, the preferred range is also the same.

In addition, as the structural unit represented by the formula (3), a structural unit represented by the following formula (3A) or formula (3B) is more preferable from the viewpoint of the dispersion stability and developability of the composition.

[Chemical Formula 4]

Formula (3A) or (3B) in, ^3, Y ^3, Z ³ and same ^{p X 3, Y 3, Z} 3 and p are defined for the formula X (3) is, preferred ranges are also the same.

As a structural unit having a graft chain, the polymer compound preferably has a structural unit represented by formula (1A).

In the polymer compound, the structural unit having a graft chain (for example, the structural unit represented by the above formula (1) to formula (4)) is 2 to 90% by mass conversion with respect to the total mass of the polymer compound. The range is preferable, and the range of 5 to 30% is more preferable. When the structural unit having a graft chain is included within this range, the dispersibility of the titanium nitride-containing particles is high, and the developability when forming a cured film is good.

In addition, it is preferable that the polymer compound has a hydrophobic structural unit different from the structural unit having a graft chain (that is, does not correspond to the structural unit having a graft chain). In the present invention, the hydrophobic structural unit is a structural unit that does not have an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphate group, a phenolic hydroxyl group, and the like).

The hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, and more preferably a structural unit derived from a compound having a ClogP value of 1.2 to 8. Thereby, the effect of this invention can be shown more reliably.

The ClogP value is a value calculated by a program "CLOGP" which can be obtained from Daylight Chemical Information System, Inc. This program provides the "calculated logP" value calculated from the fragmentapproach (see below) of Hansch, Leo. Fragmentapproach divides the chemical structure into partial structures (fragments) based on the chemical structure of the compound, and totals the logP contribution amount allocated to the fragment to estimate the logP value of the compound. The details are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used. AJ Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, PG Sammnens, JB Taylor and CA Ramsden, Eds., P.295, Pergamon Press, 1990 C. Hansch & AJ Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. AJ Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993.

logP represents the common logarithm of the partition coefficient P (partition coefficient). It is a quantitative value representing the physical property value of how an organic compound is distributed in the two-phase equilibrium of oil (usually 1-octanol) and water. Expression. logP = log (Coil / Cwater) In the formula, Coil represents the Mohr concentration of the compound in the oil phase, and Cwater represents the Mohr concentration of the compound in the water phase. If the value of logP increases with a positive (plus) value between 0, it means that the oil solubility increases, and if the absolute value increases with minus (minus), it means an increase in water solubility, which has a negative correlation with the water solubility of organic compounds. Parameters for estimating the hydrophobicity of organic compounds are widely used.

The polymer compound, as the hydrophobic structural unit, preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulae (i) to (iii).

[Chemical Formula 5]

In the formulae (i) to (iii), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.) or an alkyl group having 1 to 6 carbon atoms ( For example, methyl, ethyl, propyl, etc.). R ¹ , R ² and R ³ are more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R ² and R ³ are particularly preferably hydrogen atoms. X represents an oxygen atom (-O-) or an imine group (-NH-), and an oxygen atom is preferred.

L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkylene group, a substituted alkylene group, an alkylene group, a substituted alkylene group), a divalent Aromatic group (eg, arylene, substituted arylene), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted An amine group (-NR ^31- , wherein R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), a combination thereof, and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15 and even more preferably 1 to 10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but a saturated aliphatic group is preferred. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group.

The carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15 and even more preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocyclic ring may be condensed with other heterocyclic rings, aliphatic rings or aromatic rings. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (= O), a thio group (= S), an imino group (= NH), and a substituted imino group (= NR ³²⁾ . ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group.

An L-based single bond, an alkylene group, or a divalent linking group containing an alkylene oxide structure is preferred. The alkylene oxide structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L may include a polyoxyalkylene structure containing two or more alkylene oxide structures repeatedly. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferred. The polyoxyethylene structure is represented by-(OCH ₂ CH ₂ ) n-, where n is an integer of 2 or more is preferable, and an integer of 2 to 10 is more preferable.

Examples of Z include an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, and a substituted unsaturated alkyl group), and an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, and a substituted arylene group). Aryl), heterocyclyl and combinations thereof. These groups may include an oxygen atom (-O-), a sulfur atom (-S-), an imine group (-NH-), a substituted imine group (-NR ^31- , wherein R ³¹ is an aliphatic group , Aromatic or heterocyclic) or carbonyl (-CO-).

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15 and even more preferably 1 to 10. The aliphatic group also includes a ring group hydrocarbon group and a crosslinked cyclic hydrocarbon group. Examples of the ring group hydrocarbon group include dicyclohexyl, perhydronaphthyl, biphenyl, 4-cyclohexylphenyl, and the like. Examples of the crosslinked cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, and bicyclic octane ring (bicyclic [2.2.2 ] Octane ring, bicyclic [3.2.1] octane ring, etc.) and other bicyclic hydrocarbon rings; homoblane (homobledane), adamantane, tricyclic [5.2.1.02,6] decane and tricyclic [4.3. 1.12,5] undecane ring and other 3-ring hydrocarbon rings; tetracyclic [4.4.0.12, 5.17, 10] dodecane, perhydro-1,4-methylene-5,8-methylene naphthalene ring Etc. 4-ring hydrocarbon ring and so on. In addition, the cross-linked cyclic hydrocarbon ring also includes a fused ring hydrocarbon ring, such as perhydronaphthalene (decahydronaphthalene), perhydroanthracene, perhydrophenanthrene, perhydroperylene, perhydroperylene, perhydroindene, and perhydro Condensed rings such as fluorene rings are condensed with a plurality of 5 to 8-membered cycloalkane rings. Compared with an unsaturated aliphatic group, an aliphatic group is a saturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. Among them, the aliphatic group does not have an acid group as a substituent.

The number of carbon atoms of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.

The heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocyclic ring may be condensed with other heterocyclic rings, aliphatic rings or aromatic rings. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (= O), a thio group (= S), an imino group (= NH), and a substituted imino group (= NR ³²⁾ . ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.

In the formula (iii), R ⁴ , R ^5, and R ⁶ each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), and an alkyl group having 1 to 6 carbon atoms (for example, methyl , Ethyl, propyl, etc.), Z or LZ. Here, the meanings of L and Z are the same as those of L and Z described above. As R ⁴ , R ⁵ and R ⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred, and a hydrogen atom is more preferred.

In the present invention, as the monomer represented by the general formula (i), R ¹ , R ^2, and R ³ are a hydrogen atom or a methyl group, L is a single bond or an alkylene group, or a divalent link including an alkylene oxide structure Compounds in which X is an oxygen atom or an imine group, and Z is an aliphatic group, a heterocyclic group or an aromatic group are preferred. In addition, as the monomer represented by the general formula (ii), a compound in which R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable. Further, as the monomer represented by the general formula (iii), a compound in which R ⁴ , R ⁵ and R ⁶ are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferred.

Examples of the representative compounds represented by the formulae (i) to (iii) include radical polymerizable compounds selected from the group consisting of acrylates, methacrylates, and styrenes. In addition, as examples of the representative compounds represented by the formulae (i) to (iii), the compounds described in paragraphs 0089 to 0093 of Japanese Patent Application Laid-Open No. 2013-249417 can be referred to, and these contents are incorporated herein.

In the polymer compound, the hydrophobic structural unit is preferably contained in a range of 10 to 90% with respect to the total mass of the polymer compound in terms of mass, and more preferably contained in a range of 20 to 80%. When the content is in the above range, sufficient pattern formation can be achieved.

The polymer compound can introduce a functional group that can interact with pigments such as titanium nitride-containing particles. Among them, it is preferable that the polymer compound further includes a structural unit having a functional group capable of interacting with pigments such as titanium nitride-containing particles. Examples of the functional group that can interact with the pigment such as the titanium nitride-containing particles include an acid group, a basic group, a coordinating group, and a reactive functional group. When a polymer compound has an acid group, a basic group, a coordinating group, or a reactive functional group, it contains a structural unit having an acid group, a structural unit having a basic group, a structural unit having a coordination group, or It is preferred to include reactive structural units. In particular, the polymer compound further has an alkali-soluble group such as a carboxylic acid group as an acid group, whereby the polymer compound can be provided with developability for pattern formation by alkali development. That is, by introducing an alkali-soluble group into the polymer compound, in the composition of the present invention, the polymer compound that is a dispersant that facilitates the dispersion of pigments such as titanium nitride particles is alkali-soluble. A composition containing such a polymer compound becomes an excellent light-shielding property of the exposed portion, and the alkali developability of the unexposed portion is improved. In addition, since the polymer compound has a structural unit containing an acid group, the polymer compound tends to be easily integrated with a solvent and the coating property is also improved. This is presumably because the acid group in the structural unit having acid groups easily interacts with pigments such as titanium nitride-containing particles, the polymer compound stably disperses the pigments such as titanium nitride-containing particles, and the titanium nitride-containing particles, etc. The viscosity of the pigment-dispersed polymer compound becomes low, and the polymer compound itself is easily and stably dispersed.

Among them, the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the structural unit having a graft chain described above, or may be a different structural unit, but has a structural unit having an alkali-soluble group as an acid group It is a structural unit different from the above-mentioned hydrophobic structural unit (that is, does not correspond to the above-mentioned hydrophobic structural unit).

As the functional group that can interact with pigments containing titanium nitride particles, that is, an acid group, for example, there are a carboxylic acid group, a sulfonic acid group, a phosphate group, or a phenolic hydroxyl group. At least one of these is preferable, and a carboxylic acid group is particularly preferable from the viewpoints of good adsorption of pigments containing titanium nitride particles and the like and high dispersibility of the colored pigment. That is, it is preferable that the polymer compound further includes a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound may have one or two or more kinds of structural units having an acid group. The polymer compound may or may not contain a structural unit having an acid group, but when contained, the content of the structural unit having an acid group is calculated in terms of mass, and it is preferably 5 to 80% relative to the total mass of the polymer compound. From the viewpoint of suppressing damage to the image intensity due to alkali development, 10 to 60% is more preferable.

Basic groups that are functional groups that can interact with pigments such as titanium nitride-containing particles include primary amine groups, secondary amine groups, tertiary amine groups, heterocyclic rings containing N atoms, and fluorene. Amine groups and the like are preferred from the viewpoint of good adsorption of pigments containing titanium nitride particles and the like and high pigment dispersibility. The polymer compound may have one or more of these basic groups. The polymer compound may or may not contain a structural unit having a basic group. When contained, the content of the structural unit having a basic group is calculated in terms of mass, and is 0.01% or more and 50% or less with respect to the total mass of the polymer compound. Preferably, from the viewpoint of suppressing the development resistance, 0.01% or more and 30% or less are more preferable.

Examples of the functional group that can interact with pigments such as titanium nitride-containing particles, that is, a complexing group and a reactive functional group include, for example, acetamidine, trialkoxysilyl, and isocyanate. Base, anhydride, and chlorin. From the viewpoints of good adsorption of pigments containing titanium nitride particles and the like and high dispersibility of the pigment, acetamidine is preferred. The polymer compound may have one or two or more of these groups. The polymer compound may contain a structural unit having a coordinating group or a functional group having a reactivity, or it may not be contained, but when it is contained, the content of these structural units is expressed in terms of mass relative to the total mass of the polymer compound, 10% It is more preferable that it is more than 80%, and it is more preferable that it is 20% or more and 60% or less from the viewpoint of suppressing the obstructive development property.

When the polymer compound in the present invention has a functional group that can interact with pigments such as titanium nitride-containing particles in addition to the graft chain, it contains various functions that can interact with pigments such as titanium nitride-containing particles as described above. The functional group is not particularly limited, but the polymer compound has one or more structural units selected from structural units derived from monomers represented by the following general formulae (iv) to (vi). Is better.

[Chemical Formula 6]

In the general formulae (iv) to (vi), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or the like) or a carbon number of 1 to 6 alkyl (eg, methyl, ethyl, propyl, etc.). In the general formulae (iv) to (vi), it is preferable that R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each is independently a hydrogen atom or a methyl group. The base is better. In the general formula (iv), R ¹² and R ¹³ are each preferably a hydrogen atom.

X ₁ in the general formula (iv) represents an oxygen atom (-O-) or an imine group (-NH-), and an oxygen atom is preferred. In addition, Y in the general formula (v) represents a methine group or a nitrogen atom.

In addition, L ₁ in the general formulae (iv) to (v) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkylene group, a substituted alkylene group, an alkylene group, and a substituted alkylene group), 2 Valence aromatic group (for example, arylene group and substituted arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), Substituted imine bond (-NR ³¹ '-, wherein R ³¹ ' is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), a combination thereof, and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15 and even more preferably 1 to 10. It is preferable that the aliphatic group is a saturated aliphatic group compared with an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

The carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. In the heterocyclic ring, one or more of other heterocyclic rings, aliphatic rings, or aromatic rings may be condensed. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (= O), a thio group (= S), an imino group (= NH), and a substituted imino group (= NR ³²⁾ . ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group.

L ₁ is preferably a single bond, an alkylene group, or a divalent linking group containing an alkylene oxide structure. The alkylene oxide structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L ₁ may include a polyoxyalkylene structure including two or more alkylene oxide structures repeatedly. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferred. The polyoxyethylene structure is represented by-(OCH ₂ CH ₂ ) n-, where n is an integer of 2 or more is preferable, and an integer of 2 to 10 is more preferable.

In the general formulae (iv) to (vi), Z ₁ represents a functional group other than the graft chain that can interact with pigments such as titanium nitride-containing particles. A carboxylic acid group and a tertiary amine group are preferred. Acid groups are more preferred.

In the general formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), and an alkyl group having 1 to 6 carbon atoms (for example, , methyl, ethyl and propyl, etc.), - Z ₁ or L ₁ -Z _1. Wherein, L ₁ and Z ₁ meaning the same as the above L ₁ and Z _1, preferred embodiments are also the same. R ¹⁴ , R ^15, and R ¹⁶ are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

In the present invention, as the monomer represented by the general formula (iv), R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group, L ₁ is an alkylene group or a divalent link including an alkylene oxide structure. A compound in which X ₁ is an oxygen atom or an imine group, and Z ₁ is a carboxylic acid group is preferred. Further, as the monomer represented by the general formula (v), a compound in which R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is a methine group is preferable. In addition, as the monomer represented by the general formula (vi), a compound in which R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a methyl group, L ₁ is a single bond or an alkylene group, and Z is a carboxylic acid group is Better.

Representative examples of the monomer (compound) represented by the general formulae (iv) to (vi) are shown below. Examples of the monomer include a reaction of methacrylic acid, crotonic acid, isocrotonic acid, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. Reactants of compounds having addition polymerizable double bonds and hydroxyl groups in the molecule and phthalic anhydride, reactants of compounds having addition polymerizable double bonds and hydroxyl groups in the molecule and tetrahydroxyphthalic anhydride, Reactant of compound having addition polymerizable double bond and hydroxyl group in the molecule and trimellitic anhydride, reactant of compound having addition polymerizable double bond and hydroxyl group in the molecule and pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid Oligomers, maleic acid, itaconic acid, fumaric acid, 4-vinyl benzoic acid, vinyl phenol, 4-hydroxybenzylpropene, and the like.

From the viewpoints of interaction with pigments such as titanium nitride particles, dispersion stability, and permeability to a developer, the content of the structural unit having a functional group that can interact with pigments such as titanium nitride particles is relative to The total mass of the polymer compound is preferably from 0.05% by mass to 90% by mass, more preferably from 1.0% by mass to 80% by mass, and even more preferably from 10% by mass to 70% by mass.

In addition, in order to improve various properties such as image strength, the polymer compound may be added before the effects of the present invention are impaired, and may further include a structural unit having a graft chain, a hydrophobic structural unit, and a polymer having titanium nitride-containing particles. The structural unit of the functional group that the pigment forms interacts with is different from other structural units having various functions (for example, a structural unit having a functional group having an affinity with the dispersion medium used for the dispersion, etc.). Examples of such other structural units include structural units derived from a radical polymerizable compound selected from acrylonitrile and methacrylonitrile. The polymer compound can use one or two or more of these other structural units, and its content is expressed in terms of mass, and relative to the total mass of the polymer compound, 0% to 80% is preferred, and 10% to 60% is preferred. The following are particularly preferred. When the content is within the above range, sufficient pattern-formability can be maintained.

The range of the acid value of the polymer compound is from 0 mgKOH / g to 160 mgKOH / g, more preferably from 10 mgKOH / g to 140 mgKOH / g, and from 20 mgKOH / g to 120 mgKOH / g. good. When the acid value of the polymer compound is 160 mgKOH / g or less, the pattern peeling during development when forming a cured film is more effectively suppressed. In addition, when the acid value of the polymer compound is 10 mgKOH / g or more, alkali developability is further improved. In addition, when the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of pigments such as titanium nitride-containing particles can be more suppressed, the number of coarse particles can be reduced, and the stability of the composition over time can be further improved.

In the present invention, the acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound. In addition, a resin having a desired acid value can be obtained by changing the content of a structural unit that is a component containing a polymer compound, that is, an acid group.

When forming a cured film, the weight average molecular weight of the polymer compound in the present invention is a polystyrene conversion value based on the GPC (gel permeation chromatography) method from the viewpoints of suppression of pattern peeling at the time of development and developability, 4,000 or more and 300,000 or less are preferable, 5,000 or more and 200,000 or less are more preferable, 6,000 or more and 100,000 or less are more preferable, and 10,000 or more and 50,000 or less are more preferable. The GPC method is based on a method using HLC-8020GPC (manufactured by TOSOH CORPORATION.), Using TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6mmID × 15cm) as the column, and using THF as the eluent (Tetrahydrofuran).

The polymer compound can be synthesized by a known method. Examples of the solvent used in the synthesis of the polymer compound include dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene glycol. Monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethyl Methylformamide, N, N-dimethylacetamide, dimethylmethylene, toluene, ethyl acetate, methyl lactate, ethyl lactate, and the like. These solvents may be used alone or in combination of two or more.

Specific examples of the polymer compound that can be used in the present invention include "DA-7301" manufactured by Kusumoto Chemicals, Ltd., and "Disperbyk-101 (Polyamidamine Phosphate), 107 (Carboxylic Acid) manufactured by BYK Chemie. Acid ester), 110 (copolymers containing acid groups), 111 (phosphoric acid-based dispersant), 130 (polyamidamine), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymers) "," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) "," EFKA4047, 4050-4010-4165 (polyurethane), EFKA4330-4340 (block copolymer), 4400-4440 (modified Polyacrylic acid ester), 5010 (polyurethane), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative), Ajinomoto "AJISPER PB821, PB822, PB880, PB881" manufactured by Fine-Techno Co., Inc., "Floren TG-710 (urethane oligomer)", "Polyflow No. 50E, No. 300" manufactured by KYOEISHA CHEMICAL Co., LTD. (Acrylic Copolymer) "," Disparlon KS-86 "manufactured by Kusumoto Chemicals, Ltd. 0, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725 "," DEMOL RN, N (naphthalenesulfonate) manufactured by Kao Corporation Acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "," Homogenol L-18 (polymeric polycarboxylic acid) "," EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) "," ACETAMIN 86 (stearylamine acetate) "," SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative) manufactured by The Lubrinzol Corporatin, 13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymer with functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer) ", Nikko Chemicals Co., Ltd. Manufacture of "Nikkor T106 (polyoxyethylene sorbitol monooleate), MYS-IEX (polyoxyethylene monostearate)", Kawaken Fine Chemicals Co., Ltd., Hinoakuto T-8000E, etc., Shin-Etsu Chemical Co., Ltd. manufactures polyorganosiloxane polymer KP341, Yusho Co Ltd manufactures "W001: cationic interfacial activity ", Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, Nonionic surfactants such as polyethylene glycol distearate and sorbitan fatty acid esters, anionic surfactants such as "W004, W005, W017", and "EFKA-46" manufactured by MORISHITA & CO., LTD. , EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 ", manufactured by SAN NOPCO LIMITED" Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 "Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ", And" Ionet (trade name) S-20 "manufactured by Sanyo Chemical Industries, Ltd. and the like. In addition, Acrylicbase FFS-6752, Acrylicbase FFS-187, Akurikuya-RD-F8, and Cyclomer P can also be used. Examples of commercially available amphoteric resins include DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, manufactured by BYK Additives & Instruments. DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, AJISPER PB821, AJISPER PB822, and AJISPER PB881 manufactured by Ajinomoto Fine-Techno Co., Inc. and the like. These polymer compounds may be used alone or in combination of two or more kinds.

In addition, as examples of specific examples of the polymer compound, reference may be made to the polymer compound described in paragraphs 0127 to 0129 of Japanese Patent Application Laid-Open No. 2013-249417, which are incorporated into this specification.

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

When the composition contains a dispersant, the content of the dispersant is preferably 0.1 to 50% by mass, and more preferably 0.5 to 30% by mass, relative to the total solid content of the composition. The dispersant may be used singly or in combination of two or more kinds. When two or more kinds are used, it is preferable that the total measurement falls within the above range.

<Binder resin> The composition of the present invention preferably contains a binder resin. As the binder resin, a linear organic polymer is preferably used. As such a linear organic polymer, a known one can be arbitrarily used. In order to achieve water development or weak alkaline water development, it is preferable to select a linear organic polymer that is soluble or swellable to water or weak alkaline water. Among them, alkali-soluble resins (resins having a group that promotes alkali-solubility) are particularly preferred as the binding resin. As the binder resin, it is possible to have at least one group that promotes alkali solubility from a linear organic polymer and a molecule (preferably a molecule having a (meth) acrylic copolymer or a styrene copolymer as a main chain). The alkali-soluble resin is appropriately selected. From the viewpoint of heat resistance, polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, (meth) acrylic acid / (meth) acrylic resin Amine copolymer resins are preferred, and from the viewpoint of controllability of developability, (meth) acrylic resins, (meth) acrylamide resins, and (meth) acrylic acid / (meth) acrylamide copolymer resins are Better. Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxyl group, a phosphate group, a sulfonic acid group, and a phenolic hydroxyl group. Among them, those which are soluble in an organic solvent and can be developed with a weakly alkaline aqueous solution are preferred, and more preferred are alkali-soluble resins having a structural unit derived from (meth) acrylic acid. These acid groups may be only one kind, or two or more kinds.

Examples of the binder resin include a radical polymer having a carboxylic acid group in a side chain, for example, Japanese Patent Laid-Open No. 59-44615, Japanese Patent Laid-Open No. 54-34327, Japanese Patent Laid-Open No. 58-12577, and Japanese Patent No. As disclosed in Kosho 54-25957, Japanese Unexamined Patent Application No. 54-92723, Japanese Unexamined Patent Application No. 59-53836, and Japanese Unexamined Patent Application No. 59-71048, that is, monomers having a carboxyl group alone or copolymerized therewith Resin, monomer having acid anhydride alone or copolymerized, and resin having acid anhydride unit hydrolyzed or semi-esterified or semi-fluorinated, and epoxy acrylic acid modified by unsaturated monocarboxylic acid and anhydride Esters, etc. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Examples of the monomer having an acid anhydride include: Examples include maleic anhydride. Moreover, the acidic cellulose derivative which similarly has a carboxylic acid group in a side chain is mentioned as an example. It is also useful to add a cyclic acid anhydride to a polymer having a hydroxyl group. In addition, European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463 have excellent balance between film strength and developability of the acetal-modified polyvinyl alcohol-based adhesive resin having an acid group and the like. Is better. Moreover, as a water-soluble linear organic polymer, polyvinylpyrrolidone, polyethylene oxide, etc. are useful. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon and polyether, which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, are also useful.

In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition polymerizable ethylene monomers as necessary] copolymers) and [allyl (meth) acrylate / (methyl) ) Acrylic acid / other addition polymerizable ethylene monomers as required] Copolymers are excellent in film strength, sensitivity, and developability, and are preferred. Examples of commercially available products include Acrylicbase FF-187, FF-426 (manufactured by FUJIKURA KASEI CO., LTD.), Akurikuya-RD-F8 (NIPPON SHOKUBAI CO., LTD.), And DAICEL-ALLNEX LTD. Cyclomer P (ACA) 230AA, etc.

In the production of the binder resin, for example, a method based on a known radical polymerization method can be applied. Those skilled in the art can easily set polymerization conditions such as temperature, pressure, the type and amount of the radical initiator, and the type of the solvent when the alkali-soluble resin is produced by the radical polymerization method.

In addition, as the binder resin, it is also preferable to use a polymer containing a structural unit having a graft chain and a structural unit having an acid group (alkali-soluble group). The definition of the structural unit having a graft chain is the same as the structural unit having a graft chain in the dispersant described above, and the preferred range is also the same. Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphate group, and a phenolic hydroxyl group. At least one kind of the carboxylic acid group, the sulfonic acid group, and the phosphoric acid group is preferable, and the carboxylic acid group is more preferable.

As the structural unit having an acid group, it is preferable to have one or more structural units selected from structural units derived from a singular body represented by the following general formula (vii) to general formula (ix).

[Chemical Formula 7]

In the general formulae (vii) to (ix), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or the like) or a carbon number of 1 to 6 alkyl (eg, methyl, ethyl, propyl, etc.). In the general formulae (vii) to (ix), R ²¹ , R ^22, and R ²³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each is independently a hydrogen atom or a methyl group. good. In the general formula (vii), R ²¹ and R ²³ are each preferably a hydrogen atom.

X ₂ in the general formula (vii) represents an oxygen atom (-O-) or an imine group (-NH-), and an oxygen atom is preferred. In addition, Y in the general formula (viii) represents a methine group or a nitrogen atom.

In addition, L ₂ in the general formulae (vii) to (ix) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkylene group, a substituted alkylene group, an alkylene group, and a substituted alkylene group), 2 Valence aromatic group (for example, arylene group and substituted arylene group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), Substituted imine bond (-NR ⁴¹ '-, wherein R ⁴¹ ' is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), a combination thereof, and the like.

The divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15 and even more preferably 1 to 10. As for the aliphatic group, a saturated aliphatic group is more preferable than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

The carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15 and even more preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. One or more other heterocycles, aliphatic rings, or aromatic rings may be condensed on the heterocyclic ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (= O), a thio group (= S), an imino group (= NH), and a substituted imino group (= NR ⁴²⁾ . ⁴² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group.

L ₂ is preferably a single bond, an alkylene group, or a divalent linking group containing an alkylene oxide structure. The alkylene oxide structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L ₂ may include a polyoxyalkylene structure that repeatedly includes two or more oxyalkylene structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferred. The polyoxyethylene structure is represented by-(OCH ₂ CH ₂ ) n-, where n is an integer of 2 or more is preferable, and an integer of 2 to 10 is more preferable.

In the general formulae (vii) to (ix), Z ₂ is an acid group, and a carboxylic acid group is preferred.

In the general formula (ix), R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), and an alkyl group having 1 to 6 carbon atoms (for example, , methyl, ethyl, propyl, etc.), - Z ₂ or L ₂ -Z _2. Wherein, L _2, and the meaning is the same as Z ₂ in the above-described L ₂ and Z _2, preferred examples are also the same. R ²⁴ , R ^25, and R ²⁶ are each preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

In the present invention, as a singular body represented by the general formula (vii), R ²¹ , R ^22, and R ²³ are each independently a hydrogen atom or a methyl group, and L ₂ is an alkylene group or a divalent compound containing an alkylene oxide structure. A compound in which the linking group, X ₂ is an oxygen atom or an imine group, and Z ₂ is a carboxylic acid group is preferred. In addition, as a single body represented by the general formula (vii), a compound in which R ²¹ is a hydrogen atom or a methyl group, L ₂ is an alkylene group, Z ₂ is a carboxylic acid group, and Y is a methine group is preferable. Further, as the singular body represented by the general formula (ix), compounds in which R ²⁴ , R ²⁵ and R ²⁶ are each independently a hydrogen atom or a methyl group, and Z ₂ is a carboxylic acid group are preferred.

The above-mentioned adhesive resin can be synthesized by the same method as the above-mentioned dispersant containing a structural unit having a graft chain, and its preferred acid value and weight average molecular weight are also the same.

The adhesive resin may have one or more structural units having an acid group. The content of the structural unit having an acid group is, in terms of mass conversion, preferably 5 to 95% relative to the total mass of the above-mentioned adhesive resin. From the viewpoint of suppressing damage to the image strength by alkali development, 10 to 90% is Better.

The content of the binder resin in the composition of the present invention is preferably 0.1 to 30% by mass, and more preferably 0.3 to 25% by mass relative to the total solid content of the composition. The adhesive resin can be used alone or in combination of two or more. When two or more kinds are used, it is preferable that the total measurement falls within the above range.

In the composition of the present invention, the content ratio of the dispersant to the titanium nitride-containing particles (dispersant / titanium nitride-containing particles (hereinafter, also referred to as "D / P") mass ratio) is 0.3 or less. Preferably, 0.05 to 0.3 is more preferable, and 0.1 to 0.3 is more preferable. When the content ratio D / P is within the above range, the performance of the dispersion is excellent in reproducibility, and the pattern forming property (resolution) of the cured film is also excellent.

<Polymerizable Compound> The composition of the present invention preferably contains a polymerizable compound. The polymerizable compound is preferably a compound containing one or more ethylenically unsaturated groups, more preferably two or more compounds, more preferably three or more compounds, and even more preferably five or more compounds. The upper limit is, for example, 15 or less. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acrylfluorenyl group.

The polymerizable compound may be, for example, any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture of these, and a polymer of these, and a monomer is preferred. The molecular weight of the polymerizable compound is preferably 100 to 3000, and more preferably 250 to 1500. The polymerizable compound is preferably a 3 to 15-functional (meth) acrylate compound, and more preferably a 3 to 6-functional (meth) acrylate compound. Examples of monomers and prepolymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amines thereof. And these polymers, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amidines of unsaturated carboxylic acids and aliphatic polyamine compounds, and these polymers are preferred. Further, an addition reaction product of an unsaturated carboxylic acid ester or amidoamine having a nucleophilic substituent such as a hydroxyl group, an amine group, or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, or the above may be appropriately used. Dehydration condensation reactants of unsaturated carboxylic acid esters or amidoamines with monofunctional or polyfunctional carboxylic acids, and the like. In addition, unsaturated carboxylic acid esters having an electrophilic substituent such as isocyanate group and epoxy group, or reactants of amidoamines with monofunctional or polyfunctional alcohols, amines, thiols, halogen groups or toluene Unsaturated carboxylic acid esters such as sulfonyl groups and the like or reactants of amidoamines with monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. Further, instead of the unsaturated carboxylic acid, a styrene derivative such as an unsaturated phosphonic acid or styrene, or a compound group substituted with a vinyl ether, an allyl ether, or the like can be used. As these specific compounds, the compounds described in paragraphs [0095] to [0108] of Japanese Patent Application Laid-Open No. 2009-288705 can also be suitably used in the present invention.

In the present invention, as the polymerizable compound, a compound containing one or more groups having an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure is also preferable. As examples thereof, the compounds described in paragraphs 0227 of Japanese Patent Application Laid-Open No. 2013-29760 and paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970 can be referred to, and the contents are incorporated herein.

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 commercial product) Sale product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and these (meth) acrylfluorenyl groups are passed through ethylene glycol residues and propylene glycol residues The basic structure (for example, SR454, SR499 marketed by Sartomer company Inc.) is preferable. These oligomer types can also be used. In addition, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), and the like can also be used. The following is a description of the state of a preferable polymerizable compound.

The polymerizable compound may have acid groups such as a carboxyl group, a sulfonic acid group, and a phosphate group. As the polymerizable compound having 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 the 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 preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and when it is 40 mgKOH / g or less, it is advantageous in terms of manufacturing and handling. In addition, the photopolymerization performance is good and the curability is excellent.

As for the polymerizable compound, a compound having a caprolactone structure is also preferable. The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, and trihydroxymethyl. Polyols such as methylpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerin, and trimethylol melamine are obtained by esterification with (meth) acrylic acid and ε-caprolactone Ε-caprolactone modified polyfunctional (meth) acrylate. Among them, a compound having a caprolactone structure represented by the following general formula (Z-1) is preferable.

[Chemical Formula 8]

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

[Chemical Formula 9]

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

[Chemical Formula 10]

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

A polymerizable compound having a caprolactone structure is commercially available, for example, from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series. DPCA-20 (in the above formulas (Z-1) to (Z-3), m = 1, and The number of groups represented by formula (Z-2) = 2, compounds where R ^{1 is} all a hydrogen atom), DPCA-30 (same formula, m = 1, the number of groups represented by formula (Z-2) = 3. Compounds in which all of R ¹ are hydrogen atoms), DPCA-60 (same formula, m = 1, the number of groups represented by formula (Z-2) = 6, compounds in which all of R ¹ are hydrogen atoms), and DPCA -120 (a compound in which m = 2, the number of groups represented by the formula (Z-2) = 6, and all of R ¹ is a hydrogen atom) and the like.

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

[Chemical Formula 11]

In the general formulae (Z-4) and (Z-5), E each independently represents-((CH ₂ ) _y CH ₂ O)-, or-((CH ₂ ) _y CH (CH ₃ ) O)-, y each independently represents an integer of 0 to 10, and X each independently represents a (meth) acrylfluorenyl group, a hydrogen atom, or a carboxyl group. In the general formula (Z-4), the total number of (meth) acrylfluorenyl groups is three or four, m each independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40. In the general formula (Z-5), the total number of (meth) acrylfluorenyl groups is five or six, n each independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.

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

The compound represented by the general formula (Z-4) or the general formula (Z-5) may be used singly or in combination of two or more kinds. In particular, at least one of the six X's in the general formula (Z-5) is a propylene fluorenyl group, and the six X's in the general formula (Z-5) are all acryl fluorinyl groups. The state of a mixture of compounds which are hydrogen atoms is preferred. With such a structure, developability can be further improved.

The total content of the compound represented by the general formula (Z-4) or the general formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

The compound represented by the general formula (Z-4) or the general formula (Z-5) can be synthesized by a process known as a conventionally known process: through ring-opening addition reaction, ethylene oxide or propylene oxide is mixed with pentaerythritol Or a process of dipentaerythritol bonding; and, for example, a process of introducing a (meth) acrylfluorenyl group by reacting (meth) acrylfluorene chloride with a terminal hydroxyl group of a ring-opening skeleton. Each process is a well-known process, and those skilled in the art can easily synthesize compounds represented by the general formula (Z-4) or (Z-5).

Among the compounds represented by the general formula (Z-4) or the general formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative is more preferable. Specific examples include compounds represented by the following formulae (a) to (f). Among them, exemplary compounds (a), (b), (e), and (f) are preferred.

[Chemical Formula 12]

[Chemical Formula 13]

Examples of commercially available polymerizable compounds represented by the general formulae (Z-4) and (Z-5) include SR-, which is a four-functional acrylic ester having four ethylene oxide chains manufactured by Sartomer company Inc. 494. DPCA-60, a 6-functional acrylate with 6 pentyleneoxy chains, which is manufactured by Nippon Kayaku Co., Ltd., and TPA-330, a 3-functional acrylate with 3 isobutylene oxide chains, etc. .

Examples of the polymerizable compound include urethane acrylates described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. The urethane having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. Compounds are also preferred. Furthermore, it is also possible to have an amine structure and a thioether structure in the molecule by using those described in JP-A-63-277653, JP-A-63-260909, and JP-A-105238. The addition of a polymerizable compound results in a composition having a very high speed of light. Examples of commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd), and DPHA-40H (Manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by KYOEISHA CHEMICAL Co., LTD), etc.

In addition, the SP (solubility parameter) value of the polymerizable compound used in the present invention is preferably 9.50 or more, more preferably 10.40 or more, and even more preferably 10.60 or more. In this specification, the SP value is obtained by the Hoy method unless otherwise specified (HLHoy Journal of Painting, 1970, Vol. 42, 76-118). In addition, the SP value is shown by omitting the unit, but the unit is cal ^1/2 cm ^-3/2 .

In addition, from the viewpoint of reducing development residues, it is also preferable that the composition contains a polymerizable compound having a Cardo skeleton. As the polymerizable compound having a Cardo skeleton, a polymerizable compound having a 9,9-diarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.

Formula (Q3) [Chemical Formula 14]

In the general formula (Q3), Ar ¹¹ to Ar ¹⁴ each independently represent an aryl group including a benzene ring surrounded by a dotted line. X ¹ to X ⁴ each independently represent a substituent having a polymerizable group, and a carbon atom in the substituent may be substituted with a hetero atom. a and b each independently represent an integer of 1 to 5, and c and d each independently represent an integer of 0 to 4. R ¹ to R ⁴ each independently represent a substituent, e, f, g, and h each independently represent an integer of 0 or more, and the upper limits of e, f, g, and h are respectively from Ar ¹¹ to Ar ¹⁴ The number of substituents minus the value of a, b, c or d. Here, when Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group including a benzene ring surrounded by a dotted line as one of the fused rings, X ¹ to X ⁴ and R ¹ to R ⁴ may be independently substituted with The benzene ring surrounded by a dotted line may be replaced by a ring other than the benzene ring surrounded by a dotted line.

In the general formula (Q3), the aryl group represented by Ar ¹¹ to Ar ¹⁴ containing a benzene ring surrounded by a dotted line is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms ( For example, phenyl, naphthyl) is more preferred, and phenyl (limited to a benzene ring surrounded by a dotted line) is more preferred.

In the general formula (Q3), X ¹ to X ⁴ each independently represent a substituent having a polymerizable group, and a carbon atom in the substituent may be substituted with a hetero atom. The substituent having a polymerizable group represented by X ¹ to X ⁴ is not particularly limited, but an aliphatic group having a polymerizable group is preferred. The aliphatic group having a polymerizable group represented by X ¹ to X ⁴ is not particularly limited, but an alkylene group having 1 to 12 carbon atoms other than the polymerizable group is preferred, and the number of carbon atoms is 2 An alkylene group of -10 is more preferable, and an alkylene group of 2 to 5 carbons is more preferable. In the aliphatic group having a polymerizable group represented by X ¹ to X ⁴ , when the aliphatic group is substituted with a hetero atom, it is substituted with -NR- (R is a substituent), an oxygen atom, or a sulfur atom. Jia, the aliphatic group of non-adjacent -CH ₂ - is substituted with an oxygen atom or a sulfur atom is more preferably the aliphatic group of non-adjacent -CH ₂ - is substituted with an oxygen atom is further preferred. With X ¹ ~ X ⁴ represents an aliphatic group of the polymerizable group at the 1 to 2 hetero atoms is substituted are preferred, substituted heteroatom is more preferably 1, and Ar ¹¹ ~ Ar ¹⁴ is represented to include It is further preferred that the aryl group of the benzene ring surrounded by a dashed line is substituted with a hetero atom next to it. As the polymerizable group contained in the aliphatic group having a polymerizable group represented by X ¹ to X ⁴ , a polymerizable group capable of radical polymerization or cationic polymerization (hereinafter, also referred to as a radical polymerizable property, respectively) And a cationic polymerizable group) are preferred. As the radically polymerizable group, a generally known radically polymerizable group can be used, and a preferable one includes a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization, and specifically, Examples include vinyl, (meth) acryloxy, and the like. Among them, (meth) acrylic fluorenyloxy is more preferable, and propylene fluorenyloxy is more preferable. As the cationically polymerizable group, generally known cationically polymerizable groups can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, and a spiro Cyclic orthoester groups and vinyloxy groups. Among them, an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferable. It is preferable that the polymerizable group included in the substituents included in Ar ¹ to Ar ⁴ is a radical polymerizable group. Two or more of Ar ¹ to Ar ⁴ include a substituent having a polymerizable group, two to four of Ar ¹ to Ar ⁴ include a substituent having a polymerizable group, and Ar ¹ to Ar ⁴ More preferably, 2 or 3 of the substituents having a polymerizable group are included, and 2 of Ar ¹ to Ar ⁴ further include a substituent of a polymerizable group. When Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group including a benzene ring surrounded by a dotted line as one of the fused rings, X ¹ to X ⁴ may be independently replaced by a benzene ring surrounded by a dotted line, or may be substituted. It is a ring other than a benzene ring surrounded by a dotted line.

In the above general formula (Q3), a and b each independently represent an integer of 1 to 5, 1 or 2 is more preferred, and a and b are both more preferably 1. In the above general formula (Q3), c and d each independently represent an integer of 0 to 5, 0 or 1 is more preferable, and both c and d are more preferably 0.

In the general formula (Q3), R ¹ to R ⁴ each independently represent a substituent. The substituents represented by R ¹ to R ⁴ are not particularly limited, and examples thereof include a halogen atom, a halogenated alkyl group, an alkyl group, an alkenyl group, a fluorenyl group, a hydroxyl group, a hydroxyalkyl group, an alkoxy group, and an aromatic group. Group, heteroaryl group and alicyclic group. The substituent represented by R ¹ to R ⁴ is preferably an alkyl group, an alkoxy group, or an aryl group, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group is more preferable. Of these, methyl, methoxy or phenyl is further preferred. In the general formula (Q3), when Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group including a benzene ring surrounded by a dotted line as one of the fused rings, R ¹ to R ⁴ may be independently substituted by dotted lines. The surrounding benzene ring may be replaced by a ring other than the benzene ring surrounded by a dotted line.

In the general formula (Q3), e, f, g, and h each independently represent an integer of 0 or more, and the upper limits of e, f, g, and h are the numbers of substituents that can be included from Ar ¹¹ to Ar ¹⁴ respectively. Subtract the value of a, b, c, or d. e, f, g, and h are each independently 0 to 8 is preferable, 0 to 2 is more preferable, and 0 is further preferable. When Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group including a benzene ring surrounded by a dotted line as one of the fused rings, e, f, g, and h are preferably 0 or 1, and 0 is more preferable.

Examples of the compound represented by the formula (Q3) include 9,9'-di [4- (2-propenyloxyethoxy) phenyl] fluorene and the like. As the polymerizable compound having a 9,9-diarylfluorene skeleton, the compounds described in Japanese Patent Application Laid-Open No. 2010-254732 can also be preferably used.

When the composition of the present invention contains a polymerizable compound, the content of the polymerizable compound is preferably from 0.1 to 40% by mass based on the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, preferably 30% by mass or less, and more preferably 20% by mass or less. The polymerizable compound may be used alone or in combination of two or more. When two or more kinds are used, it is preferable that the total measurement falls within the above range.

<Polymerization initiator> The composition of the present invention preferably has a polymerization initiator. The polymerization initiator is not particularly limited, and can be appropriately selected from known polymerization initiators. For example, those having a photosensitivity (so-called photopolymerization initiator) are preferred. When the composition of the present invention contains a photopolymerization initiator and the above-mentioned polymerizable compound in addition to the titanium nitride particles, it is hardened by irradiation with active light or radiation, so it is sometimes called a "photosensitive composition" . The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have sensitivity from the ultraviolet region to visible light. In addition, the polymerization initiator may be an active agent that has some effect with a photo-excited photosensitizer and generates active radicals, or may be an initiator that initiates cationic polymerization depending on the type of monomer. In addition, the photopolymerization initiator preferably contains at least one compound having a light absorption coefficient of at least about 50 moles in a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm.).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton and those having an oxadiazole skeleton), fluorenylphosphine compounds such as fluorenylphosphine oxide, hexaarylbisimidazole, Oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenone. Examples of the halogenated hydrocarbon compound having a triazine skeleton include a compound described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1384492, and Japanese special Compounds described in Japanese Patent Publication No. 53-133428, compounds described in German Patent No. 3337024, compounds based on J. Org. Chem. Of FC Schaefer, etc .; compounds described in 29, 1527 (1964), Japanese Patent Application Laid-Open No. 62-58241 The compounds described in the gazette, the compounds described in Japanese Unexamined Patent Publication No. 5-281728, the compounds described in Japanese Unexamined Patent Publication No. 5-34920, and the compounds described in the specification of US Patent No. 4212976.

From the viewpoint of exposure sensitivity, it is selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, a fluorenylphosphine compound, a phosphine oxide compound, Metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes, and Compounds in the group consisting of a salt, a halomethyloxadiazole compound, and a 3-aryl substituted coumarin compound are preferred.

Trihalomethyltriazine compounds, α-aminoketone compounds, fluorenylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzophenone compounds, and acetophenone compounds are further Preferably, at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-amino ketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is particularly preferred.

In particular, when a light-shielding film for a solid-state imaging element is produced using the composition of the present invention, it is necessary to form a fine pattern in a sharp shape, and it is therefore important to develop it without residue in an unexposed portion together with hardenability. From such a viewpoint, it is particularly preferable to use an oxime compound as a photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging element, step exposure is used for hardening exposure, but the exposure machine may be damaged by halogen, and it is necessary to suppress the addition amount of the photopolymerization initiator to be low. Taking these aspects into consideration, it is particularly preferable to use an oxime compound as a photopolymerization initiator when forming a fine pattern such as a solid-state imaging element. In addition, by using an oxime compound, color transfer properties can be optimized. As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of Japanese Patent Application Laid-Open No. 2013-29760 can be referred to, and the contents are incorporated into the specification of the present application.

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

Examples of the photopolymerization initiator include an oxime compound. In particular, the oxime-based initiator is preferable because it has high sensitivity and high polymerization efficiency, and can be hardened regardless of the color material concentration. It is easy to design the color material concentration to be high. As specific examples of the oxime compound, a compound described in JP 2001-233842, a compound described in JP 2000-80068, and a compound described in JP 2006-342166 can be used. As the oxime compound that can be preferably used in the present invention, for example, 3-benzyloxyiminobutane-2-one and 3-ethoxyiminobutane-2-one can be mentioned. Ketone, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane- 1-keto, 2-benzyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxy Carbonyloxyimino-1-phenylpropane-1-one and the like. In addition, JCSPerkin II (1979) pp.1653-1660), JCSPerkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, Japan Compounds described in JP-A-2000-66385, JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166. Among commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronics New Material Co., Ltd.), Adeka Arkls NCI-831, and Adeka Arkls NCI-930 (manufactured by ADEKA CORPORATION) can also be used. In addition, N-1919 (manufactured by ADEKA CORPORATION) can be used.

In addition, as the oxime compound other than the above, U.S. Patent No. 7,626,957 may be used as described in Japanese Patent Publication No. 2009-519904, in which an oxime is linked to the N-position of carbazole, and a heterosubstituent is introduced into a diphenyl ketone. Compounds described in Japanese Patent Publication No. 2010-15025 and US Patent Publication No. 2009-292039, in which a nitro group is introduced into a pigment, ketoxime compounds described in International Patent Publication No. 2009-131189, Compounds described in U.S. Patent No. 7,565,910, which contains a triazine skeleton and an oxime skeleton in the same molecule, and compounds described in Japanese Patent Application Laid-Open No. 2009-221114, which have a maximum absorption at 405 nm and have good sensitivity to a g-ray light source. For example, paragraphs 0274 to 0275 of Japanese Patent Application Laid-Open No. 2013-29760 can be referred to preferably, and the contents are incorporated into the present specification. Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferred. The N-O bond of the oxime may be the oxime compound of the (E) form, the oxime compound of the (Z) form, or a mixture of the (E) form and the (Z) form.

[Chemical Formula 15]

In the general 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 the general formula (OX-1), a monovalent non-metal atomic group is preferred. Examples of the monovalent nonmetal atomic group include an alkyl group, an aryl group, a fluorenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. The substituent may be further substituted with another substituent. Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, a fluorenyloxy group, a fluorenyl group, an alkyl group, and an aryl group. As the monovalent substituent represented by B in the general formula (OX-1), an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group is preferred. These groups may have one or more substituents. Examples of the substituent include the aforementioned substituents. As the divalent organic group represented by A in the general 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 one or more substituents. Examples of the substituent include the aforementioned substituents.

In the present invention, as the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include compounds described in Japanese Patent Laid-Open No. 2010-262028, compounds 24, 36-40 of Japanese Patent Laid-Open No. 2014-500852, and Japanese Patent Laid-Open No. 2013-164471. Compound (C-3) and the like described in the Gazette. This content is incorporated into this specification.

In the present invention, as the photopolymerization initiator, a compound represented by the following general formula (1) or (2) can also be used.

[Chemical Formula 16]

In formula (1), R ¹ and R ² each 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 a carbon number An aralkyl group of 7 to 30. When R ¹ and R ² are phenyl groups, the phenyl groups can be bonded to each other to form a fluorenyl group. R ³ and R ⁴ each independently represent a hydrogen atom and an alkyl group having 1 to 20 carbon atoms. An aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a single 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 A hydroxyl group, R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a mono A bond or a carbonyl group, a represents an integer of 0 to 4.

In the above formula (1) and formula (2), it is preferable that R ¹ and R ² are each independently methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl. R ³ is preferably methyl, ethyl, phenyl, tolyl or xylyl. R ⁴ is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R ⁵ is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably a single bond. Specific examples of the compounds represented by the formulas (1) and (2) include, for example, compounds described in paragraphs 0076 to 079 of Japanese Patent Application Laid-Open No. 2014-137466. This content is incorporated into this specification.

Specific examples of the oxime compound that can be preferably used in the present invention are shown below, but the present invention is not limited to these.

[Chemical Formula 17]

In the present invention, as the photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in WO2015 / 036910.

In addition, the commercially available polymerization initiator is not particularly limited, and examples include IRGACURE OXE 01 (1.2-octanedione, 1- [4- (phenylthio)-, 2- ( O-benzidine oxime)]), IRGACURE OXE 02 (ethyl ketone, 1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl]-, 1 -(O-acetamoxime)), 2- (acetamyloxyiminomethyl) thioxan-9-one, O-fluorimoxime-based compounds (for example, ADEKAOPTOMER N-1919, Adeka Arkls, manufactured by ADEKA CORPORATION) NCI-831), Adeka ArklsNCI-930, IRGACURE-OXE03, IRGACURE-OXE04, etc., which are incorporated into this specification.

The oxime compounds are preferably those having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, and those having a maximum absorption wavelength in a wavelength region of 360 nm to 480 nm are more preferred, and those having higher absorbances at 365 nm and 405 nm are particularly preferred. Among the oxime compounds, the Mohr absorption coefficient at 365 nm or 405 nm is more preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and even more preferably 5,000 to 200,000 from the viewpoint of sensitivity. The Molar absorption coefficient of the compound can be measured by a known method, for example, using a UV-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian Corporation) and an ethyl acetate solvent at a concentration of 0.01 g / L. The photopolymerization initiator used in the present invention can be used in combination of two or more kinds as necessary.

When the composition of the present invention contains a polymerization initiator, the content of the polymerization initiator relative to the total solid content in the composition is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and 1 to 10% by mass. % Is further preferred. The composition of the present invention may contain only one kind of polymerization initiator, or may contain two or more kinds. When two or more kinds are included, it is preferable that the total measurement falls within the above range.

<Solvent> The composition of the present invention preferably contains a solvent, and more preferably contains an organic solvent. Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethylene, 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 ether acetate, ethylene glycol monoisopropyl Ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxyethoxyethanol, 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, ethyl 3-ethoxypropionate (Ethyl 3-ethoxypropionate), 3-methoxypropyl acetate, N, N-dimethylformamide, dimethylmethylene, γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and the like are not limited thereto.

The composition of the present invention may contain one type of organic solvent, or may contain two or more types of organic solvents. However, from the viewpoint that the particle size variation of the titanium nitride-containing particles can be suppressed when the composition of the present invention is adjusted, it contains two types. Above organic solvents. When two or more organic solvents are contained, it is selected from the group consisting of the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethylene glycol. Methyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol mono A mixed solution of two or more types of methyl ether, ethyl 3-ethoxypropionate, and propylene glycol monomethyl ether acetate is particularly preferred.

When the composition of the present invention contains an organic solvent, the content of the organic solvent is preferably 10 to 90% by mass, and more preferably 60 to 90% by mass relative to the total mass of the composition. When two or more kinds of organic solvents are contained, the total amount thereof is preferably in the above range.

<Water> The composition of the present invention may contain water. Water may be intentionally added, or may be inevitably contained in the composition by adding each component contained in the composition of the present invention. The content of water is more preferably 0.1 to 1% by mass, more preferably 0.1 to 0.8% by mass, and still more preferably 0.1 to 0.4% by mass. When the content of water is within the above range, the pattern formation property (resolution) when the cured film is produced is excellent, and the electrode material is also excellent in corrosion resistance. In addition, by setting the content of water to 0.1 to 1% by mass based on the total mass of the composition, the amount of particles in the composition can be further reduced, and the viscosity of the composition over time can be more excellent.

<Other components> The composition of this invention may contain other components other than the above-mentioned components. Hereinafter, each component is demonstrated in detail.

(Silane coupling agent) A silane coupling agent refers to a compound having a hydrolyzable group and other functional groups in the molecule. A hydrolyzable group such as an alkoxy group is bonded to a silicon atom. A hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond through a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, a fluorenyloxy group, and an alkenyloxy group. When the hydrolyzable group has a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. An alkoxy group having 4 or less carbon atoms or an alkenyl group having 4 or less carbon atoms is particularly preferred. In addition, in order to improve the adhesion between the substrate and the cured film, it is preferable that the silane coupling agent does not include fluorine atoms and silicon atoms (except for silicon atoms bonded by hydrolyzable groups), and does not include fluorine atoms and silicon. Atoms (except for silicon atoms bonded to hydrolyzable groups), alkylene groups substituted by silicon atoms, linear alkyl groups having 8 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms are preferred .

The silane coupling agent preferably has a group represented by the following formula (Z). * Indicates the bonding position. Formula (Z) *-Si- (R _Z1 ) _{3 In} formula (Z), R _Z1 represents a hydrolyzable group, and its definition is as described above.

It is preferred that the silane coupling agent has one or more hardenable functional groups selected from the group consisting of (meth) acrylic fluorenyloxy, epoxy, and oxetanyl. The hardening functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom through a linking group. Moreover, as a preferable aspect of the curable functional group contained in the said silane coupling agent, a radical polymerizable group is mentioned.

The molecular weight of the silane coupling agent is not particularly limited. From the viewpoint of operability, there are many cases of 100 to 1,000. From the viewpoint of more excellent effects of the present invention, 270 or more is preferable, and 270 to 1,000 is more preferable.

One of the preferable aspects of the silane coupling agent includes a silane coupling agent X represented by the formula (W). The formula (W) R _Z2 -Lz-Si- (R _Z1 ) ₃ R _z1 represents a hydrolyzable group, and is defined as described above. R _z2 represents a hardenable functional group, as defined above, and the preferred range is also as described above. Lz represents a single bond or a divalent linking group. When Lz represents a divalent linking group, examples of the divalent linking group include a halogen atom-substituted alkylene group, a halogen atom-substituted alkylene group, -NR ^12- , -CONR ^12- , -CO- , -CO _2- , SO ₂ NR ^12- , -O-, -S-, -SO ₂ -and combinations thereof. Among them, at least one selected from the group consisting of a substituted alkyl group having a halogen atom of 2 to 10 carbon atoms and a substituted alkyl group having a halogen atom of 6 to 12 carbon atoms, or including these groups And at least one group selected from the group consisting of -NR ^12- , -CONR ^12- , -CO-, -CO _2- , SO ₂ NR ^12- , -O-, -S-, and SO _2- The combination of the groups is preferably a group including an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms, -CO _2- , -O-, -CO-, -CONR ¹² -or these groups. The combination group is more preferable. Here, the above R ¹² represents a hydrogen atom or a methyl group.

Examples of the silane coupling agent X include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name: KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.), N -β-aminoethyl-γ-aminopropyl-trimethoxysilane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-tri Ethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-trimethoxysilane (trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-Aminopropyl-triethoxysilane (Shin-Etsu Chemical Co., Ltd. product name KBE-903), 3-Methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co. , Ltd. (trade name: KBM-503), Glycidoxyoctyltrimethoxysilane (trade name, KBM-4803, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

Other preferable aspects of the silane coupling agent include a silane coupling agent Y having at least a silicon atom, a nitrogen atom, a hardenable functional group in the molecule, and a hydrolyzable group bonded to the silicon atom. The silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. These may be the same atom or substituent, or may be different. Examples of the bondable atom and substituent include a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, and an amine group which may be substituted by an alkyl group and / or an aryl group. , Silyl, alkoxy groups having 1 to 20 carbon atoms, and aryloxy groups. These substituents may be further substituted by silyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, thioalkoxy, amine groups which may be substituted with alkyl and / or aryl, halogen atoms, Sulfonamido, alkoxycarbonyl, amido, urea, ammonium, alkylammonium, carboxyl or its salt, sulfo or its salt, and the like. In addition, at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above. The silane coupling agent Y may contain a group represented by the above formula (Z).

The silane coupling agent Y has at least one nitrogen atom in the molecule, and it is preferable that the nitrogen atom exists in the form of a secondary amine group or a tertiary amine group, that is, the nitrogen atom has at least one organic group as a substituent. Mission is better. The structure of the amine group may exist in the molecule in the form of a partial structure of a nitrogen-containing heterocyclic ring, or may exist as a substituted amine group such as aniline. Among them, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent, and examples of the substituent that can be introduced include silyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, thioalkoxy, amine, and halogen atoms. , Sulfonylamino, alkoxycarbonyl, carbonyloxy, fluorenylamino, urea, alkoxyammonium, alkylammonyl, carboxyl or its salt, sulfo, and the like. In addition, the nitrogen atom is preferably bonded to the curable functional group via an arbitrary organic linking group. Preferred examples of the organic linking group include substituents which can be introduced into the nitrogen atom and an organic group bonded thereto.

The definition of the hardenable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above. The silane coupling agent Y may have at least one hardenable functional group in one molecule, but may also take the form of two or more hardenable functional groups. From the viewpoint of sensitivity and stability, it has 2 -20 hardenable functional groups are preferred, 4-15 are more preferred, and 6-10 hardenable functional groups in the molecule are most preferred.

The molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, and examples thereof include the above range (270 or more is preferred).

The content of the silane coupling agent in the composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and even more preferably 1.0 to 6% by mass, relative to the total solids in the composition. .

The composition of the present invention may contain one kind of silane coupling agent alone, or may contain two or more kinds. When the composition contains two or more kinds of silane coupling agents, the total amount may be within the above range.

(Ultraviolet Absorbent) The composition of the present invention may contain an ultraviolet absorbent. Thereby, the pattern shape can be made more excellent (fine). As the ultraviolet absorber, a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based ultraviolet absorber can be used. As specific examples of these, compounds of paragraphs 0137 to 0142 of Japanese Patent Application Laid-Open No. 2012-068418 (corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) can be used, and these contents can be incorporated into this specification. In addition, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by DAITO CHEMICAL CO., LTD., Trade name: UV-503) and the like can also be preferably used. Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of Japanese Patent Application Laid-Open No. 2012-32556. The composition of the present invention may or may not include an ultraviolet absorber, but when included, the content of the ultraviolet absorber is preferably 0.001 to 15% by mass, and more preferably 0.01 to 10% by mass relative to the total solid content of the composition. , 0.1 to 5 mass% is more preferable.

(Surfactant) The composition of the present invention may contain various surfactants from the viewpoint of further improving the coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

By containing a fluorine-based surfactant in the composition of the present invention, the liquid characteristics (especially, flowability) when preparing a coating liquid are further improved, and the uniformity of coating thickness and liquid saving can be further improved. That is, when a coating liquid containing a composition containing a fluorine-based surfactant is used to form a film, the interfacial tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is improved. The applicability to the surface to be coated is improved. Therefore, it is possible to form a film having a uniform thickness with less variation in thickness.

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. A fluorine-based surfactant having a fluorine content within this range is effective in terms of the uniformity of the thickness of the coating film and the liquid saving property, and the solubility in the composition is also good.

Examples of the fluorine-based surfactant include Megaface F171, Megaface F172, Megaface F173, Megaface F176, Megaface F177, Megaface F141, Megaface F142, Megaface F143, Megaface F144, Megaface R30, Megaface F437, Megaface F475, Megaface F479 , Megaface F482, Megaface F554, Megaface F780, RS-72-K (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 SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above, manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA SOLUTIONS INC.). As the fluorine-based surfactant, a compound described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used. As the fluorine-based surfactant, a block polymer can also be used. As a specific example, for example, a compound described in Japanese Patent Application Laid-Open No. 2011-89090 can be mentioned. The fluorine-based surfactant can also preferably be used as a fluorine-containing polymer compound including a repeating unit derived from a (meth) acrylate compound having a fluorine atom and derived from a compound having 2 or more (5 or more is preferred) ) Repeating units of (meth) acrylate compounds of alkoxy (vinyloxy and propyleneoxy are preferred). The following compounds are also exemplified as fluorine-based surfactants used in the present invention.

[Chemical Formula 18]

The weight average molecular weight of the compound is preferably 3,000 to 50,000, and is, for example, 14,000. In addition, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can be used as a fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Laid-Open No. 2010-164965, such as Megaface RS-101, RS-102, RS-718K, and RS-72 manufactured by DIC Corporation. -K and so on.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates (for example, glycerol propoxylate) , Glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylen Glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, TETRONIC 304, 701, 704, 901, 904, 150R1, SOLSPERSE 20000 (manufactured by The Lubrizol Corporatin), etc. In addition, NCW-101, NCW-1001, and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

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

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co Ltd) and Sandetto BL (manufactured by Sanyo Chemical Industries, Ltd.).

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

The surfactant may be used singly or in combination of two or more kinds. The content of the surfactant is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass based on the total solid content of the composition of the present invention.

In addition to the above components, the following components may be further added to the composition of the present invention. Examples include sensitizers, co-sensitizers, cross-linking agents, hardening accelerators, fillers, thermal hardening accelerators, polymerization inhibitors, plasticizers, diluents, and sensitizers. Need to add adhesion promoters and other additives to the substrate surface (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension regulators, and Chain transfer agents, etc.) and other well-known additives. These components can be referred to, for example, Japanese Patent Application Publication No. 2012-003225, paragraph numbers 0183 to 0228 (corresponding to US Patent Application Publication No. 2013/0034812, <0237> to <0309>), Japanese Patent Application Laid-Open No. 2008-250074 The descriptions of paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, and paragraph numbers 0159 to 0184 of Japanese Patent Application Laid-Open No. 2013-195480 are incorporated in this specification.

(Colorant) The composition of the present invention can use a coloring agent (hereinafter, simply referred to as a “coloring agent”) other than the above-mentioned titanium nitride-containing particles. The colorant is used, for example, to adjust the chromaticity of the composition, and a part of titanium nitride can be replaced with the colorant within a range in which the OD value does not decrease. Examples of such coloring agents include pigments (organic pigments and inorganic pigments of black organic pigments and colored organic pigments) and dyes.

As the colorant, a pigment is preferably used. This makes it easy to produce a film having a small standard deviation in transmittance in a wavelength range of 400 to 700 nm. In particular, when a black pigment (a black organic pigment and a black inorganic pigment) is used as the pigment, it is easy to produce a film having a standard deviation of the transmittance in the above range of 10% or less.

((Pigment)) Examples of the pigment include various conventionally known pigments. As a color organic pigment, the following are mentioned. However, the present invention is not limited to these. Dye Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35 : 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94 , 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137 , 138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176 , 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc., CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38 , 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc., CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10 , 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53 : 1,57: 1,60: 1,63: 1,66,67,81: 1,81: 2,81 : 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179 , 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc., CI Pigment Green 7, 10, 36, 37, 58, 59, etc. CI Pigment Purple 1, 19, 23, 27, 32, 37, 42 and other CI Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15 : 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc.

In addition, as the green pigment, a zinc halide phthalocyanine pigment having an average number of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms can be used. Specific examples include compounds described in International Publication No. 2015/118720. These organic pigments can be used alone or in combination in order to improve color purity.

As the black pigment, various known black pigments can be used. Examples thereof include carbon black and a black metal-containing organic pigment shown below. Examples of the black metal-containing organic pigment include metal oxidation containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. Materials, metal nitrides. These can be used alone, and can also be used as a mixture of two or more. In addition, a black pigment can be further combined with an inorganic pigment of another hue to produce a desired light-shielding property. Examples of specific inorganic pigments that can be used in combination include zinc white, lead white, zinc barium white, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, lead red, and oxide. Iron red, chrome yellow, zinc yellow (1 zinc yellow, 2 zinc yellow), ultramarine blue, Prussian blue (ferrous potassium ferrocyanide), zircon gray, ochre yellow, chrome titanium yellow, chrome green, peacock, Victoria Green, iron blue (unrelated to Prussian blue), vanadium zirconium blue, chrome tin red, manganese red, orange red, etc. In particular, in order to express light-shielding properties in a wide wavelength range from ultraviolet to infrared, not only these black pigments or other shades, but also a plurality of pigments may be used in combination.

The black pigment is preferably carbon black or titanium black, and titanium black is particularly preferred from the viewpoint of having light-shielding properties in a wide wavelength range from ultraviolet to infrared. Titanium black is black particles with titanium atoms. Low-order titanium oxide, titanium oxynitride, and the like are preferred. Although not particularly limited, as the titanium oxynitride, for example, International Publication No. 2008/123097, Japanese Patent Laid-Open No. 2009-58946, Japanese Patent Laid-Open No. 2010-14848, Japanese Patent Laid-Open No. 2010-97210, and Japanese Patent Laid-Open No. 2011-2274670 can be used. As the titanium oxynitride, a mixture of titanium oxynitride and titanium carbide such as Japanese Patent Application Laid-Open No. 2010-95716 can be used. In order to improve dispersibility, suppress cohesion, and the like, the surface of the titanium black particles can be modified as necessary. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, and zirconia, and can also be treated with a hydrophobic substance as shown in Japanese Patent Application Laid-Open No. 2007-302836. In order to adjust the dispersibility and colorability, titanium black may contain one kind of composite oxides of Cu, Fe, Mn, V, Ni, etc., black pigments such as cobalt oxide, iron oxide, and carbon black, or a combination of two or more kinds. contain.

As a method for producing titanium black, there is a method of heating and reducing a mixture of titanium dioxide and metallic titanium under a reducing atmosphere (Japanese Patent Application Laid-Open No. 49-5432), and using tetrachloride under a reducing atmosphere containing hydrogen. Method for reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium (Japanese Patent Application Laid-Open No. 57-205322), and method for high-temperature reduction of titanium dioxide or titanium hydroxide in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069) Gazette, Japanese Patent Laid-Open No. 61-201610), a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide, and performing high-temperature reduction in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), and the like. However, the present invention is not limited to these.

The specific surface area of titanium black is not particularly limited, but by BET (Brunauer, Emmett, Teller) method for the determination of the value of 5m ² / g or more 150m ² / g or less is preferred, 20m ² / g or more 120m ² / g or less For the better. Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade names: manufactured by Mitsubishi Materials Corporation), and Tilack (Tilack). D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.

The average primary particle diameter of the black pigment is preferably 5 nm or more, and more preferably 10 nm or more. From the same viewpoint, the upper limit is preferably 10 μm or less, more preferably 1 μm or less, and even more preferably 100 nm or less. The average primary particle diameter of the black pigment is a value measured by the following method. It is assumed that the mixed solution containing a black pigment was diluted 80 times with propylene glycol monomethyl ether acetate, and the obtained diluted solution was measured by a dynamic light scattering method. In this measurement, the average particle diameter obtained by using Microtrac (trade name) UPA-EX150 manufactured by NIKKISO CO., LTD.

Furthermore, it is also preferable to use a dispersion containing titanium black and Si atoms as the titanium black. In this form, titanium black is contained in the composition as a dispersion. The content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersion is preferably 0.05 or more in mass conversion, and 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is further more preferable. However, the above-mentioned to-be-dispersed body includes both a state in which titanium black is a primary particle and a state in which an aggregate (a secondary particle) is in a state. In order to change the Si / Ti of the dispersion (for example, 0.05 or more), the following means can be adopted. First, a dispersion is obtained by dispersing titanium oxide and silicon dioxide particles with a disperser, and the dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C), thereby obtaining titanium black particles as a main component. It contains a dispersion of Si and Ti. The reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia. Examples of the titanium oxide include TTO-51N (trade name: manufactured by Ishihara Sangyo Kaisha, Ltd.). Titanium oxide produced by the plasma method has a smaller particle size than commercially available titanium oxide particles, so it can be preferably used (see the Japanese Society of Metals Journal Vol. 63 No. 1 (1999) 74-81). Examples of commercially available products of silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, and 380 (trade names: manufactured by Evonik Japan Co., Ltd.). A dispersant can also be used in the dispersion of titanium oxide and silicon dioxide particles. Examples of the dispersant include those described above in the column of dispersant. The above dispersion can be performed in a solvent. Examples of the solvent include water and organic solvents. Examples of the organic solvents mentioned above can be mentioned. The titanium black whose Si / Ti is adjusted to, for example, 0.05 or more can be produced, for example, by the methods described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of Japanese Patent Application Laid-Open No. 2008-266045.

The content ratio (Si / Ti) of the Si atom and the Ti atom in the dispersion including titanium black and Si atoms is adjusted to an appropriate range (for example, 0.05 or more), and the composition is formed using the composition including the dispersion In the case of the light-shielding film, residues originating from the composition outside the region where the light-shielding film is formed are reduced. In addition, the residue system includes components derived from components such as titanium black particles and resin components. Although the reason for the reduction of the residue is not clear, it is inferred as follows: as described above, the dispersion has a tendency to become smaller in particle size (for example, the particle diameter is 30 nm or less), and the component of the dispersion containing Si atoms increases, This film has a reduced adsorption to the substrate as a whole, which contributes to improving the development and removal properties of the unhardened composition (especially, titanium black) when the light-shielding film is formed. In addition, titanium black has excellent light-shielding properties against light in a wide wavelength range from ultraviolet light to infrared light. Therefore, the above-mentioned dispersion containing titanium black and Si atoms is used (Si / Ti is 0.05 or more in mass conversion) It is preferred that the light-shielding film formed to exhibit excellent light-shielding properties. The content ratio (Si / Ti) of the Si atom and the Ti atom in the dispersion can be, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of Japanese Patent Application Laid-Open No. 2013-249417. Determination. In addition, when the dispersion contained in the light-shielding film obtained by curing the composition is judged whether the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is 0.05 or more, Japanese Patent Application Laid-Open No. 2013 is used. Method (2) described in paragraph 0035 of Japanese Patent Publication No. -249417.

Among the dispersions containing titanium black and Si atoms, titanium black can be used. In addition, in this dispersion, in order to adjust dispersibility, colorability, and the like, together with titanium black, one or two or more kinds of composite oxides containing Cu, Fe, Mn, V, Ni, etc., cobalt oxide, Black pigments such as iron oxide, carbon black, nigrosine, etc., are used as dispersions. In this case, it is preferable that the dispersion containing titanium black accounts for 50% by mass or more of all the dispersions. In addition, in this dispersion, in order to adjust the light-shielding properties and the like, other colorants (organic pigments, dyes, etc.) may be used together with titanium black, as long as the effect of the present invention is not impaired. The materials used when introducing Si atoms into the dispersion will be described below. When introducing Si atoms into the dispersion, a Si-containing substance such as silicon dioxide may be used. Examples of usable silica include precipitated silica, fumed silica, colloidal silica, and synthetic silica, and these can be appropriately selected and used. In addition, if the particle diameter of the silicon dioxide particles is smaller than the film thickness when the light-shielding film is formed, the light-shielding property is more excellent. Therefore, it is preferable to use particulate silicon dioxide as the silicon dioxide particles. In addition, as an example of the fine particle type silicon dioxide, for example, the silicon dioxide described in paragraph 0039 of Japanese Patent Application Laid-Open No. 2013-249417 can be cited, and these contents are incorporated herein.

In addition, as the pigment, a tungsten compound and a metal boride can also be used. Tungsten compounds and metal borides have higher absorption relative to infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, higher light-shielding properties (shielding properties) relative to infrared rays), and infrared rays having lower absorption relative to visible light. Shielding material. Therefore, the photosensitive composition of the present invention can form a pattern having a high light-shielding property in the infrared region and a high light-transmitting property in the visible light region by containing a tungsten compound and / or a metal boride. In addition, tungsten compounds and metal borides absorb light with a shorter wavelength than light in the visible region used in the exposure of high-pressure mercury lamps, KrF, and ArF used for image formation.

Examples of the tungsten compound include tungsten oxide-based compounds, tungsten boride-based compounds, tungsten sulfide-based compounds, and the like, and tungsten oxide-based compounds represented by the following general formula (compositional formula) (I) are preferred. M _x W _y O _z (I) M represents metal, W represents tungsten, and O represents oxygen. 0.001≤x / y≤1.1 2.2≤z / y≤3.0

Examples of the metal of M include alkali metals, alkaline earth metals, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, and Cd. Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, etc., alkali metals are preferred. The metal of M may be one kind, or two or more kinds.

M is preferably an alkali metal, Rb or Cs is more preferred, and Cs is further preferred.

When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, it is possible to reliably avoid generation of an impurity phase in the tungsten compound. When z / y is 2.2 or more, the chemical stability of the material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.

Specific examples of the tungsten oxide-based compound represented by the general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _3, and the like, Cs _0.33 WO ₃ or Rb _0.33 WO. ₃ is more preferable, and Cs _0.33 WO ₃ is more preferable.

The tungsten compound is preferably fine particles. The average primary particle diameter of the tungsten particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. With the average primary particle diameter in this range, tungsten particles are difficult to shield visible light due to light scattering, and therefore, the light transmittance in the visible light region can be reliably achieved. From the standpoint of avoiding light scattering, the smaller the average primary particle diameter is, the better, but for reasons such as ease of handling during production, the average primary particle diameter of the tungsten particles is usually 1 nm or more.

In addition, two or more tungsten compounds can be used.

The tungsten compound can be obtained as a commercial product. When the tungsten compound is, for example, a tungsten oxide-based compound, the tungsten oxide-based compound can be obtained by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (see Japanese Patent) No. 4096205). The tungsten oxide-based compound can also be obtained as a dispersion of tungsten particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

Examples of the metal boride include lanthanum boride (LaB ₆ ), praseodymium boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), Titanium boride (TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), One or more types of molybdenum boride (MoB ₂ , Mo ₂ B ₅ , MoB), tungsten boride (W ₂ B ₅ ), etc., and lanthanum boride (LaB ₆ ) is preferred.

It is preferable that the metal boride is a fine particle. The average primary particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and even more preferably 100 nm or less. When the average primary particle diameter is in this range, the metal boride fine particles are difficult to block visible light due to light scattering, so that the light transmittance in the visible light region can be achieved more reliably. From the standpoint of avoiding light scattering, the smaller the average primary particle diameter is, the better, but for reasons such as ease of handling during production, the average primary particle diameter of the metal boride fine particles is usually 1 nm or more.

In addition, two or more kinds of metal borides can be used.

The metal boride can be obtained as a commercial product, for example, it can also be obtained as a dispersion of metal boride fine particles such as KHF-07AH manufactured by Sumitomo Metal Mining Co., Ltd.

((Dye)) As the dye, for example, Japanese Patent Laid-Open No. 64-90403, Japanese Patent Laid-Open No. 64-91102, Japanese Patent Laid-Open No. 1-94301, Japanese Patent Laid-Open No. 6-11614, and Japanese Patent No. 6-11614 can be used. No. 2592207, U.S. Patent No. 4,850,001, U.S. Patent No. 5,667,920, U.S. Patent No. 5,505,950, U.S. Patent No. 5,667,920, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application No. 6-35183, Japanese Patent Application No. 6 The pigment disclosed in -51115, Japanese Unexamined Patent Publication No. 6-194828, and the like. When distinguished as a chemical structure, a pyrazole azo compound, a pyrrole methylene compound, an aniline azo compound, a triphenylmethane compound, an anthraquinone compound, a benzylidene compound, an oxonol compound, and pyridine can be used. Zolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazomethine compounds, and the like. As the dye, a pigment multimer can be used. Examples of the pigment multimer include compounds described in Japanese Patent Application Laid-Open No. 2011-213925 and Japanese Patent Application Laid-Open No. 2013-041097.

The composition of the present invention may contain an extender pigment in addition to the colorant, if necessary. Examples of such constitution pigments include barium sulfate, barium carbonate, calcium carbonate, silicon dioxide, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. These extender pigments can be used alone or in combination of two or more. The usage-amount of an extender pigment is 0-100 mass parts normally with respect to 100 mass parts of colorants, 5-50 mass parts is preferable, 10-40 mass parts is more preferable. In the present invention, the colorant and extender pigment can be used by modifying the surface of the polymer with the case.

The colorant may be used singly or in combination of two or more kinds. The colorant may contain colored organic pigments such as red, blue, yellow, green, and purple. When using a light-shielding pigment (specifically, containing titanium nitride particles) and a colored organic pigment, it is preferable to use 1 to 40% by mass of the colored organic pigment relative to the light-shielding pigment. From the viewpoint of adjusting color tone, red pigments and light-shielding pigments are preferred, and although not particularly limited, pigment red 254 is preferred as the red pigment. In addition, from the viewpoint of improving light-shielding properties, yellow pigments and light-shielding pigments are preferred. Although not particularly limited, pigment yellow 150 is preferred as a yellow pigment.

When the composition of the present invention contains a colorant, the content of the colorant is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and even more preferably 35 to 60% by mass relative to the total solid content of the composition. .

(Pigment Derivative) The composition of the present invention can contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the organic pigment is substituted by an acidic group, a basic group, or an iminomethyl phthalate. Examples of the organic pigment used to constitute the pigment derivative include dioxopyrrolopyrrole-based pigments, azo-based pigments, phthalocyanine-based pigments, anthraquinone-based pigments, quinacridone-based pigments, and dioxazine-based pigments. , Ringtone-based pigments, fluorene-based pigments, thioindigo-based pigments, isoindolinone-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, Shihlin-based pigments, metal complex-based pigments, and the like. In addition, as the acidic group of the pigment derivative, a sulfonic acid group, a carboxylic acid group, and a quaternary ammonium salt group thereof are preferred, a carboxylic acid group and a sulfonic acid group are further preferred, and a sulfonic acid group is particularly preferred. As the basic group of the pigment derivative, an amine group is preferred, and a tertiary amine group is particularly preferred. Specific examples of the pigment derivative include the following compounds. In addition, reference can be made to the descriptions in paragraphs 0162 to 0183 of Japanese Patent Application Laid-Open No. 2011-252065, which are incorporated into this specification.

[Chemical Formula 19]

When the composition of the present invention contains a pigment derivative, the content of the pigment derivative relative to the total mass of the colorant is preferably 1 to 30% by mass, and more preferably 3 to 20% by mass. The composition of the present invention may contain only one pigment derivative, or may contain two or more pigment derivatives. When two or more kinds are included, it is preferable that the total measurement falls within the above range.

<Method for preparing composition> The composition of the present invention can be prepared by mixing the above-mentioned various components by a known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsification device, a wet pulverizer, and a wet disperser). In order to remove foreign matter or reduce defects, it is preferable to filter the composition of the present invention with a filter. The filter can be used without particular limitation as long as it has been conventionally used for filtering purposes and the like. Examples include filters based on fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight), and the like. . Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred. The pore diameter of the filter is preferably about 0.1 to 7.0 μm, more preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and even more preferably 0.3 to 0.7 μm. By setting it as this range, it is possible to suppress filtration clogging of the pigment, and to reliably remove fine foreign matters such as impurities or aggregates contained in the pigment. When using filters, different filters can be combined. In this case, the filtration by the first filter may be performed only once, or may be performed twice or more. When two or more filtrations are performed by combining different filters, the pore diameter after the second filtration is preferably the same as or larger than the pore diameter of the first filtration. In addition, the first filters having different pore diameters 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, various filters provided by NIHON PALL LTD., Toyo Roshi Kaisha, Ltd., Nihon Entegris K.K. (formerly Mykrolis Corpration), or KITZ MICROFILTER CORPORATION can be selected. The second filter can be formed using the same material as that of the first filter. The pore diameter of the second filter is preferably about 0.2 to 10.0 μm, more preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm.

The solid content of the composition of the present invention is preferably 10 to 40% by mass, and more preferably 12 to 35% by mass. When the solid content of the composition is 10% by mass or more, the light-shielding property of the cured film is further improved. In addition, when the solid content of the composition is 40% by mass or less, the viscosity stability over time of the composition is further improved.

[Curable Film (Light-shielding Film)] The cured film of the present invention is obtained using the composition described above. The cured film preferably has a surface uneven structure. By doing so, the reflectance of the light-shielding film or the light-shielding layer having the light-shielding film can be reduced. The uneven structure may be one having a uneven structure on the surface of the light-shielding film itself, or another layer may be provided on the light-shielding film to provide the uneven structure. The shape of the surface uneven structure is not particularly limited, and the surface roughness is preferably in a range of 0.55 μm to 1.5 μm. The reflectance of the light-shielding film is preferably 5% or less, more preferably 3% or less, and even more preferably 2% or less. The method of making the surface uneven structure is not particularly limited, and it may be a method of containing an organic filler or an inorganic filler in a light-shielding film or other layers, or a lithography method using exposure development, or etching or sputtering, nanometer A method of roughening the surface of a light-shielding film or other layer by an imprint method or the like. Further, as a method of reducing the reflectance of the cured film, in addition to the above, a method of providing a low refractive index layer on a light-shielding film, or further providing a plurality of layers having different refractive indexes (for example, a high refractive index layer) ), Or a method for forming a low optical density layer and a high optical density layer described in, for example, Japanese Patent Application Laid-Open No. 2015-1654. The hardened film of this invention mainly contains the said titanium nitride containing particle. The cured film of the present invention is preferably used as a light-shielding film, and specifically, it is preferably used as a light-shielding film (frame light-shielding film) around an image sensor such as a CCD image sensor or a CMOS image sensor. Hereinafter, a case where a cured film is used as a light shielding film around an image sensor will be described as an example. When a cured film is used as a light-shielding film around an image sensor, a light-shielding film around the image sensor may be formed in a color filter. This is suitable for a CCD image sensor or a CMOS image sensor. Appearance. That is, the above-mentioned cured film can be formed in a region where a color filter is in contact with a frame region such as a CCD image sensor or a CMOS image sensor. The color filter having the light-shielding film around the image sensor of the present invention is formed using the above-mentioned composition (in particular, the above-mentioned photosensitive composition). An image sensor surrounding a light-shielding film obtained using the composition of the present invention is excellent in pattern-forming properties and electrode corrosion resistance.

When used as a light-shielding film around an image sensor, the thickness of the light-shielding film is not particularly limited. From the viewpoint of more effectively obtaining the effect of the present invention, the thickness of the film after drying is 0.2 μm or more and 50 μm or less. Preferably, it is more preferably 0.5 μm or more and 30 μm or less, and more preferably 0.7 μm or more and 20 μm or less. In addition, as the size (length of one side) of the light-shielding film, from the viewpoint of more effectively obtaining the effect of the present invention, 0.001 mm to 5 mm is preferable, 0.05 mm to 4 mm is more preferable, and 0.1 mm to 3.5 mm is more preferable. The following are further preferred.

<The manufacturing method of a cured film> Next, the manufacturing method of the cured film (light-shielding film) of this invention is not specifically limited, A well-known method can be employ | adopted. Hereinafter, as a representative example, a method for producing a patterned cured film will be described in detail.

The method for producing a patterned cured film according to the present invention includes a process of applying a composition of the present invention on a substrate to form a composition layer (coating film) (hereinafter, referred to as “composition layer formation as appropriate”). Process ".); A process of exposing the composition layer through a mask (hereinafter, appropriately referred to as" exposure process "); and a process of developing the composition layer after exposure to form a patterned cured film ( Hereinafter, it is appropriately abbreviated as "developing process.").

Specifically, the composition of the present invention is coated on a substrate directly or via another layer to form a composition layer (composition layer forming process), and exposure is performed through a predetermined mask pattern, so that only the composition irradiated with light The layer is partially cured (exposure process), and a patterned cured film including pixels is formed by developing with a developing solution (development process). Hereinafter, each process will be described.

(Composition Layer Formation Process) In the composition layer formation process, the composition of the present invention is applied on a substrate to form a composition layer (coating film).

As the substrate, for example, alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display devices, and photoelectric conversion element substrates for solid-state imaging elements such as those with a transparent conductive film attached thereto ( For example, a silicone substrate, etc.), a CCD (Charge Coupled Device) substrate, and a CMOS (Complementary Metal-Oxide Semiconductor) substrate. In addition, in order to improve adhesion to the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate, an undercoat layer may be provided on these substrates as needed.

As a coating method for applying the composition of the present invention to a substrate, various coatings such as a slit coating method, an inkjet method, a spin coating method, a cast coating method, a roll coating method, and a screen printing method can be applied. method.

When manufacturing a color filter with a light shielding film around the image sensor, the coating film thickness of the composition is preferably from 0.35 μm to 2.0 μm, and from 0.40 μm to 1.5 μm from the viewpoint of resolution and developability. The following is better.

The composition coated on the substrate is usually dried at a temperature of 70 ° C or higher and 110 ° C or lower, and is dried for about 2 minutes to 4 minutes. Thereby, a composition layer can be formed.

(Exposure Process) In the exposure process, the composition layer (coating film) formed in the composition layer forming process is exposed through a mask, and only a part of the coating film irradiated with light is hardened. It is preferable to perform exposure by irradiation with active light or radiation. In particular, ultraviolet rays such as g-rays, h-rays, and i-rays are preferably used, and a high-pressure mercury lamp is more preferable. The irradiation intensity is preferably 5 to 1500 mJ / cm ^{2, and more} preferably 10 to 1000 mJ / cm ² .

(Development process) The exposure process is followed by an alkali development process (development process), and the light-irradiated part in an exposure process is melt | dissolved in alkaline aqueous solution. Thereby, only the light-hardened portion (the portion of the coating film irradiated with light) remains. As the developing solution, when a color filter having a light shielding film around the image sensor is produced, an organic alkali developing solution that does not cause damage to the circuit of the substrate is preferred. The development temperature is usually 20 to 30 ° C, and the development time is 20 to 90 seconds.

Examples of the alkaline aqueous solution include an inorganic developer and an organic developer. Examples of the inorganic developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate, which are dissolved at a concentration of 0.001 to 10% by mass, and preferably 0.01 to 1% by mass alkaline aqueous solution. Examples of the organic developer include ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8- An organic basic compound such as diazabicyclo- [5.4.0] -7-undecene is dissolved into an alkaline aqueous solution having a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. To the alkaline aqueous solution, for example, an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant can be added. In addition, when using a developing solution containing such an alkaline aqueous solution, it is usually preferable to wash (rinse) with pure water after development.

As a development method, a spin-on immersion development method, a shower development method, etc. can be used, for example.

In addition, in the method for manufacturing a color filter having the cured film of the present invention, after the above-mentioned composition layer forming process, exposure process, and development process are performed, the formed by heating and / or exposure may be included as necessary. The hardened film undergoes a hardening process.

[Color filter, light-shielding film] The hardened film formed by using the composition of the present invention can be preferably used as a pixel black matrix of a color filter or a peripheral light-shielding film (frame light-shielding film) as described above or A light-shielding film suitable for various components in an image display device or a sensor module described later.

(Color filter) The color filter can be preferably used for solid-state imaging elements such as CCD (Charge Coupled Device) or CMOS (Complementary Metal Oxide Semiconductor), and is particularly suitable for high-resolution CCDs such as more than 1 million pixels or CMOS and so on. The color filter can be used, for example, by being disposed between a light receiving portion of each pixel constituting a CCD or CMOS and a micro lens for condensing light. In addition, the color filter may have a structure in which a hardened film of each color pixel is embedded in a space partitioned into a grid shape by a partition wall, for example. It is preferable that the partition wall has a low refractive index for each color pixel. Examples of the imaging element having such a structure include the devices described in Japanese Patent Application Laid-Open No. 2012-227478 and Japanese Patent Application Laid-Open No. 2014-179577. The shape of the color filter of the present invention is not particularly limited as long as it has the cured film. In the color filter, the cured film can be preferably used as, for example, a pixel black matrix of a color filter or a peripheral light-shielding film (frame light-shielding film) as described above.

(Light-shielding film) The light-shielding film can be formed in various components in an image display device or a sensor module (for example, an infrared light cut-off filter, a peripheral portion of a solid-state imaging element, a wafer-level lens peripheral portion, and a back surface of a solid-state imaging element Etc.) and so on. In addition, a light-shielding film may be formed on at least a part of the surface of the infrared-light-cut filter as the infrared-light-cut filter with a light-shielding film. The thickness of the light-shielding film is not particularly limited, but is preferably 0.2 to 25 μm, and more preferably 1.0 to 10 μm. The above thickness is an average thickness, and is a value obtained by measuring the thickness of any five points or more of the light-shielding film and arithmetically averaging the thicknesses. The reflectance of the light-shielding film is preferably 10% or less, more preferably 8% or less, even more preferably 6% or less, and even more preferably 4% or less. The reflectance of the light-shielding film is such that light having a wavelength of 400 to 700 nm is incident on the light-shielding film at an incident angle of 5 °, and the reflectance is measured by a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation.

[Solid-state imaging element] The solid-state imaging element of the present invention includes the above-mentioned cured film (color filter, light-shielding film, etc.). The structure of the solid-state imaging element of the present invention is not particularly limited as long as it has the above-mentioned cured film and functions as a solid-state imaging element, and examples thereof include the following structures.

The structure is as follows: a plurality of transfer electrodes including a photodiode, polycrystalline silicon, and the like are provided on a substrate to form a light-receiving area of a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.); The body and the transfer electrode are provided with a light-shielding film which is opened only to the light-receiving part of the photodiode, and the light-shielding film is provided with a device composed of silicon nitride or the like formed to cover the front surface of the light-shielding film and the light-receiving part of the photodiode. Film, which has a color filter on the device protection film. Furthermore, it may be a structure having a light-concentrating mechanism (for example, a micro lens, etc. below) under the color filter (close to one side of the substrate) on the device protective layer, or a light-condensing mechanism having a light-condensing mechanism on the color filter. Structure, etc. In addition, the color filter may have a structure in which a hardened film forming each color pixel is embedded in a space partitioned into a grid shape by a partition wall, for example. It is preferable that the partition wall has a low refractive index for each color pixel. Examples of the imaging device having such a structure include the devices described in Japanese Patent Application Laid-Open No. 2012-227478 and Japanese Patent Application Laid-Open No. 2014-179577.

[Image Display Device] The cured film (color filter, light-shielding film, etc.) of the present invention can be used for an image display device such as a liquid crystal display device or an organic electroluminescence display device.

Definitions of display devices or details of each display device are described, for example, in "Electronic Display Devices (by Sasaki Akio, Kogyo Chosakai Publishing Co., Ltd., 1990)", "Display Devices (Ibuki Shunshu, Industrial Books) Co., Ltd. issued in the first year of Heisei) ". The liquid crystal display device is described in, for example, "Second-generation liquid crystal display technology (edited by Ryuo Uchida, Kogyo Chosakai Publishing Co., Ltd., 1994). The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the liquid crystal display device can be applied to various types of liquid crystal display devices described in the "second generation liquid crystal display technology".

When the color filter in the present invention is applied to a liquid crystal display device, its form is not particularly limited. Hereinafter, a case where the color filter of the present invention is applied to a liquid crystal display device will be described in detail. The color filter of the present invention can be used for a liquid crystal display device of a color TFT (Thin Film Transistor) system. A color TFT-type liquid crystal display device is described in, for example, "color TFT liquid crystal display (KYORITSU SHUPPAN CO., LTD. 1996)". In addition, the color filter of the present invention can also be applied to a liquid crystal display device or a STN (Super-Twist) with an enlarged viewing angle such as a lateral electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), and the like. Nematic, TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), and R-OCB (Reflective Optically Compensated Bend). In addition, the color filter in the present invention can also be used in a bright and high-definition COA (Color-filter On Array) method. With regard to the liquid crystal display device of the COA method, the required characteristics of the color filter, in addition to the usual required characteristics as described above, may also require the required characteristics of the interlayer insulation film, that is, low dielectric constant and resistance to peeling liquid. The color filter of the present invention is excellent in light resistance and the like, and therefore can provide a liquid crystal display device of the COA type with high resolution and excellent long-term durability. In addition, in order to meet the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer. These image display methods are described in, for example, page 43 of "EL, PDP, and LCD Display-Latest Trends in Technology and Market-(TORAY Research Center, Inc. Survey and Research Division 2001)".

In addition to the color filter of the present invention, the liquid crystal display device of the present invention may be composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, or a viewing angle protection film. The color filter of the present invention can be applied to a liquid crystal display device including these known members. These components are described in, for example, "'94 Liquid Crystal Display Peripheral Materials and Chemicals Market (Shimadaro CMC-Group. Issued in 1994)", "Current Status and Future Outlook of the Liquid Crystal Related Market in 2003 (Volume 2) (Table Ryoji Fuji Chimera Research Institute, Inc., 2003). " Regarding the backlight, in addition to SID meeting Digest 1380 (2005) (A. Konno et.al), it is described in the monthly display December, 2005, pages 18 to 24 (Island Kangyu), and in SID meeting Digest 1380 (2005) 25 ~ 30 pages (Yaki Taki).

In addition, the cured film of the present invention can be used in portable devices such as personal computers, tablet computers, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as multifunction printers or scanners; surveillance cameras, bar code readers, and Industrial equipment such as automatic teller machines (ATMs), high-speed cameras, or personal authentication using face image authentication; vehicle camera equipment; medical camera equipment such as endoscopes, capsule endoscopes, or catheters; biosensory Sensors, biosensors, military reconnaissance cameras, stereo map cameras, meteorological or ocean observation cameras, land resource reconnaissance cameras, or space astronomy or deep space target exploration cameras and other space equipment. A light-shielding member or light-shielding layer of an optical filter or module. The cured film of the present invention can be used for an anti-reflection member or an anti-reflection layer of an optical film or module.

The cured film of the present invention can also be used in applications such as micro LED (Light Emitting Diode) or micro OLED (Organic Light Emitting Diode). Although it is not particularly limited, in addition to an optical filter or an optical film used in a micro LED or a micro OLED, it can also be preferably used as a member that imparts a light-shielding function or an anti-reflection function. Examples of the micro LED and the micro OLED include those described in Japanese Patent Application Publication No. 2015-500562 and Japanese Patent Application Publication No. 2014-533890.

The cured film of the present invention can also be used in applications such as quantum dot displays. Although it is not particularly limited, in addition to an optical filter and an optical film used in a quantum dot display, it can also be preferably used as a member that imparts a light-shielding function and an anti-reflection function. Examples of quantum dot displays include U.S. Patent Application Publication No. 2013/0335677, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, and U.S. Patent Application Publication No. 2014/0035960 Recorder. [Example]

Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, proportions, processing contents, processing steps, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be interpreted restrictively by the examples shown below.

Hereinafter, the present invention will be described in detail using examples. However, the present invention is not limited to this. In addition, unless otherwise specified, "parts" and "%" are mass standards.

[Composition] Hereinafter, when preparing the compositions of Examples and Comparative Examples, each component contained in the composition will be described first.

<Titanium Nitride-Containing Particles> As the titanium nitride-containing particles, titanium nitride-containing particles TiN-1 to TiN-19 manufactured as described below were used.

(Titanium Nitride-Containing Particles TiN-1) The titanium nitride-containing particles TiN-1 were produced using an apparatus of the black composite fine particle manufacturing apparatus described in FIG. 1 according to International Publication No. 2010/147098. In the black composite particle manufacturing apparatus, a high-frequency voltage of about 4 MHz and about 80 kVA is applied to a high-frequency oscillation coil of a plasma torch, and 50 L / min of argon and 50 L of nitrogen are supplied as a plasma gas from a plasma gas supply source. / min, the argon-nitrogen plasma flame is generated in the plasma torch. Then, a carrier gas of 10 L / min was supplied from a spray gas supply source of the material supply device. In addition, titanium tetrachloride (liquid) as the particle raw material 1, liquid ammonia (made by Ube Industries, Ltd.) as the particle raw material 2, and Ti powder particles (made by TOHO TECHNICAL SERVICE CO., LTD.) As the particle raw material 3 "TC-200"), together with the carrier gas, that is, argon, is supplied to the thermoplasma flame in the plasma torch, which causes it to evaporate in the thermoplasma flame and is highly dispersed in the gas phase. The flow rate ratios (volume ratios) of the particle materials 1 to 3 are shown in Table 1. Further, nitrogen was used as a gas supplied into the chamber by a gas supply device. The flow velocity in the chamber at this time was set to 5 m / sec, and the supply amount was set to 1000 L / min. The pressure in the cyclone was set to 50 kPa, and the speed at which titanium particles were supplied from the chamber toward the cyclone was set to 10 m / s (average value). Next, the particles were subjected to a heat treatment using Laboratory Kiln L / K manufactured by Narabashi Manufacturing Co., Ltd. as a sintering furnace. Specifically, nitrogen was supplied to the grate furnace as an atmosphere gas at 100 mL / min, and heat treatment was performed at 240 ° C. for 0.2 hours. In this way, TiN-1 containing titanium nitride particles was obtained.

With respect to the obtained titanium nitride-containing particles TiN-1, the contents of titanium (Ti) atoms and chlorine (Cl) atoms were measured by ICP emission spectrometry. In the ICP emission spectroscopic analysis method, an ICP emission spectroscopic analysis device "SPS3000" (trade name) manufactured by Seiko Instruments Inc. was used. The nitrogen atom content was measured using an oxygen and nitrogen analyzer "EMGA-620W / C" (trade name) manufactured by HORIBA, Ltd., and calculated by an inert gas fusion thermal conductivity method. The results are shown in Table 1. In addition, with respect to the titanium nitride-containing particles TiN-2 to TiN-19 described later, the content of Ti atoms, Cl atoms, and nitrogen atoms was also measured by the same method as the titanium nitride-containing particles TiN-1. In addition, the balance in each particle is impurities such as oxygen derived from an oxide, a metal element, and the like, which are present in the particles. The results are shown in Tables 1 and 2.

For X-ray diffraction of titanium nitride-containing particles TiN-1, a powder sample was loaded into an aluminum standard sample holder, and was subjected to a wide-angle X-ray diffraction method (manufactured by Rigaku Corporation, trade name "RU-200R"). Determination. As the measurement conditions, the X-ray source was set to CuKα rays, the output was set to 50kV / 200mA, the slit system was set to 1 ° -1 ° -0.15mm-0.45mm, the measurement step (2θ) was set to 0.02 °, and the scanning speed was set to 2 ° / min. The diffraction angle (2θ) derived from the peak of the TiN (200) plane was measured. In addition, based on the half-value amplitude of the peak, the size of the crystallites constituting the particles was obtained by using the Scherrer formula. The results are shown in Table 1. In addition, for the following titanium nitride-containing particles TiN-2 to TiN-19, the diffraction angle 2θ and the crystallite size were measured by the same method as the titanium nitride-containing particles TiN-1. The results are shown in Tables 1 and 2.

The measurement of the average primary particle diameter of the titanium nitride-containing particles TiN-1 was performed using a transmission electron microscope (TEM) according to the method described above. In addition, the particle shape observation was performed simultaneously with the above measurement. As a result, it was confirmed that 60 or more of the 100 titanium nitride-containing particles to be observed were spherical. These results are shown in Table 1. In addition, regarding the particle shape observation evaluation, when 60% or more of the measurement object is spherical, it is shown as "spherical" in the table. When the number of spherical particles is less than 60% of the measurement object, it is shown in the table as "spherical is less than 60%". When "cubic" is described in the table, it means that the number of particles of the cube is 60% or more of the measurement target. In addition, the cube is not limited to those who are observed as cubes. Polyhedrons with observable corners are also measured as cubes. In addition, about the following titanium nitride-containing particles TiN-2 to TiN-19, the average primary particle diameter was also measured by the same method as the titanium nitride-containing particles TiN-1, and the shape was further observed. The results are shown in Tables 1 and 2.

Regarding the specific surface area of the titanium nitride-containing particles TiN-1, a high-precision automatic gas adsorption device ("BELSORP" 36) manufactured by nippon-bel Co., Ltd. was used to perform vacuum degassing at 100 ° C, and then N _{2 was} measured. The adsorption isotherm at the liquid nitrogen temperature (77K) of the gas was analyzed by the BET method to determine the specific surface area. The results are shown in Table 1. In addition, the specific surface areas of the following titanium nitride-containing particles TiN-2 to TiN-19 were determined by the same method as the titanium nitride-containing particles TiN-1. The results are shown in Tables 1 and 2.

(Titanium nitride-containing particles TiN-2) The particle raw materials 1 to 3 used in the production of titanium nitride-containing particles TiN-1 particles, their flow rate ratios, and heat treatment conditions are shown in Table 1. A titanium nitride-containing particle TiN-2 was produced by the same method as the titanium nitride-containing particle TiN-1.

(Titanium nitride-containing particles TiN-3) The particle raw materials 1 to 3 used in the production of the titanium nitride-containing particles TiN-1 particles, their flow rate ratios, and heat treatment conditions are shown in Table 1. A titanium nitride-containing particle TiN-3 was produced by the same method as the titanium nitride-containing particle TiN-1.

(Titanium Nitride-Containing Particles TiN-4) The particle raw materials 1 to 3 used in the production of the titanium nitride-containing particles TiN-1 particles, their flow ratios, and heat treatment conditions are shown in Table 1. The titanium nitride-containing particles TiN-4 were produced by the same method as the titanium nitride-containing particles TiN-1.

(Titanium Nitride-Containing Particles TiN-5) The particle raw materials 1 to 3 used in the production of the titanium nitride-containing particles TiN-1 particles, their flow ratios, and heat treatment conditions are shown in Table 1. A titanium nitride-containing particle TiN-5 was produced by the same method as the titanium nitride-containing particle TiN-1.

(Titanium nitride-containing particles TiN-6) The particle raw materials 1 to 3 used in the production of titanium nitride-containing particles TiN-1 particles, their flow ratios, heat treatment conditions, and the flow velocity in the chamber are shown in Table 1. Except for this, titanium nitride-containing particles TiN-6 were produced by the same method as titanium nitride-containing particles TiN-1.

(TiN-7 particle-containing TiN-7) A titanium nitride-containing particle TiN- was produced in the same manner as in the titanium nitride-containing particle TiN-6 except that the flow velocity in the chamber was as shown in Table 1. 7.

(TiN-8-containing particles TiN-8) The particle raw materials 1 to 3 used in the production of the titanium nitride-containing particles TiN-1 particles, their flow ratios, heat treatment conditions, and the flow velocity in the chamber are shown in Table 1. Except for this, titanium nitride-containing particles TiN-8 were produced by the same method as titanium nitride-containing particles TiN-1.

(TiN-9-containing TiN-9 particles) Titanium nitride-containing TiN particles were produced in the same manner as in the TiN-8-containing TiN-8 particles except that the flow velocity in the chamber was as shown in Table 1. -9.

(Titanium nitride-containing particles TiN-10) The particle raw materials 1 to 3 used in the production of the titanium nitride-containing particles TiN-1 particles, their flow rate ratios, and heat treatment conditions are shown in Table 1. A titanium nitride-containing particle TiN-10 was produced by the same method as the titanium nitride-containing particle TiN-1.

(Titanium Nitride-Containing Particles TiN-11) The particle raw materials 1 to 3 used in the production of the titanium nitride-containing particles TiN-1 particles, their flow ratios, and heat treatment conditions are shown in Table 2. The titanium nitride-containing particles TiN-11 were produced by the same method as the titanium nitride-containing particles TiN-1. In addition, the particle raw material 3 was not used for TiN-11.

(Titanium nitride-containing particles TiN-12) The particle raw materials 1 to 3 used in the production of the titanium nitride-containing particles TiN-1 particles, their flow rate ratios, and heat treatment conditions are shown in Table 2. The titanium nitride-containing particles TiN-12 were produced by the same method as the titanium nitride-containing particles TiN-1. In addition, TiN-12 did not use particle raw materials 1 and 2.

(Titanium nitride-containing particles TiN-13) The particle raw materials 1 to 3 used in the production of the titanium nitride-containing particles TiN-1 particles, their flow rate ratios, and heat treatment conditions are shown in Table 2. A titanium nitride-containing particle TiN-13 was produced by the same method as the titanium nitride-containing particle TiN-1. The heat treatment temperature of the titanium nitride-containing particles TiN-13 was set to 250 ° C.

(Titanium nitride-containing particles TiN-14) The particle raw materials 1 to 3 used in the production of the titanium nitride-containing particles TiN-1 particles, their flow ratios, and heat treatment conditions are shown in Table 2. The titanium nitride-containing particles TiN-14 were produced by the same method as the titanium nitride-containing particles TiN-1.

(Titanium nitride-containing particles TiN-15) The particle raw materials 1 to 3 used in the production of the titanium nitride-containing particles TiN-1 particles, their flow ratios, and heat treatment conditions are shown in Table 2. The titanium nitride-containing particles TiN-15 were produced by the same method as the titanium nitride-containing particles TiN-1.

(TiN-16 particle-containing TiN-16) A titanium nitride-containing particle TiN-16 was produced by the same method as the titanium nitride-containing particle TiN-15 except that the heat treatment conditions were as shown in Table 2. .

(Titanium nitride-containing particles TiN-17) The particle raw materials 1 to 3 used in the production of the titanium nitride-containing particles TiN-1 particles and their flow ratios are shown in Table 2. In addition, Titanium nitride-containing particles TiN-1 were produced in the same manner as titanium nitride-containing particles TiN-17.

(Titanium nitride-containing particles TiN-18) The particle raw materials 1 to 3 used in the production of the titanium nitride-containing particles TiN-1 particles and their flow ratios are shown in Table 2. In addition, Titanium nitride-containing particles TiN-1 were produced in the same manner as titanium nitride-containing particles TiN-18.

(Titanium nitride-containing particles TiN-19) The particle raw materials 1 to 3 used in the production of the titanium nitride-containing particles TiN-1 particles, their flow rate ratios, and heat treatment conditions are shown in Table 2. The titanium nitride-containing particles TiN-19 were produced by the same method as the titanium nitride-containing particles TiN-1.

The manufacturing conditions and physical properties of the titanium nitride-containing particles TiN-1 to titanium nitride-containing particles TiN-19 are shown in Tables 1 and 2 below. In addition, in the table, all of the titanium nitride-containing particles other than TiN-11, TiN-12, TiN-13, and TiN-14 have a heat treatment temperature of 240 ° C.

(Table 1) [Table 1]

(Table 2) [Table 2]

<Dispersant> As a dispersant, the following dispersants A to E were used. In the dispersants A, B, and D, the numerical value described in each structural unit represents the mass% of each structural unit with respect to all the structural units. In addition, in the dispersant C, the numerical values (a to e) described in each structural unit represent the molar ratio of each structural unit to all the structural units, and x and y represent the number of connections. In the dispersant E, the numerical value described in the linking group linked to Z indicates the number of links to Z.

[Chemical Formula 20]

[Chemical Formula 21]

<Adhesive resin> As the adhesive resin, the following adhesive resins A and B were used.・ Adhesive resin A (manufactured by Akurikuya RD-F8 NIPPON SHOKUBAI CO., LTD., Please refer to the following structure) ・ Adhesive resin B (Cyclomer P (ACA) 230AA DAICEL CORPORATION)

[Chemical Formula 22]

<Polymerizable compound> ・ Polymerizable compound M1 (manufactured by Nippon Kayaku Co., Ltd., trade name "KAYARAD", see structure below)

[Chemical Formula 23]

PET-30 (Pentaerythritol triacrylate, manufactured by Nippon Kayaku Co., Ltd.)

<Polymerization initiator> ・ OXE-02: Irgacure OXE02 (trade name, manufactured by BASF JAPAN LTD.) ・ OXE-03: Irgacure OXE03 (trade name, manufactured by BASF JAPAN LTD.) ・ N-1919: Trade name, ADEKA CORPORATION Manufacturing ・ IRGACURE-907: Product name, manufactured by BASF JAPAN LTD.

<Solvent> PGMEA: Propylene glycol monomethyl ether acetate, cyclopentanone, butyl acetate, ethyl 3-ethoxypropionate, distilled butyl acetate, and distilled cyclopentanone. The cyclopentanone was distilled, and a commercially available butyl acetate and cyclopentanone were distilled and purified.

<Polymerization inhibitor> ・ P-methoxyphenol

<Surfactant> F-1: The following mixture (weight average molecular weight (Mw) = 14000)

[Chemical Formula 24]

<Preparation of Pigment Dispersion> First, a titanium nitride-containing particle, a dispersant, and a solvent were mixed with a mixer (Eurostar, manufactured by IKA COMPANY) for 15 minutes to obtain a dispersion. Next, the obtained dispersion was subjected to a dispersion treatment under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises Corporation to obtain a pigment dispersion. (Dispersion conditions) ・ Bead diameter: 0.05mm, (NIKKATO CORPORATION YTZ) ・ Bead filling rate: 65% by volume ・ Grinding peripheral speed: 10m / sec ・ Separator peripheral speed: 13m / s ・ Mixed liquid for dispersion treatment Amount: 15kg ・ Circulation flow rate (pump supply): 90kg / hour ・ Processing liquid temperature: 19 ～ 21 ℃ ・ Cooling water: Water ・ Processing time: 22 hours

<Preparation of composition> Next, the pigment dispersion liquid, the binder resin, the polymerizable compound, the polymerization initiator, and the solvent were mixed and stirred to obtain the examples and comparisons shown in Tables 3 to 5 below. Examples of each composition. Contents (mass%) of each component contained in each composition of an Example and a comparative example are shown in Table 3-Table 5. In addition, the ratio ((mass ratio) D / P) of the dispersant to the titanium nitride-containing particles, the solid content concentration (mass%) in the composition, and the moisture content (mass%) in the composition are measured below. Method.). Each composition was prepared so that the pigment concentration (% by mass) in the solid content became the ratio shown in each of Examples and Comparative Examples in Tables 3 to 5.

(Measurement of Water Content in Compositions) The water content of each composition in the examples and comparative examples was manufactured by MKV-710 (trade name, KYOTO ELECTRONICS MANUFACTURING CO., LTD.) Using the Karl Fischer method as a measuring principle. ). The results are shown in Tables 3 to 5.

[Evaluation Test] The following evaluation tests were performed on each composition of Examples and Comparative Examples.

<Degassing> A frame for a color filter was produced using each composition of Examples and Comparative Examples. Specifically, on a semiconductor substrate composed of an image sensor on an 8-inch substrate, the composition of Examples and Comparative Examples was spin-coated so that the film thickness after pre-baking became 1.5 μm. membrane. Next, a binary mask capable of forming a light shielding film having a width of 250 μm and a total width of 200 μm was placed on the outer periphery of 720 μm in width and 520 μm in length, and exposure was performed using an i-ray exposure device (FPA-3000 + i5, manufactured by Canon Inc.) (exposure 500 mJ / cm ² ), development was further performed. The obtained semiconductor substrate having a plurality of color filter frames was cut into a size of 10 mm × 10 mm, and the amount of Cl in the degassed was measured by a thermal desorption spectrum analysis (TDS), and evaluated based on the following criteria. The count intensity ratio of the peak position derived from Cl in the total degassing amount (detected total ion current value) from 1 to 199 when the count of atmospheric-derived components included in the background was cancelled was measured, and was performed based on the following criteria Evaluation. The degree of vacuum at the time of measurement is 1 × 10 ^-7 Torr or less. "A": The amount of Cl in degassed 1L is 10 ppm or less. "B": The amount of Cl in degassed 1L exceeds 10 ppm and 50 ppm or less. "C": The amount of Cl in degassed 1L exceeds 50 ppm and 100 ppm or less. "D": In degassing 1L, the amount of Cl exceeds 100ppm

<Number of Particles> A sample solution in which the above composition was diluted 500 times was prepared by PGMEA, and the sample solution was measured by a flow-type particle image analysis apparatus (trade name "FPIA-3000", manufactured by Malvern Instruments Ltd) The number of particles of 10 μm or more contained in 10 ml.

<OD value> The composition of the examples and comparative examples was spin-coated on a glass plate (manufactured by EagleXG, Corning Inc.) with a thickness of 0.7 mm and an angle of 10 cm at a rotation speed of 1.0 μm to form a film, and the film was formed on a hot plate A dry film was obtained by a heat treatment at 100 ° C for 2 minutes. The obtained substrate was measured for OD by a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation.), And the lowest OD value was measured from 400 nm to 1200 nm in the measurement wavelength range, and evaluated based on the following criteria. "A": minimum OD is 4.2 or more "B": minimum OD is 3.8 or more and less than 4.2 "C": minimum OD is 3.5 or more and less than 3.8 "D": minimum OD is less than 3.5

<Filterability> The compositions of the examples and comparative examples were evaluated for filterability using a capsule filter DFA (manufactured by NIHON PALL LTD., Nylon pore diameter 0.45 μm, 2 inch). In addition, 16 kg of the composition was filtered at a flow rate of 400 ml / min, and evaluated based on the following criteria. "A": Filtered all 16kg. "B": After filtering more than 12kg and less than 16kg, the flow rate becomes less than 400mL / min. "C": After filtering more than 8kg and less than 12kg, the flow rate becomes less than 400mL / min. "D": After filtering less than 8 kg, the flow rate becomes less than 400 mL / min.

<Composition Stability Over Time (CM Stability Over Time)> After the compositions of Examples and Comparative Examples were stored at 23 ° C for 30 days, they were stored at 7 ° C for 9 months. Thereafter, the viscosity of each composition before and after storage was measured using an E-type viscometer (manufactured by TOKI SANGYO CO., LTD., Trade name "R85-shaped viscometer") at a speed of 10 rpm and 23 ° C. The formula calculates the viscosity increasing rate. The evaluation criteria are as follows. (Viscosity) = (Viscosity after time)-(Viscosity immediately after liquid adjustment) / (Viscosity immediately after liquid adjustment) "A": The viscosity increase ratio is less than 3% "B": The viscosity increase ratio is 3 % Or more and less than 5% "C": viscosity increase rate is 5% or more and less than 10% "D": viscosity increase rate is 10% or more

<Pattern Formability (Resolution)> Using the compositions of Examples and Comparative Examples, a coating film was formed on a substrate of an image sensing device by a spin coater. Next, the obtained coating film was subjected to a pre-baking treatment at 100 ° C. for 2 minutes on a hot plate. Next, an i-ray exposure device (manufactured by FPA, Canon Inc.) was used to expose the coating film subjected to the pre-baking treatment and further develop it, thereby forming a covered cutting line and an electrode portion on the peripheral portion of the light receiving portion on the substrate. At the same time as the other light-shielding films, 20 alignment marks having a line width of 20 μm were formed on the substrate. The number of alignment marks formed was observed with an optical microscope to evaluate the resolution. "A": 20 marks were formed. "B": 19 marks were formed. "C": Eighteen marks were formed. "D": Marked as 17 or less.

<Corrosion Resistance of Electrodes> Using the compositions of Examples and Comparative Examples, a coating film was formed on a substrate of an image sensing device by a spin coater. Next, the obtained device film was subjected to a pre-baking treatment on a hot plate at 100 ° C. for 2 minutes on the formed device substrate. Next, an i-ray exposure device (FPA-3000 + i5, manufactured by Canon Inc.) was used to expose the coating film subjected to the above-mentioned pre-baking treatment and further develop it, thereby forming a covered cutting line and Light-shielding film other than the electrode part. Then, the obtained light-shielding film was subjected to a heat treatment at 220 ° C. for 5 minutes using a hot plate (post-baking process). After the wafer having the obtained light-shielding film was stored in an environment at a temperature of 110 ° C. and a humidity of 90% RH (HAST tester EHS-411M manufactured by ESPEC CORP.) For 3 days, 300 electrodes formed on the wafer were stored. The mat was observed with a light microscope (manufactured by Olympus Corporation, trade name "LEXT OLS4500") for the occurrence of rust on the electrode pattern, and the corrosion resistance of the electrode was evaluated based on the following criteria. "A": No change is observed. "B": The electrode has less than 2 rusts. "C": The electrode has more than 2 to 10 rusts. "D": The electrode has more than 10 rusts.

The evaluation results of the above evaluation tests are shown in Tables 3 to 5. In addition, in Example 33, the mixing ratio of M1 and PET-30 was 5: 5 in terms of mass ratio.

[table 3]

[Table 4]

[table 5]

As shown in Tables 3 to 5, it is shown that the content of the chlorine atom in the titanium nitride-containing particles can be produced within a range of 0.001 to 0.3% by mass (in other words, 10 to 3,000 ppm by mass). A cured film (Example) having excellent corrosion resistance and excellent pattern formation (resolution) of an electrode. In addition, it is shown that if the content of the chlorine atom in the titanium nitride-containing particles exceeds 0.3% by mass (in other words, 3000 mass ppm), the pattern forming property (resolution) and the corrosion resistance of the electrode are poor (Comparative Example 1, Comparative Example) 2). In addition, it is shown that if the content of the chlorine atom in the titanium nitride-containing particles is less than 0.001% by mass (in other words, less than 10% by mass), the pattern formability (resolution) is poor (Comparative Example 3 and Comparative Example 4).

In addition, by comparison between Examples 17 to 21, it was confirmed that the content of water was 0.1 to 1% by mass relative to the total mass of the composition (0.1 to 0.8% by mass is preferable, and 0.1 to 0.4% by mass is more preferable). In this case, the pattern-forming property (resolution) of the cured film and the corrosion resistance of the electrode material are more excellent. Furthermore, it was confirmed that the amount of particles in the composition can be further reduced by setting the content of water to 0.1 to 1% by mass based on the total mass of the composition, and the viscosity of the composition is also more stable over time. In addition, by comparing Example 26 with Example 27, it was confirmed that when D / P is 0.3 or less, the pattern formation property (resolution) of the cured film is more excellent. By comparison of Examples 26, 31, and 32, it was confirmed that when the content of the titanium nitride-containing particles is 30 to 70% by mass relative to the total solid content of the composition, the spectroscopic property (good OD value) and the pattern forming property ( Resolution) and electrode corrosion resistance. In addition, by comparison of Examples 6 to 9, it was confirmed that when the specific surface area of the titanium nitride-containing particles determined by the BET method was 40 to 60 m ² / g, the spectroscopic properties (good OD values) and pattern formation properties were confirmed. (Resolution) is more excellent. In addition, it was confirmed that the filterability was also excellent. In addition, by comparison of Examples 10 to 14, it was confirmed that when CuKα rays were used as the X-ray source, the diffraction angle 2θ of the peak originating from the (200) plane of the titanium nitride-containing particles exceeded 42.8 ° and 43.5 ° or less. , Excellent spectroscopic properties (good OD value) and pattern formation properties (resolution). In addition, by comparison of Examples 12 to 15, it was confirmed that when the average primary particle diameter of the titanium nitride-containing particles was 10 to 30 nm, the spectroscopic property (good OD value) was more excellent. In addition, it was confirmed that the viscosity of the composition was excellent in stability over time. In addition, it was confirmed that when the average primary particle diameter of the titanium nitride-containing particles is 10 nm or more, the viscosity of the composition is excellent in stability over time. In addition, by comparison between Example 12 and Example 16, it was confirmed that the shape of the primary particles of the titanium nitride-containing particles by a transmission electron microscope was 60% by mass or more, and the spectroscopic properties (good OD Value) and pattern formability (resolution). In addition, it was confirmed that the composition has excellent filterability and viscosity over time.

Except that the surfactant F-1 was not used in Example 1, it evaluated by the same method. As a result of the evaluation, it was found that the same results as in Example 1 were obtained.

<Preparation of Carbon Black Dispersion (CB Dispersion)> In the preparation of the pigment dispersion, carbon black (trade name "Color Black S170", manufactured by Degussa-Hüls AG, average primary particle) was used instead of titanium nitride-containing particles. A carbon black dispersion was produced by the same method except that the diameter was 17 nm, the BET specific surface area was 200 m ² / g, and carbon black was produced by a gas black method.

In the preparation of the composition of Example 1, a pigment dispersion containing titanium nitride-containing particles TiN-1 was used instead of the pigment dispersion liquid added so that the composition contained 19% by mass of titanium nitride-containing particles TiN-1. A mixture of the liquid and the CB dispersion liquid [containing titanium nitride particles in the composition TiN-1: carbon black of the composition = 15: 4 (mass ratio). The total content of titanium nitride-containing particles TiN-1 and carbon black in the composition was 19% by mass. ] Except that a composition was prepared by the same method and evaluated using the composition. As a result of the evaluation, it was found that the same light-shielding property as that of Example 1 can be obtained.

<Preparation of Color Pigment Dispersion (PY Dispersion Liquid)> In the preparation of the pigment dispersion, pigment yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., trade name 6150 pigment was used instead of titanium nitride-containing particles). Yellow 5GN), a dispersion was prepared by the same method to obtain a color pigment dispersion (PY dispersion).

In the preparation of the composition of Example 1, a pigment dispersion containing titanium nitride-containing particles TiN-1 was used instead of the pigment dispersion liquid added so that the composition contained 19% by mass of titanium nitride-containing particles TiN-1. A mixture of the liquid and the above-mentioned PY dispersion liquid [the titanium nitride-containing particles TiN-1 in the composition: Pigment Yellow 150 in the composition = 17: 2 (mass ratio). The total content of the titanium nitride-containing particles TiN-1 and Pigment Yellow 150 in the composition was 19% by mass. ], Except that a composition was prepared by the same method and evaluated using the composition. As a result of the evaluation, it was found that the same light-shielding property as in Example 1 was obtained, and a film having a strong black color was obtained.

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Claims (19)

A composition containing chlorine atom-containing titanium nitride-containing particles, and a content of the chlorine atom in the titanium nitride-containing particles is 0.001 to 0.3% by mass. The composition according to item 1 of the patent application range, wherein when CuKα rays are used as the X-ray source, the diffraction angle 2θ of the peak originating from the (200) plane of the titanium nitride-containing particles is more than 42.8 ° and 43.5 ° the following. The composition according to item 1 or item 2 of the scope of patent application, wherein the specific surface area of the titanium nitride-containing particles obtained by the BET method is 40 to 60 m ² / g. The composition according to item 1 or item 2 of the patent application range, wherein the average primary particle diameter of the titanium nitride-containing particles is 10 to 30 nm. The composition according to item 1 or item 2 of the scope of patent application, wherein in the photo observation of the primary particle image of the titanium nitride-containing particles using a transmission electron microscope, 60 or more of the 100 observation objects are spherical . The composition according to item 1 or item 2 of the patent application scope, further comprising two or more solvents. The composition according to item 1 or item 2 of the scope of patent application, further comprising a dispersant. The composition according to item 7 of the scope of patent application, wherein the content ratio of the dispersant to the titanium nitride-containing particles is 0.3 or less in terms of mass ratio. The composition according to item 1 or 2 of the scope of patent application, further comprising a polymerizable compound. The composition according to item 1 or item 2 of the scope of patent application, further comprising a polymerization initiator. The composition according to item 1 or 2 of the scope of patent application, wherein the solid content in the composition is 10 to 40% by mass. The composition according to claim 1 or 2, wherein the content of the titanium nitride-containing particles is 30 to 70% by mass relative to the total solid content of the composition. The composition according to item 1 or 2 of the scope of patent application, further comprising water, and the content of the water relative to the total mass of the composition is 0.1 to 1% by mass. The composition according to item 1 or item 2 of the scope of application for a patent, further comprising a dispersant, the dispersant having a material selected from At least one structure of the formed group. A hardened film obtained by using the composition described in any one of claims 1 to 14 of the scope of patent application. A color filter having a hardened film as described in claim 15 of the scope of patent application. A light-shielding film having the hardened film described in claim 15 of the scope of patent application. A solid-state photographic element having the hardened film described in claim 15 of the scope of patent application. An image display device includes the hardened film described in claim 15 of the scope of patent application.