JP6698820B2 - Composition, cured film, color filter, light-shielding film, solid-state image sensor and image display device - Google Patents

Description

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

The solid-state image pickup device is a solid-state image pickup element such as a CCD (charge-coupled device) and a CMOS (complementary metal oxide semiconductor) which is arranged behind the image pickup lens (hereinafter, the solid-state image pickup element is referred to as an “image sensor”). (Also referred to as ".") and a circuit board on which the solid-state imaging device is mounted. This solid-state imaging device is mounted on a digital camera, a camera-equipped mobile phone, a smartphone, or the like.
In the solid-state imaging device, noise may occur due to reflection of visible light. Therefore, for the purpose of suppressing the generation of noise, a predetermined light shielding film is provided in the solid-state imaging device. A black composition containing a black pigment such as titanium black is used as the composition for forming the light-shielding film.

On the other hand, the color filters arranged in the solid-state imaging device, the liquid crystal image device, and the like include R (red), G (green), and B( for the purpose of preventing color mixture of light between colored pixels and improving contrast. A black matrix may be formed between each pixel of (blue). In addition, in the color filter, an image sensor peripheral light-shielding film (frame light-shielding film) is formed in the frame region for the purpose of preventing light leakage from the light-receiving portion of the solid-state image sensor.
A black composition containing a black pigment such as titanium black is also used in the composition for forming the above black matrix. For example, in Patent Document 1, "a black resin composition for a resin black matrix containing at least a light shielding material, a resin and a solvent, and containing at least titanium nitride particles as the light shielding material, where CuKα rays are used as an X-ray source The black resin composition for a resin black matrix, wherein the diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride particles is 42.5° or more and 42.8° or less.” 1).

Patent No. 5136139

The cured film of the black composition containing the titanium nitride particles (titanium nitride-containing particles) as described above is used, for example, as a light-shielding film of a component of a solid-state imaging device, a black matrix of a color filter, or a light-shielding film around an image sensor. When used, it may be used by being laminated on a substrate on which electrodes such as electrode patterns are arranged.
The present inventors produced a black composition containing titanium nitride particles (titanium nitride-containing particles) described in Patent Document 1, and using this, an electrode was formed on a substrate on which an electrode was arranged. A cured film was formed so as to cover, and the evaluation was performed. As a result, it was found that, depending on the type of titanium nitride particles (titanium nitride-containing particles), rust or the like may occur in the region of the electrode that contacts the light shielding film, that is, the electrode may corrode. Further, similarly, it has been clarified that when a patterned cured film is formed using the black composition, the pattern resolution (patternability) may not satisfy a desired requirement.

  Therefore, an object of the present invention is to provide a composition capable of producing a cured film having excellent corrosion resistance of electrodes and excellent patterning properties. Another object of the present invention is to provide a cured film, a color filter, a light shielding film, a solid-state image sensor and an image display device.

As a result of intensive studies to achieve the above problems, the present inventors have found that the above problems can be solved by adjusting the content of chlorine atoms in titanium nitride-containing particles to a predetermined numerical range, and the present invention Completed
That is, it was found that the above object can be achieved by the following constitution.

(1) Containing titanium nitride-containing particles containing chlorine atom,
The composition in which the content of the chlorine atom in the titanium nitride-containing particles is 0.001 to 0.3% by mass.
(2) The diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particles is more than 42.8° and 43.5° or less when CuKα ray is used as the X-ray source. ).
(3) The composition according to (1) or (2), wherein the titanium nitride-containing particles have a specific surface area of 40 to 60 m ² /g determined by the BET method.
(4) The composition according to any one of (1) to (3), wherein the titanium nitride-containing particles have an average primary particle diameter of 10 to 30 nm.
(5) In observing a photograph of the primary particle image of the titanium nitride-containing particles using a transmission electron microscope,
The composition according to any one of (1) to (4), wherein 60 or more of 100 observation objects are spherical.
(6) The composition according to any one of (1) to (5), which further contains two or more kinds of solvents.
(7) The composition according to any one of (1) to (6), which further contains a dispersant.
(8) The composition according to (7), wherein the content ratio of the dispersant to the titanium nitride-containing particles is 0.3 or less in mass ratio.
(9) The composition according to any one of (1) to (8), which further contains a polymerizable compound.
(10) The composition according to any one of (1) to (9), which further contains 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 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 mass% with respect to the total solid content of the composition.
(13) Further contains water,
The composition according to any one of (1) to (12), wherein the content of the water is 0.1 to 1 mass% with respect to the total mass of the composition.
(14) Further, containing a dispersant,
The composition according to any one of (1) to (13), wherein the dispersant has at least one structure selected from the group consisting of polycaprolactone, polyvalerolactone, polymethyl acrylate and polymethyl methacrylate. object.
(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 image sensor having the cured film according to (15).
(19) An image display device having the cured film according to (15).

  According to the present invention, it is possible to provide a composition capable of producing a cured film having excellent corrosion resistance of electrodes and excellent patterning properties. Further, the present invention can provide a cured film, a color filter, a light shielding film, a solid-state image sensor, and an image display device.

The present invention will be described below.
In the present specification, the numerical range represented by "to" means a range including the numerical values before and after "to" as the lower limit value and the upper limit value.
In the description of the group (atom group) in the present specification, the notation in which substitution and non-substitution are not included includes not only those having no substituent but also those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
The term “actinic ray” or “radiation” as used herein means, for example, a bright line spectrum of a mercury lamp, deep ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. . In the present invention, light means actinic rays or radiation. Unless otherwise specified, the term "exposure" in the present specification means not only exposure with a bright line spectrum of a mercury lamp, deep ultraviolet rays typified by excimer laser, X-ray, EUV light, etc., but also electron beam, ion beam, etc. Drawing with the particle beam is also included in the exposure.
In the present specification, “(meth)acrylate” means acrylate and methacrylate, “(meth)acrylic” means acrylic and methacrylic, “(meth)acryloyl” means acryloyl and methacryloyl, and “(meth ) Acrylamide" stands for acrylamide and methacrylamide. In addition, in the present specification, “monomer” and “monomer” have the same meaning. The monomer in the present invention is a compound having a weight average molecular weight of 2,000 or less, which is distinguished from oligomers and polymers. In the present specification, the polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer. The polymerizable group means a group involved in the polymerization reaction.

[Composition]
The composition of the present invention contains titanium nitride-containing particles containing chlorine atoms, and the content of the chlorine atoms 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 anticorrosion properties of electrodes and excellent patterning properties can be produced.
As a result of intensive studies, the inventors of the present invention have used a black composition containing, as a pigment component, titanium nitride-containing particles having a chlorine atom content of more than 0.3% by mass, on a substrate on which electrodes are arranged. It was confirmed that, when the light-shielding film was formed, the above chlorine atom reacts with moisture in the air or the like to generate hydrochloric acid, which may cause deterioration of the electrode member depending on the environmental conditions of use.
On the other hand, when a composition containing titanium nitride-containing particles having a chlorine atom content of less than 0.001% by mass as a pigment component is used, the optical density (OD) of the obtained coating film becomes high and the patterning property becomes high. We know that it tends to decrease.
From the above viewpoint, by setting the content of chlorine atoms in the titanium nitride-containing particles contained in the composition to 0.001 to 0.3 mass%, the corrosion resistance of the electrode is excellent, and the patterning property is excellent. A cured film can be formed.

<Titanium nitride-containing particles containing chlorine atom>
A gas phase reaction method is usually used for producing the titanium nitride-containing particles, and specific examples thereof include an electric furnace method and a thermal plasma method. Among these production methods, the thermal plasma method is preferable because it is less contaminated with impurities, has a uniform particle size, and has high productivity.
Examples of the method of generating thermal plasma include direct current arc discharge, multi-phase arc discharge, radio frequency (RF) plasma, and hybrid plasma, and high frequency plasma in which impurities from the electrodes are less mixed is preferable. As a specific method for producing titanium nitride-containing particles by the thermal plasma method, for example, titanium powder is vaporized by high-frequency thermal plasma, nitrogen is introduced into the device as a carrier gas, and the titanium powder is nitrided in the cooling process. , A method of synthesizing titanium nitride-containing particles, and the like. The thermal plasma method is not limited to the above.
Further, the titanium nitride-containing particles have a diffraction angle 2θ (details will be described later) of a peak derived from the (200) plane when CuKα rays are used as an X-ray source, because the titanium nitride-containing particles are obtained by using a thermal plasma method. It becomes easy to adjust in the range of more than 42.8° and 43.5° or less.

Here, the method of incorporating chlorine atoms into the titanium nitride-containing particles is not particularly limited. As an example, in the above-mentioned thermal plasma method, titanium tetrachloride is used together with titanium powder, and ammonia gas is flown as a carrier gas to synthesize titanium nitride-containing particles containing chlorine atoms.
In addition, when the content of chlorine atoms in the titanium nitride-containing particles is not less than a predetermined amount, the particles are heated to, for example, 100 to 300° C. (preferably 120 to 280° C., more preferably 120 to 250° C.). It is desirable to perform heat treatment for minutes to 72 hours (preferably 3 to 48 hours, more preferably 3 to 36 hours). Through the heat treatment, the content of chlorine atoms contained in the titanium nitride-containing particles can be reduced and adjusted to a predetermined amount.

  It is preferable that the titanium powder material (titanium particles) used for producing the titanium nitride-containing particles and titanium tetrachloride have high purity. The titanium powder material and titanium tetrachloride are not particularly limited, but titanium element purity of 99.99% or more is preferable, and 99.999% or more is more preferably used.

The titanium powder material (titanium particles) and titanium tetrachloride used for producing the 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 mass% with respect to the total mass of the titanium powder material and titanium tetrachloride. Thereby, the patterning property of the cured film is more excellent. Further, when the titanium powder material and titanium tetrachloride contain Fe atoms, the content of Fe atoms is preferably less than 0.4 mass% with respect to the total amount of titanium powder material and titanium tetrachloride. .. Thereby, the corrosion resistance of the electrode by the cured film is more excellent (corrosion of the electrode by the cured film can be further suppressed). That is, when the Fe powder contained in the titanium powder material and titanium tetrachloride used for the production of the titanium nitride-containing particles is within the above range (more than 0.001 mass% and less than 0.4 mass %), The effect can be obtained more significantly.
When the titanium powder material and titanium tetrachloride contain Si atoms, the content of Si atoms is preferably more than 0.002 mass% and less than 0.3 mass% with respect to the total mass of the titanium powder material. , 0.01 to 0.15 mass% is more preferable, and 0.02 to 0.1 mass% is still more preferable. When the content of Si atoms is more than 0.002 mass %, the patterning property of the cured film is further improved. Further, when the content of Si atoms is less than 0.3% by mass, the polarity of the outermost layer of the obtained titanium nitride-containing particles is stable, and the titanium nitride-containing particles when the titanium nitride-containing particles are dispersed. It is considered that the adsorbability of the dispersant to the dispersion is improved and the undispersed particles of the titanium nitride-containing particles are reduced, so that the generation of particles can be suppressed. That is, the effect of the present invention can be more remarkably obtained when the Si powder contained in the titanium powder material and titanium tetrachloride used for producing the titanium nitride-containing particles is within the above range.
Further, the water content in the titanium powder material (titanium particles) and titanium tetrachloride used for the production of titanium nitride-containing particles is preferably less than 1% by mass based on the total mass of the titanium powder material, and 0 It is more preferably less than 0.1% by mass, and further preferably substantially not contained. When the water content in the titanium powder material and titanium tetrachloride used for producing the titanium nitride-containing particles is within the above range, the effect of the present invention can be more remarkably obtained.

The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 50 to 85% by mass, and more preferably 50 to 80% by mass, based on the total mass of the titanium nitride-containing particles. More preferably, it is more preferably 50 to 75 mass %. The content of Ti atoms in the titanium nitride-containing particles can be analyzed by ICP (high frequency inductively coupled plasma) emission spectroscopy.
The content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 20 to 50 mass% and more preferably 20 to 45 mass% with respect to the total mass of the titanium nitride-containing particles. More preferably, it is more preferably 20 to 40% by mass. The content of nitrogen atoms can be analyzed by an inert gas melting-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 chlorine atoms in the titanium nitride-containing particles is 0.001 to 0.3 mass% with respect to the total mass of the titanium nitride-containing particles. Among them, 0.005 to 0.3 mass% is preferable, 0.01 to 0.3 mass% is more preferable, 0.1 to 0.3 mass% is further preferable, and 0.1 0.15 mass% is especially preferable. When the content of chlorine atoms is 0.001% by mass or more, the patternability of the cured film is excellent. When the content of chlorine atoms is 0.3% by mass or less, the patterning property of the cured film is excellent, and the corrosion resistance of the electrode by the cured film is excellent.
Here, the content of chlorine atoms in the titanium nitride-containing particles is measured by ICP emission spectroscopy.

  The titanium nitride-containing particles have a diffraction angle 2θ of a peak derived from the (200) plane of more than 42.8° and 43.5° or less when an X-ray diffraction spectrum is measured using CuKα ray as an X-ray source. preferable. A cured film (for example, a black matrix) obtained by using the composition containing the titanium nitride-containing particles having such characteristics has an appropriate OD value and is excellent in patterning property (resolution).

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 43.5° or less, and is 42.85 to 43.3°. Is more preferable, and it is further preferable that it is 42.9 to 43.2°.
Titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and usually become noticeable when oxygen is mixed in during its synthesis and when the particle size is small. You may contain a part oxygen atom.
However, it is preferable that the amount of oxygen contained in the titanium nitride-containing particles is small because a higher OD value (optical density) can be obtained. Further, the titanium nitride-containing particles preferably do not contain TiO ₂ as a subcomponent. When the titanium nitride-containing particles contain titanium oxide TiO ₂ as an accessory component, the peak derived from anatase-type TiO ₂ (101) has the strongest peak near 2θ=25.3°, and rutile-type TiO ₂ ( The peak derived from 110) is seen near 2θ=27.4°. However, since TiO ₂ is white and becomes a factor that deteriorates the light-shielding property of the black matrix, it is preferable that TiO ₂ is reduced to the extent that it is not observed as a peak.

  The crystallite size constituting the titanium nitride-containing particles can be determined from the half width of the X-ray diffraction peak, and is calculated using Scherrer's formula.

  The crystallite size is preferably 20 nm or more, more preferably 20 to 50 nm. When a black matrix is formed using titanium nitride-containing particles having a crystallite size of 20 nm or more, the light transmitted through the cured film exhibits a blue to violet color with a peak wavelength of 475 nm or less, high light-shielding properties, and ultraviolet light. A black matrix having both sensitivity can be obtained.

The specific surface area of the titanium nitride-containing particles can be determined by the BET method, is preferably of 40 to 60 ² / g, more preferably 40~58m ² / g, it is 42~55m ² / g Is more preferable. By setting the specific surface area of the titanium nitride-containing particles to 40 to 60 m ² /g, the obtained cured film has an OD (optical density) value in a more appropriate range and is excellent in patternability (resolution), and also has a 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, further preferably 10 to 25 nm, and further preferably 10 to 20 nm. . By setting the average primary particle diameter of the titanium nitride-containing particles to 10 to 30 nm, the obtained cured film has an OD (optical density) value in an appropriate range. Further, from the viewpoint of viscosity stability over time of the composition, the titanium nitride-containing particles preferably have an average primary particle size of 10 nm or more.
In the present invention, the average primary particle diameter of the titanium nitride-containing particles is obtained by observing the particles with a transmission electron microscope (for example, JEM-2100F type electron emission transmission electron microscope manufactured by JEOL Ltd.). The number average particle diameter of the primary particles can be determined from the photograph taken. Specifically, a dispersion liquid containing titanium nitride-containing particles was prepared by the method described in Examples, diluted with the same solvent as the dispersion liquid so that the solid content was about 1% by mass, and dispersed on a carbon foil. A transmission electron microscope image of the titanium nitride-containing particles existing on the carbon foil after the liquid is dropped and dried is observed. The projected area of primary particles of titanium nitride-containing particles is obtained by the above apparatus, and the equivalent circle diameter is obtained therefrom. The calculated average equivalent circle diameter was used as the primary particle diameter. More specifically, after measuring the primary particle diameters of 100 particles randomly selected to obtain the average primary particle diameter, 80 particles excluding 10 particles on the maximum side and 10 particles on the minimum side were measured. It is obtained by arithmetically averaging the primary particle diameters of.
Further, in the titanium nitride-containing particles, 60 or more (in other words, 60% or more) of 100 objects to be observed are spherical in photographic observation of the primary particle image using the above-mentioned transmission electron microscope. Is preferred. When 60% or more of the titanium nitride-containing particles used are spherical, the obtained cured film has an OD (optical density) value in an appropriate range, and is excellent in patternability (resolution). Moreover, since 60% or more of the titanium nitride-containing particles used are spherical, the composition has excellent filterability and viscosity stability over time.
In the present invention, it is not always necessary that the particles are “spherical”, and it is not necessarily a true sphere. For example, particles having a substantially spherical shape (the ratio of the minor axis/major axis in a projected two-dimensional figure is 0.7 to 1) Degree) and a spheroid.

The content of the titanium nitride-containing particles is preferably 30 to 70% by mass, more preferably 40 to 68% by mass, and 42 to 65% by mass with respect to the total solid content of the composition. Is more preferable. When the content of the titanium nitride-containing particles is within the above numerical range, not only the spectral property (good OD value) is excellent, but also the patterning property (resolution) and the anticorrosion property of the electrode are excellent.
In addition, in this specification, a solid content intends the component which comprises the cured film formed of a composition, and does not contain a solvent. For example, since the polymerizable compound described below is a component that constitutes the cured film, even a liquid (liquid) is included in the solid content.

<Dispersant>
The composition of the present invention preferably contains a dispersant. The dispersant contributes to improving the dispersibility of the pigment such as the titanium nitride-containing particles described above. In the present invention, the dispersant and the binder resin described below are different components.
As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
As the dispersant, a polymer dispersant (for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly(meth)acrylate, (meth)acrylic type) Copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivative.
The polymer compound can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer based on its structure.

The polymer compound is adsorbed on the surface of the object to be dispersed such as the titanium nitride-containing particles and the pigment which is optionally used together, and acts to prevent reaggregation of the object to be dispersed. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site on the pigment surface are preferable.
On the other hand, by modifying the surface of the titanium nitride-containing particles, the adsorptivity of the polymer compound to the particles can be promoted.

The polymer compound preferably has a structural unit having a graft chain. In the present specification, “structural unit” has the same meaning as “repeating unit”.
Since the polymer compound having a structural unit having such a graft chain has an affinity with a solvent due to the graft chain, the dispersibility of pigments such as titanium nitride-containing particles and the dispersion stability after aging are improved. It is excellent. Further, due to the presence of the graft chain, the polymer compound having the structural unit having the graft chain has affinity with the polymerizable compound or other resins that can be used in combination. As a result, a residue is less likely to be generated in the alkali development.
When the graft chain is long, the steric repulsion effect is high and the dispersibility of the pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorptivity of the titanium nitride-containing particles or the like to the pigment will decrease, and the dispersibility of the pigment or the like will tend to decrease. Therefore, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably has 50 to 2000 atoms excluding hydrogen atoms, and has more atoms excluding hydrogen atoms. Those of 60 to 500 are more preferable.
Here, the graft chain is from the root of the main chain of the copolymer (atoms bonded to the main chain in the group branched from the main chain) to the end of the group branched from the main chain.

The graft chain preferably has a polymer structure, and examples of such a polymer structure include a poly(meth)acrylate structure (for example, a poly(meth)acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide structure. , And a polyether structure and the like.
In order to improve the interaction between the graft chain and the solvent, and thereby enhance the dispersibility, the graft chain contains at least one selected from the group consisting of a polyester structure, a polyether structure and a poly(meth)acrylate structure. It is preferably a graft chain having, and more preferably a graft chain having at least one of a polyester structure and a polyether structure.

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

  Commercially available macromonomers corresponding to the structural unit having a graft chain of the polymer compound and suitably used for the synthesis of the polymer compound include AA-6 (trade name, Toagosei Co., Ltd.), AA-10 ( Trade name, Toagosei Co., Ltd., AB-6 (trade name, Toagosei Co., Ltd.), AS-6 (trade name, Toagosei Co., Ltd.), AN-6 (trade name, Toagosei ( Co., Ltd.), AW-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-714 (trade name, manufactured by Toagosei Co., Ltd.), AY-707 (trade name, manufactured by Toagosei Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-30 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-32 (product Name, manufactured by Toagosei Co., Ltd., Bremmer PP-100 (trade name, manufactured by NOF Corporation), BREMMER PP-500 (trade name, manufactured by NOF Corporation), BREMMER PP-800 (trade name, manufactured by NOF CORPORATION). NOF CORPORATION, BREMMER PP-1000 (trade name, NOF Corporation), BREMMER 55-PET-800 (trade name, NOF Corporation), BREMMER PME-4000 (trade name, NOF CORPORATION, BREMMER PSE-400 (trade name, manufactured by NOF CORPORATION), BREMMER PSE-1300 (trade name, manufactured by NOF Corporation), BREMMER 43PAPE-600B (trade name, NOF Corporation) (Manufactured by K.K.) and the like are used. Among them, AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (trade name, manufactured by Toagosei Co., Ltd.), AB-6 (trade name, manufactured by Toagosei Co., Ltd.) are preferable. , AS-6 (trade name, Toa Gosei Co., Ltd.), AN-6 (trade name, Toa Gosei Co., Ltd.), and Bremmer PME-4000 (trade name, NOF Co., Ltd.) and the like are used. Be done.

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

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

In Formulas (1) to (4), W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH. W ¹ , W ² , W ³ , and W ⁴ are preferably oxygen atoms.
In Formulas (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. From the viewpoint of synthetic constraints, X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms). Is more preferable, each independently a hydrogen atom or a methyl group is more preferable, and a methyl group is further preferable.

In Formulas (1) to (4), Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly limited in structure. 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 structures shown below, A and B mean the binding sites 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 because of the ease of synthesis.

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, but specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an amino group and the like. Is mentioned. Among these, as the organic group represented by Z ¹ , Z ² , Z ³ , and Z ⁴ , those having a steric repulsion effect are preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms. Is preferred, and among them, 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 is particularly preferable. The alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

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

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

Further, the polymer compound may have two or more kinds of structural units having different structures and having a graft chain. That is, in the molecule of the polymer compound, structural units represented by formulas (1) to (4) having different structures may be contained, and n and m in the formulas (1) to (4) may be included. , P, and q each represent an integer of 2 or more, in formulas (1) and (2), side chains may include structures in which j and k are different from each other, and formula (3) and In the formula (4), a plurality of R ³ , R ⁴ and X ⁵ present in the molecule may be the same or different from each other.

The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability and developability of the composition.
Further, the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability of the composition.

Wherein ^(1A), X ^1, Y 1, ^{Z 1} and n are the same as ^{X 1,} Y 1, ^{Z 1} and n in Formula (1), and preferred ranges are also the same. Wherein ^(2A), X ^2, Y 2, ^{Z 2} and m are as defined ^{X 2,} Y 2, ^{Z 2} and m in the formula (2), and preferred ranges are also the same.

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

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

  The polymer compound more preferably has a structural unit represented by the formula (1A) as a structural unit having a graft chain.

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

  Further, the polymer compound preferably 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). However, in the present invention, the hydrophobic structural unit is a structural unit having no acid group (eg, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).

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

The ClogP value is obtained from Daylight Chemical Information System, Inc. It is the value calculated by the program "CLOGP" available from This program provides the value of "calculated logP" calculated by the Hansch, Leo fragment approach (see below). The fragment approach is based on the chemical structure of a compound and estimates the compound's logP value by dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to that fragment. The details are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used.
A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.; G. Sammmens, J.M. B. Taylor and C.I. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. Leo. Calculating logPoint from structure. Chem. Rev. , 93, 1281-1306, 1993.

logP means a common logarithm of a partition coefficient P (Partition Coefficient), and quantitatively shows how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. Is a physical property value expressed as a numerical value, and is represented by the following formula.
logP=log(Coil/Cwater)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.
It means that the oil solubility increases when the value of logP increases to a positive value across 0, and the water solubility increases when the absolute value increases to a negative value, and there is a negative correlation with the water solubility of organic compounds. It is widely used as a parameter for estimating the water content.

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

In the above formulas (i) to (iii), R ¹ , R ² , and R ³ are each independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.) or a carbon number of 1 to 6 Represents an alkyl group (eg, methyl group, ethyl group, propyl group, etc.).
R ¹ , R ² , and R ³ are preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and more preferably hydrogen atoms or methyl groups. It is particularly preferable that R ² and R ³ are hydrogen atoms.
X represents an oxygen atom (-O-) or an imino group (-NH-), and is preferably an oxygen atom.

L is a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group) or a divalent aromatic group (for example, an arylene group , A substituted arylene group), a divalent heterocyclic group, an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR ³¹ —, where R ^31. Is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), and combinations thereof.

  The divalent aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for carbon number of an aliphatic group, 1-15 are more preferable, and 1-10 are more preferable. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but a saturated aliphatic group is preferable. Moreover, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.

  6-20 are preferable, as for carbon number of a bivalent aromatic group, 6-15 are more preferable, and 6-10 are more preferable. Moreover, 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 heterocycle. The heterocycle may be condensed with another heterocycle, an aliphatic ring or an aromatic ring. Moreover, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (=O), a thioxo group (=S), an imino group (=NH), a substituted imino group (=N-R ³² , where R ³² is a fat). Group group, aromatic group or heterocyclic group), aliphatic group, aromatic group, and heterocyclic group.

L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L may include a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. Polyoxyethylene structure, - _(OCH 2 _CH 2) represented by n-, n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

Z is an aliphatic group (eg, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group,) or an aromatic group (eg, an aryl group, a substituted aryl group, an arylene group, a substituted arylene group). , Heterocyclic groups, and combinations thereof. These groups an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group ^{(-NR 31} -, wherein ^{R 31} is an aliphatic group, an aromatic Group or heterocyclic group) or a carbonyl group (—CO—) may be contained.

The aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for carbon number of an aliphatic group, 1-15 are more preferable, and 1-10 are more preferable. The aliphatic group further includes a ring-assembled hydrocarbon group and a cross-linked cyclic hydrocarbon group. Examples of the ring-assembled hydrocarbon group include bicyclohexyl group, perhydronaphthalenyl group, biphenyl group and 4 -Cyclohexylphenyl group and the like are included. Examples of the bridged cyclic hydrocarbon ring include 2 such as pinane, bornane, norpinane, norbornane, and bicyclooctane ring (bicyclo[2.2.2]octane ring, bicyclo[3.2.1]octane ring, etc.). Tricyclic hydrocarbon rings such as a cyclic hydrocarbon ring, homobredan, adamantane, tricyclo[5.2.1.0 ^2,6 ]decane, and tricyclo[4.3.1.1 ^2,5 ]undecane ring , Tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodecane, and a tetracyclic hydrocarbon ring such as a perhydro-1,4-methano-5,8-methanonaphthalene ring. Further, the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring, for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a perhydrophenalene ring are condensed is also included.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Moreover, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.

  6-20 are preferable, as for carbon number of an aromatic group, 6-15 are more preferable, and 6-10 are more preferable. Moreover, 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 heterocycle. The heterocycle may be condensed with another heterocycle, an aliphatic ring or an aromatic ring. Moreover, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (═O), a thioxo group (═S), an imino group (═NH), a substituted imino group (═N—R ³² , where R ³² is a fat). Group group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.

In the above formula (iii), R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (eg, A methyl group, an ethyl group, a propyl group, etc.), Z, or LZ. Here, L and Z have the same meanings as described above. As R ⁴ , R ⁵ , and R ⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

In the present invention, as the monomer represented by the general formula (i), R ¹ , R ² , and R ³ are hydrogen atoms or methyl groups, and L is a single bond or an alkylene group or an oxyalkylene structure. A compound having a divalent linking group including, wherein X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
As the monomer represented by the general formula (ii), 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. Are preferred. Further, as the monomer represented by the general formula (iii), R ⁴ , R ⁵ , and R ⁶ are hydrogen atoms or methyl groups, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Certain compounds are preferred.

Examples of representative compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, and styrenes.
As examples of typical compounds represented by formulas (i) to (iii), the compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Be incorporated into.

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

The polymer compound can introduce a functional group capable of forming an interaction with a pigment such as titanium nitride-containing particles. Here, the polymer compound preferably further has a structural unit having a functional group capable of forming an interaction with a pigment such as particles containing titanium nitride.
Examples of the functional group capable of forming an interaction with the pigment such as titanium nitride-containing particles include an acid group, a basic group, a coordinating group, and a reactive functional group.
When the polymer compound has an acid group, a basic group, a coordinating group, or a reactive functional group, a structural unit having an acid group, a structural unit having a basic group, and a coordinating group, respectively. It is preferable to have a structural unit having or a structural unit having reactivity.
In particular, when the polymer compound further has an alkali-soluble group such as a carboxylic acid group as an acid group, the polymer compound can be imparted with developability for pattern formation by alkali development.
That is, by introducing an alkali-soluble group into the polymer compound, the composition of the present invention is such that the polymer compound as a dispersant that contributes to the dispersion of the pigment such as titanium nitride-containing particles has alkali solubility. . The composition containing such a polymer compound has an excellent light-shielding property in the exposed area and improves the alkali developability in the unexposed area.
Further, when the polymer compound has a structural unit having an acid group, the polymer compound tends to be compatible with the solvent and the coating property tends to be improved.
This is because the acid group in the structural unit having an acid group easily interacts with the pigment such as titanium nitride-containing particles, the polymer compound stably disperses the pigment such as titanium nitride-containing particles, and the titanium nitride. It is presumed that this is because the viscosity of the polymer compound in which the pigment such as the content particles is dispersed is low, and the polymer compound itself is likely to be stably dispersed.

  However, 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 a different structural unit, but an alkali-soluble group as an acid group Is a structural unit different from the above-mentioned hydrophobic structural unit (that is, does not correspond to the above-mentioned hydrophobic structural unit).

The acid group, which is a functional group capable of forming an interaction with a pigment such as titanium nitride-containing particles, includes, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and preferably, At least one selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, and particularly preferable ones have good adsorption power to pigments such as titanium nitride-containing particles and high dispersibility of pigments. In point, it is a carboxylic acid group.
That is, the polymer compound preferably further has 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 type or two or more types of structural units having an acid group.
The polymer compound may or may not contain a structural unit having an acid group, but in the case of containing, the content of the structural unit having an acid group is, in terms of mass, based on the total mass of the polymer compound. %, preferably 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage to image strength due to alkali development.

Examples of the basic group that is a functional group capable of forming an interaction with a pigment such as titanium nitride-containing particles include a primary amino group, a secondary amino group, a tertiary amino group, and a hetero atom containing an N atom. There is a ring, an amide group, and the like, and a preferable one is a tertiary amino group because it has good adsorption power to the pigment such as titanium nitride-containing particles and high dispersibility of the pigment. 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, but in the case of containing, the content of the structural unit having a basic group is, in terms of mass, the total mass of the polymer compound. On the other hand, it is preferably 0.01% or more and 50% or less, and more preferably 0.01% or more and 30% or less from the viewpoint of suppressing development inhibition.

Examples of the coordinating group that is a functional group capable of forming an interaction with a pigment such as titanium nitride-containing particles, and the reactive functional group include, for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, and an acid anhydride. And acid chlorides. Preferred is an acetylacetoxy group because of its good adsorption of pigment such as titanium nitride-containing particles and high dispersibility of the pigment. The polymer compound may have one type or two or more types of these groups.
The polymer compound may or may not contain a structural unit having a coordinating group, or a structural unit having a reactive functional group, but in the case of containing, the content of these structural units is In terms of mass, it is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less, from the viewpoint of suppressing inhibition of developability, with respect to the total mass of the polymer compound.

  When the polymer compound in the present invention has a functional group capable of forming an interaction with a pigment such as titanium nitride-containing particles other than the graft chain, as described above, with various pigments such as titanium nitride-containing particles As long as it has a functional group capable of forming an interaction, and how these functional groups are introduced is not particularly limited, the polymer compound is represented by the following general formulas (iv) to (vi). It is preferable to have at least one structural unit selected from structural units derived from the monomer represented by

In formulas (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, etc.), or a carbon number. Represents an alkyl group of 1 to 6 (eg, methyl group, ethyl group, propyl group, etc.).
In general formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably, Each independently represents a hydrogen atom or a methyl group. In general formula (iv), it is particularly preferable that R ¹² and R ¹³ are each a hydrogen atom.

X ₁ in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
Further, Y in the general formula (v) represents a methine group or a nitrogen atom.

In addition, L ₁ in the general formulas (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 alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , An arylene group, and a substituted arylene group), a divalent heterocyclic group, an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino bond (—NR ³¹ ′— Here, R ³¹ ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.

  The divalent aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for carbon number of an aliphatic group, 1-15 are more preferable, and 1-10 are more preferable. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Moreover, 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.

  6-20 are preferable, as for carbon number of a bivalent aromatic group, 6-15 are more preferable, and 6-10 are the most preferable. Moreover, 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 heterocycle. One or more of other heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (=O), a thioxo group (=S), an imino group (=NH), a substituted imino group (=N-R ³² , where R ³² is a fat). Group group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.

L ₁ is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L ₁ may include a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. Polyoxyethylene structure, - _(OCH 2 _CH 2) represented by n-, n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In the general formulas (iv) to (vi), Z ₁ represents a functional group capable of forming an interaction with a pigment such as titanium nitride-containing particles other than the graft chain, a carboxylic acid group, and a tertiary group. It is preferably an amino group, and more preferably a carboxylic acid group.

In the general formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 6 carbon atoms. (e.g., methyl group, ethyl group, propyl group, etc.), - it represents a _{Z 1} or _L 1 -Z _1,. Here, L ₁ and Z ₁ have the same meanings as L ₁ and Z ₁ described above, and preferred examples are also the same. R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently 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, and L ₁ is an alkylene group or an oxyalkylene structure. A compound having a divalent linking group including, wherein X ₁ is an oxygen atom or an imino group, and Z ₁ is a carboxylic acid group is preferred.
Further, as the monomer represented by the general formula (v), 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 methine. Compounds that are groups are preferred.
Further, as the monomer represented by the general formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom or a methyl group, and L ₁ is a single bond or an alkylene group, Compounds in which Z is a carboxylic acid group are preferred.

Below, the typical example of the monomer (compound) represented by General formula (iv)-General formula (vi) is shown.
Examples of the monomer include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound having an addition-polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) with succinic anhydride. , A reaction product of a compound having an addition-polymerizable double bond and a hydroxyl group in the molecule with phthalic anhydride, and a reaction product of a compound having an addition-polymerizable double bond and a hydroxyl group in the molecule with tetrahydroxyphthalic anhydride , A reaction product of a compound having an addition-polymerizable double bond and a hydroxyl group in the molecule with trimellitic anhydride, a reaction product of a compound having an addition-polymerizable double bond and a hydroxyl group in the molecule with pyromellitic anhydride, Examples thereof include acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4-hydroxyphenylmethacrylamide.

  The content of the structural unit having a functional group capable of forming an interaction with the pigment such as titanium nitride-containing particles depends on the interaction with the pigment such as titanium nitride-containing particles, dispersion stability, and penetrability into a developing solution. From the viewpoint of, the total mass of the polymer compound is preferably 0.05% by mass to 90% by mass, more preferably 1.0% by mass to 80% by mass, and further preferably 10% by mass to 70% by mass.

Further, the polymer compound is a structural unit having a graft chain, a hydrophobic structural unit, and titanium nitride-containing particles for the purpose of improving various properties such as image strength as long as the effects of the present invention are not impaired. Other structural units having various functions, which are different from structural units having a functional group capable of forming an interaction with the pigment (for example, structural units having a functional group having an affinity for the dispersion medium used in the dispersion). ) May be further included.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
The polymer compound may use one kind or two or more kinds of these other structural units, and the content thereof is preferably 0% or more and 80% or less with respect to the total mass of the polymer compound in terms of mass. And particularly preferably 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.

The acid value of the polymer compound is preferably in the range of 0 mgKOH/g or more and 160 mgKOH/g or less, more preferably 10 mgKOH/g or more and 140 mgKOH/g or less, and further preferably 20 mgKOH/g or more and 120 mgKOH/g. The range is as follows.
When the acid value of the polymer compound is 160 mgKOH/g or less, pattern peeling during development during formation of a cured film can be more effectively suppressed. Further, when the acid value of the polymer compound is 10 mgKOH/g or more, the alkali developability becomes better. Further, when the acid value of the polymer compound is 20 mgKOH/g or more, the sedimentation of pigments such as titanium nitride-containing particles can be further suppressed, the number of coarse particles can be further reduced, and the stability of the composition over time can be improved. You can improve more.

  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. Further, a resin having a desired acid value can be obtained by changing the content of the structural unit containing an acid group which is a constituent of the polymer compound.

The weight average molecular weight of the polymer compound in the present invention is 4,000 as a polystyrene equivalent value by GPC (gel permeation chromatography) method from the viewpoint of suppressing pattern peeling during development and developing property when forming a cured film. Or more and 300,000 or less, preferably 5,000 or more and 200,000 or less, more preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. It is particularly preferable that
The GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID×15 cm) as columns, and THF (tetrahydrofuran as eluent). ) Is used.

  The polymer compound can be synthesized based on a known method, and examples of the solvent used when synthesizing the polymer compound include ethylene dichloride, 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-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, Examples thereof include ethyl acetate, methyl lactate, and ethyl lactate. 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 Kusunoki Kasei Co., Ltd., "Disperbyk-101 (polyamidoamine phosphate)" manufactured by BYK Chemie, 107 (carboxylic acid ester), 110 (acid group). Containing copolymer), 111 (phosphoric acid-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer), "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", "EFKA4047, 4050-4010-4165 (polyurethane type), EFKA4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyester) manufactured by EFKA. Amide), 5765 (high molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)", "Ajinomoto Fine-Techno Co., Ltd." Azisper PB821, PB822, PB880, PB881", Kyoeisha "Floren TG-710 (urethane oligomer)", "Polyflow No. 50E, No. 300 (acrylic copolymer)" manufactured by Kagaku Co., Ltd., "Disparlon KS-860, 873SN, 874, #2150 (fat) manufactured by Kusumoto Kasei Co., Ltd. Group polyvalent carboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725", "Demol RN, N (naphthalenesulfonic acid formalin polycondensate)" manufactured by Kao Corporation, MS, C, SN-B (formalin polycondensate of aromatic sulfonic acid)", "homogenol L-18 (polymer polycarboxylic acid)", "emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "Acetamine 86 (stearylamine acetate)", manufactured by Nippon Lubrizol Co., Ltd. "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), 3000, 12000, 17,000, 20000, 27000 (terminal part). Having a functional part in 2), 24000, 28000, 32000, 38500 (graft copolymer), Nikko Chemicals' Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) )”, Kawaken Fine Chemicals Co., Ltd. Hinoact T-8000E, Shin-Etsu Chemical Co., Ltd., Organo Roxane polymer KP341, "W001: cationic surfactant" manufactured by Yusho Co., Ltd., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonyl Nonionic surfactants such as phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", "EFKA-46" manufactured by Morishita Sangyo Co., Ltd. EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450", "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100" manufactured by San Nopco Ltd. And the like, a polymer dispersant such as “ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, manufactured by ADEKA CORPORATION. P-123", "Ionet (trade name) S-20" manufactured by Sanyo Kasei Co., Ltd., and the like. Also, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
Moreover, as a commercially available product of amphoteric resin, for example, DISCERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001-DISPER, manufactured by Big Chemie. 2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajinomoto Fine-Techno Azisper PB821, Azisper PB822, and Azisper PB881 etc. are mentioned.
These polymer compounds may be used alone or in combination of two or more kinds.

  As specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.

Further, as the dispersant, in addition to the above-described polymer compounds, the graft copolymers of paragraphs 0037 to 0115 of JP 2010-106268 A (corresponding paragraphs 0075 to 0133 of US2011/0124824) can be used. The contents of which are incorporated herein by reference.
In addition to the above, it has a side chain structure in which the acidic groups of paragraphs 0028 to 0084 of JP 2011-153283 A (corresponding paragraphs 0075 to 0133 of US2011/0279759) are bonded via a linking group. Polymeric compounds containing components can be used, the contents of which are incorporated herein by reference.

When the composition contains a dispersant, the content of the dispersant is preferably 0.1 to 50 mass% and more preferably 0.5 to 30 mass% with respect to the total solid content of the composition.
The dispersants may be used alone or in combination of two or more. When two or more kinds are used together, the total amount is preferably within the above range.

<Binder resin>
The composition of the present invention preferably contains a binder resin.
A linear organic polymer is preferably used as the binder resin. As such a linear organic polymer, any known one can be used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to allow water development or weak alkaline water development. Among them, as the binder resin, an alkali-soluble resin (a resin having a group that promotes alkali-solubility) is particularly preferable.
The binder resin is a linear organic polymer and promotes at least one alkali solubility in a molecule (preferably a molecule having a (meth)acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resin, polysiloxane resin, (meth)acrylic resin, (meth)acrylamide resin, (meth)acrylic/(meth)acrylamide copolymer resin are preferable, and developability is preferable. From the viewpoint of control, a (meth)acrylic resin, a (meth)acrylamide resin, and a (meth)acrylic/(meth)acrylamide copolymer resin are preferable.
Examples of the group that promotes alkali solubility (hereinafter, also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Among these, those soluble in an organic solvent and developable with a weak alkaline aqueous solution are preferable, and an alkali-soluble resin having a structural unit derived from (meth)acrylic acid is more preferable. These acid groups may be only one kind or two or more kinds.

Examples of the binder resin include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, and JP-B-54-25957. Those described in JP-A-54-92723, JP-A-59-53836, and JP-A-59-71048, that is, resins and acid anhydrides obtained by homopolymerizing or copolymerizing monomers having a carboxyl group. A resin in which an acid anhydride unit is hydrolyzed or half-esterified or half-amidated by homopolymerizing or copolymerizing a monomer having, and an epoxy acrylate obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride, Can be mentioned. Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene, and examples of monomers having an acid anhydride include: Maleic anhydride etc. are mentioned. Further, similarly, an acidic cellulose derivative having a carboxylic acid group in its side chain is also given as an example. In addition to these, a polymer obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group is useful.
Further, the acetal-modified polyvinyl alcohol-based binder resin having an acid group described in each of European Patent No. 993966, European Patent No. 1204000, and JP 2001-318463 A has film strength and developability. It has excellent balance and is suitable.
In addition to these, polyvinylpyrrolidone, polyethylene oxide and the like are useful as the water-soluble linear organic polymer. Further, alcohol-soluble nylon, polyether which is a reaction product of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin, and the like are also useful for increasing the strength of the cured film.

In particular, among these, [benzyl (meth)acrylate/(meth)acrylic acid/optionally other addition-polymerizable vinyl monomer] copolymer, and [allyl(meth)acrylate/(meth)acrylic acid/necessary] Other addition-polymerizable vinyl monomers] copolymers are suitable because they are excellent in the balance of film strength, sensitivity, and developability.
Examples of commercially available products include Acrybase FF-187, FF-426 (manufactured by Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Nippon Shokubai Co., Ltd.), and Cyclomer P (ACA) manufactured by Daicel Ornex Co., Ltd. 230AA etc. are mentioned.

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

It is also preferable to use a polymer having a structural unit having a graft chain and a structural unit having an acid group (alkali-soluble group) as the binder resin.
The definition of the structural unit having a graft chain is synonymous with the structural unit having a graft chain contained 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 phosphoric acid group, or a phenolic hydroxyl group, and preferably at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. Yes, and more preferred are carboxylic acid groups.

  As the structural unit having an acid group, it is preferable to have at least one structural unit selected from structural units derived from the monomers represented by the following general formulas (vii) to (ix).

In formulas (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, etc.), or a carbon number. Represents an alkyl group of 1 to 6 (eg, methyl group, ethyl group, propyl group, etc.).
In formulas (vii) to (ix), R ²¹ , R ²² , and R ²³ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably, Each independently represents a hydrogen atom or a methyl group. In general formula (vii), it is particularly preferable that R ²¹ and R ²³ are each a hydrogen atom.

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

In addition, L ₂ in the general formulas (vii) to (ix) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (eg, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, and substituted alkynylene group), divalent aromatic group (eg, , An arylene group, and a substituted arylene group), a divalent heterocyclic group, an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino bond (—NR ⁴¹ ′— Here, R ⁴¹ ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.

  The divalent aliphatic group may have a cyclic structure or a branched structure. 1-20 are preferable, as for carbon number of an aliphatic group, 1-15 are more preferable, and 1-10 are more preferable. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Moreover, 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.

  6-20 are preferable, as for carbon number of a bivalent aromatic group, 6-15 are more preferable, and 6-10 are more preferable. Moreover, 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 heterocycle. One or more other heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (═O), a thioxo group (═S), an imino group (═NH), a substituted imino group (═N—R ⁴² , where R ⁴² is a fat). Group group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.

L ₂ is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L ₂ may include a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. Polyoxyethylene structure, - _(OCH 2 _CH 2) represented by n-, n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In general formula (vii) to general formula (ix), Z ₂ is an acid group, and preferably a carboxylic acid group.

In formula (ix), R ²⁴ , R ²⁵ , and R ²⁶ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or the like), an alkyl group having 1 to 6 carbon atoms. (e.g., methyl group, ethyl group, propyl group, etc.), - represents a _{Z 2} or _L 2 -Z _2,. Here, L ₂ and Z ₂ have the same meanings as L ₂ and Z ₂ described above, and preferred examples are also the same. As R ²⁴ , R ²⁵ , and R ²⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

In the present invention, as the monomer represented by the general formula (vii), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a methyl group, and L ₂ represents an alkylene group or an oxyalkylene structure. A divalent linking group containing is preferably a compound in which X ₂ is an oxygen atom or an imino group and Z ₂ is a carboxylic acid group.
In addition, as the monomer represented by the general formula (vii), 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 methine. Compounds that are groups are preferred.
Further, as the monomer represented by the general formula (ix), a compound 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 is preferable.

  The binder resin can be synthesized by the same method as the dispersant having the structural unit having a graft chain described above, and the preferable acid value and weight average molecular weight are also the same.

The binder resin may have one type or two or more types of structural units having an acid group.
The content of the structural unit having an acid group is, in terms of mass, based on the total mass of the binder resin, preferably 5 to 95%, and more preferably from the viewpoint of suppressing damage of image strength due to alkali development, It is 10 to 90%.

The content of the binder resin in the composition of the present invention is preferably 0.1 to 30 mass% and more preferably 0.3 to 25 mass% with respect to the total solid content of the composition.
The binder resins may be used alone or in combination of two or more. When two or more kinds are used together, the total amount is preferably 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. Is more preferable, 0.05 to 0.3 is more preferable, and 0.1 to 0.3 is further preferable. When the content ratio D/P is within the above range, not only the performance reproducibility of the dispersion liquid is excellent, but also the patterning property (resolution) of the cured film is excellent.

<Polymerizable compound>
The composition of the present invention preferably contains a polymerizable compound.
The polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having two or more groups, further preferably three or more, and particularly preferably five or more. 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)acryloyl group.

The polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof and a multimer thereof, and the monomer is preferable.
100-3000 are preferable and, as for the molecular weight of a polymeric compound, 250-1500 are more preferable.
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 (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters, amides, and multimers thereof. However, preferred are esters of unsaturated carboxylic acids with aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids with aliphatic polyhydric amine compounds, and multimers thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or an epoxy, the above unsaturated carboxylic acid A dehydration condensation reaction product of an ester or amide with a monofunctional or polyfunctional carboxylic acid is also preferably used. Further, a reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, thiol, halogen group, tosyloxy group Reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent, such as, with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. Further, instead of the above unsaturated carboxylic acid, it is also possible to use a compound group in which unsaturated phosphonic acid, vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is substituted.
As these specific compounds, the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can be preferably used in the present invention.

  In the present invention, the polymerizable compound is also preferably a compound having at least one group having an ethylenically unsaturated bond and having a boiling point of 100° C. or higher under normal pressure. As examples thereof, for example, the compounds described in paragraph 0227 of JP 2013-29760 A and paragraphs 0254 to 0257 of JP 2008-292970 A can be referred to, and the contents thereof are incorporated in the present specification.

The polymerizable compound includes dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.). , Dipentaerythritol penta(meth)acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd., and a structure in which these (meth)acryloyl groups are mediated by an ethylene glycol residue or a propylene glycol residue (for example, SR454 and SR499 commercially available from Sartomer Co., Ltd.). ) Is preferred. 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 preferred embodiments of the polymerizable compound are shown below.

  The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid. A polymerizable compound having a group is more preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.

  The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH/g, more preferably 5 to 30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the development dissolution property is good, and when it is 40 mgKOH/g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

A compound having a caprolactone structure is also a preferable embodiment of the polymerizable compound.
The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, An ε-caprolactone-modified polyfunctional (meth)acrylate obtained by esterifying (meth)acrylic acid and ε-caprolactone with a polyhydric alcohol such as tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine is given. be able to. Among them, compounds having a caprolactone structure represented by the following general formula (Z-1) are preferable.

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

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

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

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

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

In the formula (Z-4) and (Z-5), E are each _{independently, - ((CH 2) y} CH 2 O) -, or _{- ((CH 2) y CH} (CH 3) O) Represents -, y independently represents an integer of 0 to 10, and X independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxyl group.
In the general formula (Z-4), the total of (meth)acryloyl groups is 3 or 4, m each independently represents an integer of 0 to 10, and the sum of each m is an integer of 0 to 40. ..
In the general formula (Z-5), the total of (meth)acryloyl groups is 5 or 6, n is each independently an integer of 0 to 10, and the sum of each n is an integer of 0 to 60. ..

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

  The compound represented by the general formula (Z-4) or the general formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (Z-5), a form in which all six X are acryloyl groups, in the general formula (Z-5), a compound in which all six X are acryloyl groups and six X Among them, an embodiment in which at least one is a mixture with a compound having a hydrogen atom is preferable. With such a structure, the developability can be further improved.

  Further, 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) is a conventionally known process, which is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by a reaction and a step of introducing a (meth)acryloyl group by reacting, for example, (meth)acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize the compound 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 are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f), and among them, the exemplified compounds (a), (b), (e) and (f) are preferable.

  Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer Co., Ltd., Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having 6 pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having 3 isobutyleneoxy chains, etc., manufactured by K.K.

As the polymerizable compound, urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Also, urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are preferable. is there. Further, addition-polymerizable compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, can be used. By using it, a composition having a very high photosensitivity speed can be obtained.
As commercially available products, urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-. Examples include 306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha).

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

Further, it is also preferable that the composition has a polymerizable compound having a cardo skeleton from the viewpoint of reducing the development residue.
As the polymerizable compound having a cardo skeleton, a polymerizable compound having a 9,9-bisarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.

General formula (Q3)

In the general formula (Q3), Ar ^{11 to} Ar ¹⁴ each independently represent an aryl group containing a benzene ring surrounded by a broken line. X ^{1 to} X ⁴ each independently represent a substituent having a polymerizable group, and the 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 limit values of e, f, g and h are Ar ^{11 to} Ar ¹⁴ respectively. It is a value obtained by subtracting a, b, c or d from the number of substituents that can be possessed. However, when Ar ^{11 to} Ar ¹⁴ are polycyclic aromatic hydrocarbon groups each independently containing a benzene ring surrounded by a broken line as one of the condensed rings, X ^{1 to} X ⁴ and R ^{1 to} R ⁴ are respectively It may be independently substituted with a benzene ring surrounded by a broken line or may be substituted with a ring other than the benzene ring surrounded with a broken line.

In the general formula (Q3), the aryl group containing a benzene ring surrounded by a broken line and represented by Ar ^{11 to} Ar ¹⁴ is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms. (For example, a phenyl group and a naphthyl group) are more preferable, and a phenyl group (only a benzene ring surrounded by a broken line) is further preferable.

In the general formula (Q3), X ^{1 to} X ⁴ each independently represent a substituent having a polymerizable group, and the 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 preferable.
The aliphatic group having a polymerizable group represented by X ^{1 to} X ⁴ is not particularly limited, but is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, and having 2 to 10 carbon atoms. An alkylene group is more preferable, and an alkylene group having 2 to 5 carbon atoms is further preferable.
Further, in the aliphatic group having a polymerizable group represented by X ^{1 to} X ⁴ , when the above aliphatic group is substituted with a hetero atom, —NR— (R is a substituent), an oxygen atom, or a sulfur atom. It is more preferable that the non-adjacent —CH ₂ — in the aliphatic group is substituted with an oxygen atom or a sulfur atom, and the non-adjacent —CH ₂ in the aliphatic group is preferable. It is further preferred that-is substituted with an oxygen atom. The aliphatic group having a polymerizable group represented by X ^{1 to} X ⁴ is preferably substituted at 1 to 2 positions with a hetero atom, more preferably substituted at 1 position with a hetero atom, and Ar ^{11 to} Ar It is further preferred that one position adjacent to the aryl group containing a benzene ring surrounded by a broken line represented by ¹⁴ is substituted with a hetero atom.
The polymerizable group contained in the aliphatic group having a polymerizable group represented by X ^{1 to} X ⁴ is a radically polymerizable or cationically polymerizable polymerizable group (hereinafter, also referred to as a radically polymerizable group and a cationically polymerizable group, respectively). Is preferred.
As the radically polymerizable group, a generally known radically polymerizable group can be used, and a preferable example thereof is a polymerizable group having a radically polymerizable ethylenically unsaturated bond, and specifically, Examples thereof include a vinyl group and a (meth)acryloyloxy group. Among them, a (meth)acryloyloxy group is preferable, and an acryloyloxy group is more preferable.
As the cationically polymerizable group, a generally known cationically polymerizable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, Also, a vinyloxy group and the like can be mentioned. Of these, an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferable.
The polymerizable group contained in the substituents contained in Ar ^{1 to} Ar ⁴ is preferably a radical polymerizable group.
Two or more of Ar ¹ to Ar ⁴ include a substituent having a polymerizable ^group, preferably contains a substituent with 2-4 polymerizable group of Ar 1 ~Ar ^4, Ar 1 ~Ar It is more preferable that 2 or 3 of ⁴ contain a substituent having a polymerizable group, and it is further preferable that 2 of Ar ^{1 to} Ar ⁴ contain a substituent having a polymerizable group.
In the case where Ar ^{11 to} Ar ¹⁴ are polycyclic aromatic hydrocarbon groups each containing a benzene ring independently surrounded by a broken line as one of the condensed rings, X ^{1 to} X ⁴ are independently benzene surrounded by a broken line. The ring may be substituted, or the ring other than the benzene ring surrounded by the broken line may be substituted.

In the general formula (Q3), a and b each independently represent an integer of 1 to 5, preferably 1 or 2, and more preferably both a and b are 1.
In the general formula (Q3), c and d each independently represent an integer of 0 to 5, preferably 0 or 1, 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 substituent represented by R ^{1 to} R ⁴ is not particularly limited, and examples thereof include a halogen atom, a halogenated alkyl group, an alkyl group, an alkenyl group, an acyl group, a hydroxyl group, a hydroxyalkyl group, an alkoxy group, an aryl group, and a hetero group. Examples thereof include an aryl group and an alicyclic group. The substituent represented by R ^{1 to} R ⁴ is preferably an alkyl group, an alkoxy group or an aryl group, and more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group. More preferably, it is a methyl group, a methoxy group or a phenyl group.
In the general formula (Q3), when Ar ^{11 to} Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, R ^{1 to} R ⁴ are respectively The benzene ring surrounded by a broken line may be independently substituted, or the ring other than the benzene ring surrounded by a broken line may be substituted.

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 substituents that Ar ^{11 to} Ar ¹⁴ can have. Is a value obtained by subtracting a, b, c or d from the number of.
Each of e, f, g and h is preferably 0 to 8 independently, more preferably 0 to 2, and even more preferably 0.
When Ar ^{11 to} Ar ¹⁴ each independently represent a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, e, f, g and h are preferably 0 or 1. , 0 is more preferable.

  Examples of the compound represented by the above formula (Q3) include 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene. As the polymerizable compound having a 9,9-bisarylfluorene skeleton, compounds described in JP 2010-254732 A can also be suitably used.

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

<Polymerization initiator>
The composition of the present invention preferably contains a polymerization initiator.
The polymerization initiator is not particularly limited and may be appropriately selected from known polymerization initiators. For example, those having photosensitivity (so-called photopolymerization initiators) are preferable.
When the composition of the present invention contains a photopolymerization initiator and the above-mentioned polymerizable compound in addition to the titanium nitride-containing particles, the composition is cured by irradiation with actinic rays or radiation, so that the “photosensitive composition It is sometimes called.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light in the ultraviolet region are preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer, or an initiator that initiates cationic polymerization depending on the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (eg, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. And oxime compounds, 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 those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in British Patent No. 1388492, compounds described in JP-A No. 53-133428, compounds described in German Patent 3337024, F.I. C. Schaefer et al. Org. Chem. 29, 1527 (1964), the compound described in JP-A-62-58241, the compound described in JP-A-5-281728, the compound described in JP-A-5-34920, and U.S. Pat. No. 4,129,976. The compounds and the like described in the specification can be mentioned.

  From the viewpoint of exposure sensitivity, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium. A compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound and derivatives thereof, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyloxadiazole compound, and a compound selected from the group consisting of 3-aryl-substituted coumarin compounds. preferable.

  More preferably, trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, trihalomethyltriazine compounds, α-aminoketones. At least one compound selected from the group consisting of compounds, oxime compounds, triallylimidazole dimers, and benzophenone compounds is particularly preferable.

In particular, when the composition of the present invention is used for producing a light-shielding film for a solid-state image sensor, it is necessary to form a fine pattern in a sharp shape, and therefore, the curability is high and there is no residue in the unexposed area. It is important to be done. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when forming a fine pattern in a solid-state image sensor, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must also be kept low. Therefore, taking these points into consideration, it is particularly preferable to use an oxime compound as the photopolymerization initiator for forming a fine pattern such as a solid-state image sensor. Further, by using the oxime compound, the color transfer property can be further improved.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

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

An oxime compound is more preferable as the photopolymerization initiator. In particular, an oxime-based initiator is preferable because it has high sensitivity, high polymerization efficiency, can be cured regardless of the concentration of the coloring material, and the concentration of the coloring material can be easily designed.
As specific examples of the oxime compound, the compounds described in JP 2001-233842 A, the compounds described in JP 2000-80068 A, and the compounds described in JP 2006-342166 A can be used.
Examples of oxime compounds that can be preferably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyiminobutan-2-one. 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane 2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like can be mentioned.
Also, J. C. S. Perkin II (1979) pp. 1653-1660), J. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, the compound described in JP-A-2000-66385, the compound described in JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166. Be done.
Among commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.), ADEKA ARKUL'S NCI-831 and ADEKA ARKRUZ NCI-930 (manufactured by ADEKA) can also be used. N-1919 (made by ADEKA) can also be used.

In addition, as the oxime compound other than the above description, the compound described in JP 2009-519904 A in which the oxime is linked to the carbazole N position, the compound described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in JP 2010-15025 A and U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced into a dye moiety, ketoxime compounds described in WO 2009-131189, triazine skeleton and oxime skeleton are the same molecule. The compounds described in US Pat. No. 7,556,910, which are contained in US Pat. ..
Preferably, for example, paragraphs 0274 to 0275 of JP 2013-29760 A can be referred to, and the contents thereof are incorporated in the present specification.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The N—O bond of the oxime may be an (E)-form oxime compound, a (Z)-form oxime compound, or a mixture of the (E)-form and the (Z)-form. ..

In 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.
In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metal atomic group.
Examples of the monovalent non-metal atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Further, these groups may have one or more substituents. Further, the above-mentioned 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, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-mentioned substituents.
In general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-mentioned substituents.

  In the present invention, an oxime compound having a fluorine atom can be used as the photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP2010-262028A, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP2013-164471A. A compound (C-3) etc. are mentioned. This content is incorporated herein.

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

In Formula (1), R ¹ and R ² are each independently 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 When it represents an arylalkyl group having 7 to 30 carbon atoms and R ¹ and R ² are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R ³ and R ⁴ are each independently, Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a single bond or carbonyl. Indicates a group.

In the formula ^(2), R ^1, R 2, ^{R 3} and ^{R 4} have the same meanings as ^{R 1,} R 2, ^{R 3} and ^{R 4} in the formula (1), ^{R 5 is} -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 Represents an 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 arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms; X represents a single bond or a carbonyl group, and a represents an integer of 0-4.

In the above formulas (1) and (2), R ¹ and R ² are each independently preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclohexyl group or a phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a single bond.
Specific examples of the compounds represented by the formulas (1) and (2) include the compounds described in paragraph numbers 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein.

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

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

  Further, the commercially available polymerization initiator is not particularly limited, but IRGACURE OXE 01 (1.2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime) manufactured by BASF Japan Ltd. )])), IRGACURE OXE 02 (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime)), 2-(acetyl Oxyiminomethyl) thioxanthen-9-one, O-acyl oxime compound (for example, ADEKA company Adeka optomer N-1919, Adeka Arcules NCI-831), Adeka Archules NCI-930, IRGACURE-OXE03, IRGACURE. -OXE04 and the like are also included, the contents of which are incorporated herein.

The oxime compound preferably has a maximum absorption wavelength in the wavelength range of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength range of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 405 nm.
The oxime compound has a molar absorption coefficient at 365 nm or 405 nm of preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and more preferably 5,000 to 200, from the viewpoint of sensitivity. More preferably, it is 1,000.
A known method can be used for the molar extinction coefficient of the compound, for example, in an ultraviolet-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L. It is preferable to measure.
The photopolymerization initiators used in the present invention may be used in combination of two or more, if necessary.

  When the composition of the present invention contains a polymerization initiator, the content of the polymerization initiator is preferably 0.1 to 30% by mass, and preferably 1 to 25% by mass based on the total solid content in the composition. %, more preferably 1 to 10% by mass. The composition of the present invention may contain only one type or two or more types of polymerization initiators. When two or more kinds are contained, the total amount is preferably within the above range.

<Solvent>
The composition of the present invention preferably contains a solvent, more preferably an organic solvent.
Examples of the organic solvent include, for example, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxypropyl acetate, N,N-dimethylformamide, dimethyl sulfoxide, γ -Butyrolactone, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate and the like, but not limited to.

The composition of the present invention may contain one kind of organic solvent, or may contain two or more kinds of organic solvents. It is preferable to contain two or more kinds of organic solvents from the viewpoint that particle size fluctuation can be suppressed.
When two or more organic solvents are contained, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -Composed of two or more selected from the group consisting of heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate and propylene glycol monomethyl ether acetate. Preferably.

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

<Water>
The composition of the present invention may contain water. Water may be added intentionally or may be unavoidably contained in the composition by adding each component contained in the composition of the present invention.
The content of water is preferably 0.1 to 1% by mass, more preferably 0.1 to 0.8% by mass, and 0.1 to 0.4% with respect to the total mass of the composition. It is more preferable that the content is% by mass. When the water content is within the above range, the patterning property (resolution) when the cured film is produced is excellent, and the anticorrosion property of the electrode material is also excellent. 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 stability of viscosity of the composition with time is more excellent. .

<Other ingredients>
The composition of the present invention may contain components other than the components described above.
Hereinafter, each component will be described in detail.

(Silane coupling agent)
The silane coupling agent is a compound having a hydrolyzable group and a functional group other than that in the molecule. The hydrolyzable group such as an alkoxy group is bonded to the silicon atom.
The hydrolyzable group means a substituent directly bonded to a silicon atom and capable of forming a siloxane bond by a hydrolysis reaction and/or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group has a carbon atom, the carbon number thereof is preferably 6 or less, more preferably 4 or less. Particularly, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
Further, the silane coupling agent preferably does not contain a fluorine atom and a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded) in order to improve adhesion between the substrate and the cured film. Silicon atoms (excluding silicon atoms to which a hydrolyzable group is bonded), alkylene groups substituted with silicon atoms, linear alkyl groups having 8 or more carbon atoms, and branched chain alkyl groups having 3 or more carbon atoms are included. Not desirable.

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

The silane coupling agent preferably has at least one curable functional group selected from the group consisting of (meth)acryloyloxy group, epoxy group, and oxetanyl group. The curable functional group may be directly bonded to the silicon atom or may be bonded to the silicon atom via a linking group.
In addition, a radically polymerizable group is also mentioned as a suitable aspect of the curable functional group contained in the said silane coupling agent.

  The molecular weight of the silane coupling agent is not particularly limited, and from the viewpoint of handleability, it is often 100 to 1000, and from the viewpoint that the effect of the present invention is more excellent, 270 or more is preferable, and 270 to 1000 is more preferable.

One of the preferable embodiments of the silane coupling agent is the silane coupling agent X represented by the formula (W).
Formula _{(W) R Z2 -Lz-Si-} (R Z1) 3
R _z1 represents a hydrolyzable group, and the definition is as described above.
R _z2 represents a curable functional group, the definition is as described above, and the preferable range is also as described above.
Lz represents a single bond or a divalent linking group. When Lz represents a divalent linking group, the divalent linking group may be an alkylene group which may be substituted with a halogen atom, an arylene group which may be substituted with a halogen atom, -NR ¹² -, or -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 an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms and an arylene group which may be substituted by a halogen atom having 6 to 12 carbon atoms, or At least selected from the group consisting of these groups and —NR ¹² —, —CONR ¹² —, —CO—, —CO ₂ —, SO ₂ NR ¹² —, —O—, —S—, and SO ₂ —. A group consisting of a combination with one type of group is preferable, and an alkylene group having 2 to 10 carbon atoms which may be substituted with a halogen atom, —CO ₂ —, —O—, —CO—, —CONR ¹² —, or A group consisting of a combination of these groups is more preferable. Here, R ¹² represents a hydrogen atom or a methyl group.

  As the silane coupling agent X, N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-trimethoxy. Silane (Shin-Etsu Chemical Co., Ltd. trade name KBM-603), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (Shin-Etsu Chemical Co., Ltd. trade name KBE-602), γ-aminopropyl-trimethoxysilane. (Shin-Etsu Chemical Co., Ltd. trade name KBM-903), γ-aminopropyl-triethoxysilane (Shin-Etsu Chemical Co., Ltd. trade 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.

Another preferred embodiment of the silane coupling agent is a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule, and having a hydrolyzable group bonded to the silicon atom. Can be mentioned.
The silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can bond with the following atoms and substituents. They may be the same atom, substituents or different. Atoms and substituents that can be bonded are 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, an amino group substitutable with an alkyl group and/or an aryl group, and a silyl group. Examples thereof include a group, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group. These substituents further include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group substitutable with an alkyl group and/or an aryl group, a halogen atom, a sulfonamide group, It may be substituted with an alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxyl group, or a salt thereof, a sulfo group, a salt thereof, or the like.
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 formula (Z).

The silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is a substituent. It is preferred to have at least one organic group. The structure of the amino group may be present in the molecule in the form of a partial structure of the nitrogen-containing heterocycle, or may be present as a substituted amino group such as aniline.
Here, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and combinations thereof. These may further have a substituent, and examples of the substituent that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom and a sulfonamide. Examples thereof include a group, an alkoxycarbonyl group, a carbonyloxy group, an amide group, a urea group, an alkyleneoxy group, an ammonium group, an alkylammonium group, a carboxyl group, a salt thereof, and a sulfo group.
In addition, the nitrogen atom is preferably bonded to the curable functional group via any organic linking group. Examples of the preferable organic linking group include the above-mentioned nitrogen atom and a substituent that can be introduced into the organic group bonded thereto.

The definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferable range is also as described above.
The silane coupling agent Y may have at least one curable functional group in one molecule, but may have two or more curable functional groups in order to improve sensitivity and stability. From the viewpoint of, it is preferable to have 2 to 20 curable functional groups, more preferably 4 to 15, and most preferably 6 to 10 curable functional groups in the molecule.

  The molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, but include the above-mentioned range (preferably 270 or more).

  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, based on the total solid content in the composition. 0 to 6 mass% is more preferable.

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

(UV absorber)
The composition of the present invention may contain an ultraviolet absorber. Thereby, the shape of the pattern can be made more excellent (fine).
As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. As specific examples thereof, the compounds of paragraphs 0137 to 0142 (corresponding paragraphs 0251 to 0254 of US2012/0068292) of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated into the present specification. ..
Besides, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by Daito Kagaku, trade name: UV-503) and the like are also suitably used.
Examples of the ultraviolet absorber include the compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
The composition of the present invention may or may not contain an ultraviolet absorber, but in the case of containing it, the content of the ultraviolet absorber is preferably 0.001 to 15 mass% with respect to the total solid content of the composition. , 0.01 to 10% by mass is more preferable, and 0.1 to 5% by mass is further preferable.

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

  By containing a fluorosurfactant in the composition of the present invention, the liquid properties (particularly, the fluidity) when prepared as a coating liquid are further improved, and the uniformity of the coating thickness and the liquid saving property are further improved. be able to. That is, in the case of forming a film using a coating liquid to which a composition containing a fluorine-containing surfactant is applied, the interfacial tension between the coating surface and the coating liquid is lowered, and the wettability to the coating surface is reduced. It is improved and the coating property on the coated surface is improved. Therefore, it is possible to more favorably form a film having a uniform thickness with a small thickness unevenness.

  The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid saving, and also has good solubility in the composition.

Examples of the fluorinated surfactant include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475 and F479. F482, F554, F780, RS-72-K (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Ltd.), Surflon S-382, SC. -101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (all manufactured by Asahi Glass Co., Ltd.). ), PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA). As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2005-117327 can also be used. A block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include the compounds described in JP 2011-89090 A.
The fluorine-based surfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
Further, a fluoropolymer having an ethylenically unsaturated group in its side chain can also be used as the fluorosurfactant. As specific examples, compounds described in JP-A-2010-164965, paragraphs 0050 to 0090 and paragraphs 0289 to 0295, for example, Megafac RS-101, RS-102, RS-718K, and RS- manufactured by DIC Corporation. 72-K and the like.

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (eg, glycerolpropoxylate, glycerinethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene. Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, manufactured by BASF). 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, and Solspers 20000 (manufactured by Nippon Lubrizol Co., Ltd.), etc. Also, NCW- manufactured by Wako Pure Chemical Industries, Ltd. 101, NCW-1001, and NCW-1002 can also be used.

  Specific examples of the cationic surfactant include phthalocyanine derivative (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based ( Co) Polymer 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, W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Kasei Co., Ltd.).

  Examples of 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, Toray Dow Corning Co., Ltd. )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials, Inc.), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.). , BYK307, BYK323, and BYK330 (above, manufactured by Big Chemie).

  As the surfactant, only one kind may be used, or two or more kinds may be combined. The content of the surfactant is preferably 0.001 to 2.0 mass% and more preferably 0.005 to 1.0 mass% with respect to 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. For example, a sensitizer, a co-sensitizer, a cross-linking agent, a curing accelerator, a filler, a thermal curing accelerator, a polymerization inhibitor, a plasticizer, a diluent, an oil sensitizer, and further, adhesion to the substrate surface Accelerators and other auxiliaries (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension adjusting agents, chain transfer agents, etc.) You may add well-known additives, such as these, as needed.
These components are described, for example, in paragraph Nos. 0183 to 0228 of JP2012-003225A (<0237> to <0309> of corresponding US Patent Application Publication No. 2013/0034812) and JP2008-250074A. Descriptions of paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, and paragraph numbers 0159 to 0184 of JP2013-195480A can be referred to, and the contents thereof are incorporated in the present specification. ..

(Colorant)
The composition of the present invention can also use a colorant other than the titanium nitride-containing particles described above (hereinafter, also simply referred to as “colorant”). The colorant is used, for example, for adjusting the chromaticity of the composition, and it is possible to replace part of the titanium nitride with the colorant as long as the OD value does not decrease. Examples of such colorants include pigments (organic pigments such as black organic pigments and chromatic organic pigments, and inorganic pigments) and dyes.

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

((Pigment))
Examples of the pigment include various conventionally known pigments.
The chromatic organic pigments include the following. However, the present invention is not limited to these.
Color 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.
C. I. 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. ,
C. I. 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.
C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. C.I. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. C.I. I. Pigment Blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79,80 etc.

Further, as the green pigment, use is made of a halogenated zinc phthalocyanine pigment having an average number of halogen atoms in the molecule of 10 to 14, an average number of bromine atoms of 8 to 12 and an average number of chlorine atoms of 2 to 5. Is also possible. Specific examples thereof include the compounds described in WO 2015/118720.
These organic pigments can be used alone or in various combinations for increasing color purity.

  As the black pigment, various known black pigments can be used. For example, carbon black and the black metal-containing inorganic pigments shown below may be mentioned. Examples of the black metal-containing inorganic pigment include metal oxides and metals containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti and Ag. Nitrogen substances are included. These may be used alone or in the form of a mixture of two or more kinds. Further, a black pigment may be used in combination with an inorganic pigment having another hue to prepare a desired light-shielding property. Examples of specific inorganic pigments that can be used in combination include, for example, zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, and yellow lead. , Zinc yellow (1 type of zinc yellow, 2 types of zinc yellow), Ultramarine blue, Prussian blue (ferric cyanide iron) Zircon gray, Praseodymium yellow, Chrome titanium yellow, Chrome green, Peacock, Victoria green, Navy blue (Prussian blue) Unrelated), vanadium zirconium blue, chrome tin pink, ceramic red, salmon pink, etc. In particular, for the purpose of exhibiting a light-shielding property in a wide wavelength range from ultraviolet to infrared, these black pigments and inorganic pigments having other hues may be used alone or as a mixture of plural kinds of pigments. Is possible.

  The black pigment is preferably carbon black or titanium black, and titanium black is particularly preferable from the viewpoint of having a light-shielding property in a wide wavelength range from ultraviolet to infrared. Titanium black is black particles containing titanium atoms. Preferred are low order titanium oxide and titanium oxynitride. Although not particularly limited, examples of titanium oxynitride include titanium oxynitrides such as those disclosed in WO 2008/123097, JP2009-58946A, JP2010-14848A, JP2010-97210A and JP2011-2274670A. Further, a mixture of titanium oxynitride and titanium carbide as disclosed in JP-A-2010-95716 can be used. The surface of the titanium black particles can be modified, if necessary, for the purpose of improving dispersibility and suppressing cohesion. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and can be treated with a water-repellent substance as disclosed in JP2007-302836A. . Titanium black is a composite oxide of Cu, Fe, Mn, V, Ni or the like, and one or more black pigments such as cobalt oxide, iron oxide or carbon black for the purpose of adjusting dispersibility, colorability and the like. You may contain in combination.

  As a method for producing titanium black, a mixture of titanium dioxide and metallic titanium is heated in a reducing atmosphere for reduction (JP-A-49-5432), and ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (JP-A-57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (JP-A-60-65069, JP-A-60-65069). 61-201610), a method of adhering a vanadium compound to titanium dioxide or titanium hydroxide, and reducing at high temperature in the presence of ammonia (JP-A 61-201610). However, the present invention is not limited to these.

Although the specific surface area of titanium black is not particularly limited, BET (Brunauer, Emmett, Teller ) is preferably measured value is less than ^{5 m} 2 / g or more 150 meters ² / g by method, ^{20 m} 2 / g or more 120 m ² / It is more preferably g or less.
Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corp.), Tilack. D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.

  The above black pigment preferably has an average primary particle diameter of 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 further preferably 100 nm or less. The average primary particle diameter of the black pigment is a value measured by the following method. A mixed solution containing a black pigment is diluted 80 times with propylene glycol monomethyl ether acetate, and the obtained diluted solution is a value measured by a dynamic light scattering method. This measurement is an average particle diameter obtained by using a Microtrac (trade name) UPA-EX150 manufactured by Nikkiso Co., Ltd.

Further, it is also preferable to contain titanium black as a dispersed material containing titanium black and Si atoms.
In this form, titanium black is contained in the composition as a substance to be dispersed, and the content ratio (Si/Ti) of Si atoms and Ti atoms in the substance to be dispersed is 0.05 or more in terms of mass. Is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is further preferable.
Here, the dispersed material includes both titanium black in a primary particle state and an aggregate (secondary particle) state.
The following means can be used to change the Si/Ti of the substance to be dispersed (for example, 0.05 or more).
First, a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the dispersion is subjected to a reduction treatment at a high temperature (for example, 850 to 1000° C.) to mainly disperse titanium black particles. A dispersed material containing Si and Ti as components can be obtained. The reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia.
Examples of titanium oxide include TTO-51N (trade name: manufactured by Ishihara Sangyo).
Titanium oxide produced by the plasma method can be preferably used because its particle size is smaller than that of commercially available titanium oxide fine particles (see the Journal of the Japan Institute of Metals Volume 63 No. 1 (1999) 74-81). ..
Examples of commercially available silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name: manufactured by Evonik).
A dispersant may be used to disperse the titanium oxide and the silica particles. Examples of the dispersant include those described in the above section on the dispersant.
The above dispersion may be carried out in a solvent. Examples of the solvent include water and organic solvents. The thing explained in the column of the above-mentioned organic solvent is mentioned.
Titanium black whose Si/Ti is adjusted to, for example, 0.05 or more can be prepared by the method described in paragraph No. [0005] and paragraphs [0016] to [0021] of JP 2008-266045 A, for example. It can be made.

By adjusting the content ratio (Si/Ti) of Si atoms and Ti atoms in the dispersed material containing titanium black and Si atoms to a suitable range (for example, 0.05 or more), the composition containing this dispersed material is adjusted. When the light-shielding film is formed using a substance, the residue derived from the composition outside the region where the light-shielding film is formed is reduced. The residue contains components derived from the composition, such as titanium black particles and a resin component.
The reason why the residue is reduced is not clear yet, but the above-mentioned dispersed substance tends to have a small particle size (for example, the particle size is 30 nm or less), and further, the Si atom of this dispersed substance is It is speculated that the increased content of the components reduces the adsorptivity of the entire film to the underlayer, which contributes to the improvement in the removability of the uncured composition (particularly titanium black) in the formation of the light-shielding film by development. There is.
In addition, titanium black is excellent in light-shielding property against light in a wavelength range over a wide range from ultraviolet light to infrared light. Therefore, titanium black and a dispersion target containing Si atoms (preferably Si/Ti is converted to mass). The light-shielding film formed by using (1) is 0.05 or more) exhibits excellent light-shielding properties.
The content ratio (Si/Ti) of Si atoms and Ti atoms in the dispersed material is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A. ) Can be used for measurement.
In addition, regarding the substance to be dispersed contained in the light-shielding film obtained by curing the composition, whether the content ratio of Si atoms and Ti atoms (Si/Ti) in the substance to be dispersed is 0.05 or more. The method (2) described in paragraph 0035 of JP-A-2013-249417 is used to determine the above.

In the dispersed material containing titanium black and Si atoms, the titanium black described above can be used.
In addition, in this dispersed material, a composite oxide of Cu, Fe, Mn, V, Ni, etc., cobalt oxide, iron oxide, carbon black, aniline is used together with titanium black for the purpose of adjusting dispersibility, colorability and the like. You may use together the black pigment which consists of black etc. as a to-be-dispersed body by combining 1 type(s) or 2 or more types.
In this case, it is preferable that titanium black occupies 50% by mass or more of the whole dispersed object.
Further, in this dispersion object, other colorants (organic pigments, dyes, etc.) may be optionally used together with titanium black for the purpose of adjusting the light-shielding property and the like, as long as the effects of the present invention are not impaired. Good.
Hereinafter, the materials used when introducing Si atoms into the substance to be dispersed will be described. When introducing Si atoms into the substance to be dispersed, a Si-containing substance such as silica may be used.
Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, and synthetic silica, and these may be appropriately selected and used.
Furthermore, when the particle size of the silica 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 fine particle type silica as the silica particles. Examples of fine particle type silica include silica described in paragraph 0039 of JP2013-249417A, the contents of which are incorporated herein.

Further, as the pigment, a tungsten compound and a metal boride can also be used.
Tungsten compounds and metal borides have high absorption with respect to infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, high light-shielding properties (shielding properties) against infrared rays) and have high absorption with respect to visible light. It is a low infrared 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 the tungsten compound and/or the metal boride.
Further, the tungsten compound and the metal boride have small absorption for light having a shorter wavelength than the visible region used for exposure such as a high pressure mercury lamp, KrF, and ArF used for image formation.

Examples of the tungsten compound include a tungsten oxide-based compound, a tungsten boride-based compound, and a tungsten sulfide-based compound, and a tungsten oxide-based compound represented by the following general formula (compositional formula) (I) is preferable.
M _x W _y O _z ... (I)
M represents a 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 metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Examples thereof include Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, and Bi, but an alkali metal is preferable. The metal of M may be one kind or two or more kinds.

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

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 more surely avoid generation of an impurity phase in the tungsten compound. it can.
When z/y is 2.2 or more, the chemical stability as a 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 compound represented by the above 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 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 fine particles is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. When the average primary particle diameter is in such a range, it becomes difficult for the tungsten fine particles to block visible light due to light scattering, so that the translucency in the visible light region can be further ensured. From the viewpoint of avoiding light scattering, the smaller the average primary particle diameter is, the more preferable, but the average primary particle diameter of the tungsten fine particles is usually 1 nm or more for reasons such as ease of handling during production.

  Further, two or more kinds of tungsten compounds can be used.

Although the tungsten compound is commercially available, when the tungsten compound is, for example, a tungsten oxide compound, the tungsten oxide compound is 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).
In addition, the tungsten oxide compound is also available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.

As the metal boride, lanthanum boride (LaB ₆ ), praseodymium boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), boride is used. Titanium (TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), boride One or more of molybdenum (MoB ₂ , Mo ₂ B ₅ , MoB), tungsten boride (W ₂ B ₅ ) and the like can be mentioned, and lanthanum boride (LaB ₆ ) is preferable.

  The metal boride is preferably fine particles. The average primary particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and further preferably 100 nm or less. When the average particle diameter is in such a range, it becomes difficult for the metal boride fine particles to block visible light due to light scattering, so that the light-transmitting property in the visible light region can be further ensured. From the viewpoint of avoiding light scattering, the smaller the average primary particle diameter is, the more preferable. However, the average primary particle diameter of the metal boride fine particles is usually 1 nm or more for reasons such as ease of handling during production.

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

  The metal boride is available as a commercial product, for example, a dispersion of metal boride fine particles such as KHF-07AH manufactured by Sumitomo Metal Mining Co., Ltd.

((dye))
Examples of the dye include JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, Tokubo 2592207, and US Pat. No. 4,808,501. U.S. Pat. No. 5,667,920, U.S. Pat. No. 5,050,950, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6-51. The dyes disclosed in Japanese Patent No. 194828 and the like can be used. When classified as chemical structures, pyrazole azo compounds, pyrromethene compounds, anilino azo compounds, triphenyl methane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used. Further, a dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.

  The composition of the present invention may contain an extender pigment, if necessary, in addition to the colorant. Examples of such extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. These extender pigments may be used alone or in admixture of two or more. The amount of the extender pigment used is usually 0 to 100 parts by mass, preferably 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the colorant. In the present invention, the colorant and the extender pigment can be used by modifying their surface with a polymer, as the case may be.

  The colorants may be used alone or in combination of two or more. The colorant may contain colored organic pigments such as red, blue, yellow, green, and purple. When the light-shielding pigment (specifically, titanium nitride-containing particles) and the coloring organic pigment are used in combination, it is preferable to use the coloring organic pigment in an amount of 1 to 40% by mass based on the light-shielding pigment. From the viewpoint of adjusting the tint, it is preferable to use a red pigment and a light-shielding pigment in combination, and the red pigment is preferably Pigment Red 254, although not particularly limited thereto. Further, it is preferable to use a yellow pigment and a light-shielding pigment in combination from the viewpoint of enhancing the light-shielding property, but the yellow pigment is preferably Pigment Yellow 150, although not particularly limited thereto.

  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 35 relative to the total solid content of the composition. -60 mass% is still more preferred.

(Pigment derivative)
The composition of the present invention may contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of an organic pigment is replaced with an acidic group, a basic group or a phthalimidomethyl group.
The organic pigment for constituting the pigment derivative, diketopyrrolopyrrole pigment, azo pigment, phthalocyanine pigment, anthraquinone pigment, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, slene pigments, metal complex pigments and the like.
As the acidic group contained in the pigment derivative, a sulfonic acid group, a carboxylic acid group and its quaternary ammonium salt group are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is particularly preferable. As the basic group contained in the pigment derivative, an amino group is preferable, and a tertiary amino group is particularly preferable.
Specific examples of the pigment derivative include the following compounds. Further, the description in paragraphs 0162 to 0183 of JP 2011-252065 A can be referred to, and the contents thereof are incorporated in the present specification.

  When the composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, based on the total mass of the colorant. The composition of the present invention may include only one type of pigment derivative, or may include two or more types. When two or more kinds are contained, the total amount is preferably 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 emulsifier, a wet pulverizer, a wet disperser).
The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign matters and reducing defects. The filter can be used without particular limitation as long as it has been conventionally used for filtration and the like. Examples of the filter include a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, a polyolefin resin such as polyethylene and polypropylene (PP) (including high density and ultra high molecular weight). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.
A suitable pore size of the filter is about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and further preferably 0.3 to 0.0 μm. It is 7 μm. Within this range, it is possible to reliably remove fine foreign matter such as impurities and agglomerates contained in the pigment while suppressing the filter clogging of the pigment.
When using the filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once, or may be performed twice or more. When different filters are combined to perform filtering two or more times, it is preferable that the pore diameter of the second and subsequent times is the same or larger than the pore diameter of the first filtering. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above. For the pore size here, the nominal value of the filter manufacturer can be referred to. The commercially available filter can be selected from, for example, various filters provided by Japan Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.), Kits Micro Filter Co., Ltd., etc. ..
The second filter may be made of the same material as the first filter described above. A suitable pore size of the second filter is about 0.2 to 10.0 μm, 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. Further, when the solid content of the composition is 40% by mass or less, the viscosity stability over time of the composition becomes better.

[Cured film (light-shielding film)]
The cured film of the present invention is obtained using the composition described above.
The cured film preferably has an uneven surface 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 concavo-convex structure may have a concavo-convex structure on the surface of the light-shielding film itself, or another layer may be provided on the light-shielding film to provide the concavo-convex structure. The shape of the surface uneven structure is not particularly limited, but the surface roughness is preferably in the range of 0.55 μm or more and 1.5 μm or less.
The reflectance of the light-shielding film is preferably 5% or less, more preferably 3% or less, and particularly preferably 2% or less.
The method for producing the surface uneven structure is not particularly limited, but a method of containing an organic filler or an inorganic filler in the light-shielding film or other layers, a lithography method utilizing exposure and development, etching, sputtering, nanoimprint method, etc. A method of roughening the surface of the light-shielding film or other layers may be used.
As a method of reducing the reflectance of the cured film, other than the above, a method of providing a low refractive index layer on the light shielding film, or a method of providing a plurality of layers having different refractive indexes (for example, a high refractive index layer) Another example is a method of forming a low optical density layer and a high optical density layer described in JP-A-2015-1654.
The cured film of the present invention mainly contains the above-mentioned titanium nitride-containing particles. The cured film of the present invention is preferably used as a light-shielding film, specifically, as an image sensor peripheral light-shielding film (frame light-shielding film) such as a CCD image sensor or a CMOS image sensor.
Hereinafter, a case where the cured film is used as the light shielding film around the image sensor will be described as an example. When the cured film is used as the light shielding film around the image sensor, there is a form in which the light shielding film around the image sensor is formed on the color filter and is applied to the CCD image sensor or the CMOS image sensor. That is, the above-mentioned cured film can be formed in a region of the color filter that is in contact with the frame region of the CCD image sensor or the CMOS image sensor.
The color filter having the image sensor peripheral light-shielding film of the present invention is formed using the composition described above (particularly, the photosensitive composition described above). The image sensor peripheral light-shielding film obtained by using the composition of the present invention has excellent patterning properties and electrode anticorrosion properties.

  When used as an image sensor peripheral light-shielding film, the film thickness of the light-shielding film is not particularly limited, but from the viewpoint of more effectively obtaining the effect of the present invention, the film thickness after drying is 0.2 μm or more and 50 μm or less. Is preferable, 0.5 μm or more and 30 μm or less is more preferable, and 0.7 μm or more and 20 μm or less is further preferable. The size (length of one side) of the light-shielding film is preferably 0.001 mm or more and 5 mm or less, more preferably 0.05 mm or more and 4 mm or less, from the viewpoint of more effectively obtaining the effect of the present invention. It is more preferably 1 mm or more and 3.5 mm or less.

<Cured film manufacturing method>
Next, the method for producing the cured film (light-shielding film) of the present invention is not particularly limited, and a known method can be adopted. Hereinafter, as a typical example, a method for producing a patterned cured film will be described in detail.

  The method for producing a patterned cured film of the present invention comprises a step of forming a composition layer (coating film) by applying the composition of the present invention on a substrate (hereinafter, abbreviated as "composition layer forming step" as appropriate). And a step of exposing the composition layer through a mask (hereinafter, abbreviated as “exposure step” as appropriate), and developing the composition layer after exposure to form a patterned cured film. (Hereinafter, appropriately abbreviated as “development step”).

Specifically, the composition of the present invention is applied directly or through another layer on a substrate to form a composition layer (composition layer forming step), and exposure is performed through a predetermined mask pattern. By curing only the composition layer portion irradiated with light (exposure step) and developing with a developing solution (developing step), a patterned cured film composed of pixels can be formed.
Hereinafter, each step will be described.

(Composition layer forming step)
In the composition layer forming step, the composition of the present invention is applied onto the substrate to form a composition layer (coating film).

Examples of the substrate include non-alkali glass used in liquid crystal display devices, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by adhering a transparent conductive film to these, photoelectric sensors used in solid-state imaging devices, and the like. A conversion element substrate (for example, a silicon substrate or the like), a CCD (Charge Coupled Device) substrate, a CMOS (Complementary Metal-Oxide Semiconductor) substrate, or the like can be used.
If necessary, an undercoat layer may be provided on these substrates in order to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the substrate surface.

  As a method for applying the composition of the present invention onto a substrate, various application methods such as slit application, ink jet method, spin coating, cast application, roll application, and screen printing method can be applied.

  When a color filter having a light-shielding film around an image sensor is manufactured, the coating thickness of the composition is preferably 0.35 μm or more and 2.0 μm or less, and 0.40 μm or more and 1. It is more preferably 5 μm or less.

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

(Exposure process)
In the exposure step, the composition layer (coating film) formed in the composition layer forming step is exposed through a mask to cure only the light-irradiated coating film portion.
The exposure is preferably carried out by irradiation with actinic rays or radiation, and 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. Irradiation intensity 5~1500mJ / cm ² is more preferably preferably 10~1000mJ / cm ^2.

(Development process)
Subsequent to the exposure step, an alkali development treatment (development step) is performed to elute the unirradiated portion in the exposure step into the alkaline aqueous solution. As a result, only the photo-cured portion (the coating film portion irradiated with light) remains.
As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable when a color filter having a light shielding film around the image sensor is manufactured. The developing temperature is usually 20 to 30° C., and the developing time is 20 to 90 seconds.

  Examples of the alkaline aqueous solution include an inorganic developing solution and an organic developing solution. As the inorganic developer, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate, the concentration is 0.001 to 10 mass%, preferably 0.01 to 1 mass An alkaline aqueous solution that is dissolved so as to become a 100% solution is included. Examples of organic developers include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7. An alkaline aqueous solution in which an alkaline compound such as undecene is dissolved so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An appropriate amount of a water-soluble organic solvent such as methanol and ethanol and/or a surfactant may be added to the alkaline aqueous solution. When a developer made of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  As the developing method, for example, a paddle developing method, a shower developing method, or the like can be used.

  In the method for producing a color filter having a cured film of the present invention, after the above-mentioned composition layer forming step, exposure step, and developing step, the formed cured film is heated and/or heated, if necessary. A curing step of curing by exposure may be included.

[Color filter, light-shielding film]
A cured film formed by using the composition of the present invention is used as a pixel black matrix of a color filter or a light-shielding film around an image sensor (frame light-shielding film) as described above, or in an image display device or a sensor module described later. It can be preferably used as a light-shielding film applied to various members.

(Color filter)
The color filter can be suitably used for solid-state imaging devices such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor), and is particularly suitable for high-resolution CCD and CMOS having over 1 million pixels. Is. The color filter can be used, for example, disposed between the light receiving portion of each pixel forming a CCD or CMOS and the microlens for collecting light. In addition, the color filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by a partition wall in, for example, a lattice shape. In this case, the partition wall preferably has a low refractive index for each color pixel. Examples of the image pickup device having such a structure include the devices described in JP 2012-227478 A and JP 2014-179577 A.
The form of the color filter of the invention is not particularly limited as long as it has the cured film.
In the color filter, the cured film can be suitably used as, for example, the pixel black matrix of the color filter or the image sensor peripheral light shielding film (frame light shielding film) as described above.

(Shading film)
The light-shielding film may be formed and used on various members in the image display device or the sensor module (for example, infrared light cut filter, outer peripheral portion of the solid-state image sensor, wafer-level lens outer periphery, back surface of the solid-state image sensor, etc.). it can.
Further, a light-shielding film may be formed on at least a part of the surface of the infrared light-cutting filter to provide an infrared light-cutting 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, more preferably 1.0 to 10 μm. The above thickness is an average thickness, and is a value obtained by measuring the thicknesses of arbitrary 5 or more points of the light shielding film and arithmetically averaging them.
The reflectance of the light-shielding film is preferably 10% or less, more preferably 8% or less, further preferably 6% or less, and particularly preferably 4% or less. The reflectance of the light-shielding film is a value obtained by making light of 400 to 700 nm incident on the light-shielding film at an incident angle of 5° and measuring the reflectance with a spectroscope UV4100 (trade name) manufactured by Hitachi High-Technology.

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

The substrate has a plurality of photodiodes that constitute the light receiving area of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon, etc., and the photodiodes and the light receiving electrodes of the photodiodes on the transfer electrodes. Has a light-shielding film that is open only in the area, and has a device protective film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light receiving portion, and a color filter is provided on the device protective film. It is a configuration having.
Furthermore, there is a structure having a light collecting means (for example, a microlens, etc.; the same applies hereinafter) below the color filter (on the side close to the substrate) on the device protective layer, and a structure having a light collecting means on the color filter. May be. In addition, the color filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by a partition wall in, for example, a lattice shape. In this case, the partition wall preferably has a low refractive index for each color pixel. Examples of the imaging device having such a structure include the devices described in JP2012-227478A and JP2014-179577A.

[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.

  For definitions of display devices and details of each display device, see, for example, “Electronic display device (Akio Sasaki, published by Industrial Research Institute Co., Ltd., 1990)”, “Display device (Junsho Ibuki, Sangyo Tosho Co., Ltd.) First year issued)" etc. Further, the liquid crystal display device is described in, for example, "Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Industrial Research Institute Co., Ltd., 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned “next-generation liquid crystal display technology”.

When the color filter of the present invention is applied to a liquid crystal display device, its form is not particularly limited.
Hereinafter, modes in which 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 may be used in a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT liquid crystal display device is described, for example, in "Color TFT liquid crystal display (Kyoritsu Shuppan Co., Ltd., 1996)". Further, the color filter of the present invention is a liquid crystal display device having a wide 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), or STN (Super). -Twist Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringing field switching), and R-OCB (Reflective Optimized).
Further, the color filter in the invention can be applied to a bright and high-definition COA (Color-filter On Array) system. In the COA type liquid crystal display device, the required characteristics for the color filter require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the peeling liquid resistance, in addition to the usual required characteristics as described above. Sometimes. Since the color filter of the present invention is excellent in light resistance and the like, it is possible to provide a COA type liquid crystal display device having high resolution and excellent long-term durability. A resin coating may be provided on the color filter layer in order to satisfy the required characteristics of low dielectric constant.
These image display systems are described, for example, on page 43 of "EL, PDP, LCD display-Technology and latest market trends-(published by Toray Research Center, Research and Research Division 2001)".

The liquid crystal display device of the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, or a viewing angle assurance film, in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. For these materials, see, for example, “The Market for Liquid Crystal Display Peripheral Materials/Chemicals ('94 Kentaro Shima Shima Co., Ltd., 1994)”, “Current status and future outlook of the 2003 liquid crystal related market (second volume)” Fuji Chimera Research Institute Co., Ltd., 2003)."
Regarding the backlight, see SID meeting Digest 1380 (2005) (A.Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Have been described.

  In addition, the cured film of the present invention is applied to portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as printer multifunction devices or scanners; surveillance cameras, bar code readers, cash automatics. ATMs, high-speed cameras, or industrial equipment such as personal identification using facial image authentication; vehicle-mounted camera equipment; medical cameras such as endoscopes, capsule endoscopes, or catheters; Optics used for space equipment such as sensors, biosensors, military reconnaissance cameras, 3D map cameras, weather or ocean observation cameras, land resource exploration cameras, or exploration cameras for space astronomical or deep space targets. It can be used as a light shielding member or a light shielding layer of a filter or a module. Furthermore, the cured film of the present invention can be used as an antireflection member or an antireflection layer of the above optical filter or module.

Further, the cured film of the present invention can be used for applications such as a micro LED (Light Emitting Diode) and a micro OLED (Organic Light Emitting Diode). It is not particularly limited, but it is preferably used for an optical filter or an optical film used for a micro LED or a micro OLED, as well as a member for imparting a light shielding function or an antireflection function.
Examples of the micro LED and the micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.

The cured film of the present invention can also be used for applications such as quantum dot displays. Although not particularly limited, it is suitably used for a member that has a light-shielding function and an antireflection function, as well as an optical filter and an optical film used for a quantum dot display.
Examples of quantum dot displays are US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960. The ones mentioned are mentioned.

  Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the following examples.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to this. In addition, "part" and "%" are based on mass unless otherwise specified.

[Composition]
In preparing the compositions of Examples and Comparative Examples, each component contained in the compositions will be described below.

<Titanium nitride-containing particles>
As the titanium nitride-containing particles, the titanium nitride-containing particles TiN-1 to TiN-19 produced as follows were used.

(Titanium nitride-containing particles TiN-1)
The titanium nitride-containing particles TiN-1 were produced using an apparatus similar to the black composite fine particle production apparatus shown in FIG. 1 of International Publication No. 2010/147098.
In the black composite fine particle manufacturing apparatus, a high frequency voltage of about 4 MHz and about 80 kVA is applied to the high frequency oscillation coil of the plasma torch, and argon gas of 50 L/min and nitrogen of 50 L/min are mixed as plasma gas from the plasma gas supply source. A gas was supplied to generate an argon-nitrogen thermal plasma flame in the plasma torch. Further, a carrier gas of 10 L/min was supplied from the atomizing gas supply source of the material supply device.
Then, titanium tetrachloride (liquid) as the particle raw material 1, liquid ammonia (made by Ube Industries) as the particle raw material 2, and Ti powder particles ("TC-200" made by Toho Tech Co., Ltd.) as the particle raw material 3 are carrier gases. It was fed into a hot plasma flame in a plasma torch with argon gas, evaporated in the hot plasma flame and highly dispersed in the gas phase. The flow rate ratio (volume ratio) of each of the particle raw materials 1 to 3 is as shown in Table 1.
Further, nitrogen was used as the gas supplied into the chamber by the gas supply device. At this time, the flow rate in the chamber was 5 m/sec, and the supply amount was 1000 L/min. The pressure in the cyclone was 50 kPa, and the supply rate of titanium particles from the chamber to the cyclone was 10 m/s (average value).
Next, heat treatment was performed on the particles using a lab kiln L/K manufactured by Narabashi Co., Ltd. as a firing furnace. Specifically, heat treatment was performed at 240° C. for 0.2 hours while supplying nitrogen as an atmosphere gas at 100 mL/min to the firing furnace.
In this way, titanium nitride-containing particles TiN-1 were obtained.

With respect to the obtained titanium nitride-containing particles TiN-1, the content of titanium (Ti) atoms and chlorine (Cl) atoms was measured by ICP emission spectroscopy. For the ICP emission spectroscopic analysis method, an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.
The content of nitrogen atoms was measured using an oxygen/nitrogen analyzer “EMGA-620W/C” (trade name) manufactured by Horiba Ltd., and calculated by an inert gas melting-thermal conductivity method. The results are shown in Table 1.
Also, with respect to titanium nitride-containing particles TiN-2 to TiN-19 described later, the content of Ti atoms, Cl atoms, and nitrogen atoms was measured by the same method as the titanium nitride-containing particles TiN-1. The remaining amount in each particle is an impurity such as oxygen and a metal element derived from an oxide present in the particle.
The results are shown in Tables 1 and 2.

The X-ray diffraction of titanium nitride-containing particles TiN-1 was measured by packing a powder sample in an aluminum standard sample holder and using a wide-angle X-ray diffraction method (manufactured by Rigaku Denki Co., Ltd., trade name “RU-200R”). As the measurement conditions, the X-ray source was CuKα ray, the output was 50 kV/200 mA, the slit system was 1°-1°-0.15 mm-0.45 mm, the measurement step (2θ) was 0.02°, and the scanning speed was 2°/min.
Then, the diffraction angle (2θ) of the peak derived from this TiN (200) plane was measured. From the half-width of this peak, the crystallite size constituting the particles was determined using Scherrer's formula. The results are shown in Table 1.
The diffraction angle 2θ and the crystallite size of the following titanium nitride-containing particles TiN-2 to TiN-19 were measured by the same method as that for the titanium nitride-containing particles TiN-1. The results are shown in Tables 1 and 2.

The average primary particle diameter of the titanium nitride-containing particles TiN-1 was measured using a transmission electron microscope (TEM) according to the method described above. Further, when the shape of the particles was observed at the same time as the above measurement, it was confirmed that 60 or more of 100 titanium nitride-containing particles to be observed were spherical. The results are shown in Table 1. Regarding the evaluation of particle shape observation, when 60% or more of the measurement targets were spherical, they were shown as “spherical” in the table. When the number of spherical particles was less than 60% of the measurement target, it was shown in the table as "spherical less than 60%". In addition, when “cube” is described in the table, the case where the number of cubic particles is 60% or more of the measurement target is shown. The cube is not limited to one that is visually recognized as a cube, and a polyhedron with visually recognized corners is also measured as a cube.
In addition, regarding the following titanium nitride-containing particles TiN-2 to TiN-19, the average primary particle diameter was 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.

The specific surface area of the titanium nitride-containing particles TiN-1 was measured using a high-precision full-automatic gas adsorption device (“BELSORP” 36) manufactured by Nippon Bell Co., Ltd. after vacuum degassing at 100° C., and then the liquid nitrogen temperature of N ₂ gas. The adsorption isotherm at (77K) was measured, and this isotherm was analyzed by the BET method to determine the specific surface area. The results are shown in Table 1.
The specific surface areas of the following titanium nitride-containing particles TiN-2 to TiN-19 were also 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)
Titanium nitride-containing particles TiN-1 In the same manner as the titanium nitride-containing particles TiN-1, except that the particle raw materials 1 to 3 used for the production of the particles, the flow rate ratios thereof, and the heat treatment conditions were as shown in Table 1. , Titanium nitride containing particles TiN-2 were produced.

(Titanium nitride-containing particles TiN-3)
Titanium nitride-containing particles TiN-1 In the same manner as the titanium nitride-containing particles TiN-1, except that the particle raw materials 1 to 3 used for the production of the particles, the flow rate ratios thereof, and the heat treatment conditions were as shown in Table 1. , Titanium nitride containing particles TiN-3 were produced.

(Titanium nitride-containing particles TiN-4)
Titanium nitride-containing particles TiN-1 In the same manner as the titanium nitride-containing particles TiN-1, except that the particle raw materials 1 to 3 used for the production of the particles, the flow rate ratios thereof, and the heat treatment conditions were as shown in Table 1. , Titanium nitride-containing particles TiN-4 were produced.

(Titanium nitride-containing particles TiN-5)
Titanium nitride-containing particles TiN-1 In the same manner as the titanium nitride-containing particles TiN-1, except that the particle raw materials 1 to 3 used for the production of the particles, the flow rate ratios thereof, and the heat treatment conditions were as shown in Table 1. , Titanium nitride containing particles TiN-5 were produced.

(Titanium nitride-containing particles TiN-6)
Titanium nitride-containing particles TiN-1 Titanium nitride-containing particles TiN-1 except that the particle raw materials 1 to 3 used for the production of the particles, the flow rate ratios thereof, the heat treatment conditions, and the flow velocity in the chamber are as shown in Table 1. In the same manner as in No. 1, titanium nitride-containing particles TiN-6 were produced.

(Titanium nitride-containing particles TiN-7)
Titanium nitride-containing particles TiN-7 were produced in the same manner as titanium nitride-containing particles TiN-6, except that the flow rate in the chamber was set as shown in Table 1.

(Titanium nitride-containing particles TiN-8)
Titanium nitride-containing particles TiN-1 Titanium nitride-containing particles TiN-1 except that the particle raw materials 1 to 3 used for the production of the particles, the flow rate ratios thereof, the heat treatment conditions, and the flow velocity in the chamber are as shown in Table 1. In the same manner as in No. 1, titanium nitride-containing particles TiN-8 were produced.

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

(Titanium nitride-containing particles TiN-10)
Titanium nitride-containing particles TiN-1 In the same manner as the titanium nitride-containing particles TiN-1, except that the particle raw materials 1 to 3 used for the production of the particles, the flow rate ratios thereof, and the heat treatment conditions were as shown in Table 1. , Titanium nitride containing particles TiN-10 were produced.

(Titanium nitride-containing particles TiN-11)
Titanium nitride-containing particles TiN-1 In the same manner as titanium nitride-containing particles TiN-1 except that the particle raw materials 1 to 3 used for the production of particles, the flow rate ratios thereof, and the heat treatment conditions were as shown in Table 2. , Titanium nitride containing particles TiN-11 were produced. In addition, the particle raw material 3 was not used in TiN-11.

(Titanium nitride-containing particles TiN-12)
Titanium nitride-containing particles TiN-1 In the same manner as titanium nitride-containing particles TiN-1 except that the particle raw materials 1 to 3 used for the production of particles, the flow rate ratios thereof, and the heat treatment conditions were as shown in Table 2. , Titanium nitride containing particles TiN-12 were produced. In addition, the particle raw materials 1 and 2 were not used in TiN-12.

(Titanium nitride-containing particles TiN-13)
Titanium nitride-containing particles TiN-1 In the same manner as titanium nitride-containing particles TiN-1 except that the particle raw materials 1 to 3 used for the production of particles, the flow rate ratios thereof, and the heat treatment conditions were as shown in Table 2. , Titanium nitride-containing particles TiN-13 were produced. The heat treatment temperature of the titanium nitride-containing particles TiN-13 was 250°C.

(Titanium nitride-containing particles TiN-14)
Titanium nitride-containing particles TiN-1 In the same manner as titanium nitride-containing particles TiN-1 except that the particle raw materials 1 to 3 used for the production of particles, the flow rate ratios thereof, and the heat treatment conditions were as shown in Table 2. , Titanium nitride containing particles TiN-14 were produced.

(Titanium nitride-containing particles TiN-15)
Titanium nitride-containing particles TiN-1 In the same manner as titanium nitride-containing particles TiN-1 except that the particle raw materials 1 to 3 used for the production of particles, the flow rate ratios thereof, and the heat treatment conditions were as shown in Table 2. , Titanium nitride-containing particles TiN-15 were produced.

(Titanium nitride-containing particles TiN-16)
Titanium nitride-containing particles TiN-16 were produced in the same manner as titanium nitride-containing particles TiN-15, except that the heat treatment conditions were as shown in Table 2.

(Titanium nitride-containing particles TiN-17)
Titanium nitride-containing particles TiN-1 In the same manner as titanium nitride-containing particles TiN-1 except that the particle raw materials 1 to 3 used for the production of the particles and the flow rate ratios thereof are as shown in Table 2. Material-containing particles TiN-17 were produced.

(Titanium nitride-containing particles TiN-18)
Titanium nitride-containing particles TiN-1 In the same manner as titanium nitride-containing particles TiN-1 except that the particle raw materials 1 to 3 used for the production of the particles and the flow rate ratios thereof are as shown in Table 2. Material-containing particles TiN-18 were produced.

(Titanium nitride-containing particles TiN-19)
Titanium nitride-containing particles TiN-1 In the same manner as titanium nitride-containing particles TiN-1 except that the particle raw materials 1 to 3 used for the production of particles, the flow rate ratios thereof, and the heat treatment conditions were as shown in Table 2. , Titanium nitride-containing particles TiN-19 were produced.

The production 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 the table, the heat treatment temperature is 240° C. except for titanium nitride-containing particles TiN-11, TiN-12, TiN-13 and TiN-14.

(Table 1)

(Table 2)

<Dispersant>
As the dispersant, Dispersants A to E having the following structures were used. In the dispersants A, B, and D, the numerical value described in each structural unit means the mass% of each structural unit with respect to all the structural units. Further, in the dispersant C, the numerical values (a to e) described in each structural unit are intended the molar ratio of each structural unit to all structural units, and x and y are the number of linkages. In the dispersant E, the numerical value described in the linking group linked to Z means the number linked to Z.

<Binder resin>
The following binder resins A and B were used as the binder resin.
Binder resin A (Acrycure RD-F8 manufactured by Nippon Shokubai, see the structure below)
-Binder resin B (Cyclomer P (ACA) 230AA manufactured by Daicel)

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

  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, manufactured by ADEKA ・IRGACURE-907: trade name, manufactured by BASF Japan

<Solvent>
-PGMEA: Propylene glycol monomethyl ether acetate-Cyclopentanone-Butyl acetate-Ethyl 3-ethoxypropionate-Distilled butyl acetate-Distilled cyclopentanone As the above-mentioned distilled butyl acetate and distilled cyclopentanone, commercially available butyl acetate The product obtained by distilling and purifying cyclopentanone was used.

<Polymerization inhibitor>
・P-methoxyphenol

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

<Preparation of pigment dispersion>
First, the titanium nitride-containing particles, the dispersant, and the solvent were mixed for 15 minutes with a stirrer (EUROSTAR manufactured by IKA) to obtain a dispersion. Next, the obtained dispersion was subjected to dispersion treatment using NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd. under the following conditions to obtain a pigment dispersion.
(Dispersion condition)
・Bead diameter: φ0.05 mm, (YTZ made by Nikkato)
・Bead filling rate: 65% by volume
・Mill peripheral speed: 10 m/sec
・Separator peripheral speed: 13m/s
・Amount of mixed liquid for dispersion treatment: 15 kg
・Circulation flow rate (pump supply rate): 90 kg/hour
・Treatment temperature: 19~21℃
・Cooling water: Water・Treatment time: 22 hours

<Preparation of composition>
Next, the pigment dispersion, the binder resin, the polymerizable compound, the polymerization initiator and the solvent were mixed and stirred to obtain each composition of Examples and Comparative Examples shown in Tables 3 to 5 below. The content (% by mass) of each component contained in each composition of Examples and Comparative Examples is shown in Tables 3 to 5.
The ratio of the dispersant to the titanium nitride-containing particles ((mass ratio) D/P), the solid content concentration (mass %) in the composition, and the water content (mass %) in the composition are shown below. Each of the compositions was prepared so that the pigment concentration (mass %) in the solid content was the ratio shown in each of Examples and Comparative Examples in Tables 3 to 5.

(Measurement of water content in composition)
The water content of each composition of Examples and Comparative Examples was measured by MKV-710 (trade name, manufactured by Kyoto Electronics Manufacturing Co., Ltd.) using the Karl Fischer method as a measurement principle. The results are shown in Tables 3 to 5.

[Evaluation test]
The following evaluation tests were carried out on the compositions of Examples and Comparative Examples.

<Outgas>
A frame for a color filter was produced using each composition of Examples and Comparative Examples.
Specifically, the compositions of Examples and Comparative Examples were spin-coated on a semiconductor substrate, which was constructed assuming an image sensor with an 8-inch substrate, so that the film thickness after prebaking was 1.5 μm. A coating film was formed. Subsequently, a binary mask capable of forming a light-shielding film having a horizontal width of 250 μm and a vertical width of 200 μm is arranged on the outer periphery of 720 μm in width and 520 μm in length, and exposed (exposure) using an i-line exposure device (FPA-3000+i5, manufactured by Canon). Amount of 500 mJ/cm ² ) and then further developed.
The obtained semiconductor substrate having a plurality of frames for color filters was cut into a size of 10 mm×10 mm, the amount of Cl in the outgas was detected by thermal desorption gas analysis (TDS), and evaluated according to the following criteria. went. The count intensity ratio of the peak position derived from Cl in the total outgas amount (detected total ion current value) from mass number 1 to 199 when the count derived from atmospheric components contained in the background is canceled is measured, and evaluated according to the following criteria. I went. The degree of vacuum during measurement was set to 1×10 ⁻⁷ Torr or less.
"A": 1 L of outgas, Cl content of 10 ppm or less "B": 1 L of outgas, Cl content of more than 10 ppm and 50 ppm or less "C": 1 L of outgas, Cl content of more than 50 ppm and 100 ppm or less "D": 1 L of outgas ,Cl amount exceeds 100ppm

<Number of particles>
A sample solution prepared by diluting the above composition by 500 times with PGMEA was prepared, and the number of particles having a size of 10 μm or more contained in 10 ml of this sample solution was measured by a flow type particle image analyzer (trade name “FPIA-3000”, Malvern). (Manufactured by the company).

<OD value>
A glass plate (EagleXG, Corning) having a thickness of 0.7 mm and 10 cm square was spin-coated with the compositions of Examples and Comparative Examples at a rotation speed of 1.0 μm to form a film, which was hot. A dry film was obtained on the plate by heat treatment at 100° C. for 2 minutes. The OD of the obtained substrate was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation), and the minimum OD value was measured in the wavelength region of 400 nm to 1200 nm, and the evaluation was performed according to 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 3. Less than 5

<Filterability>
The compositions of Examples and Comparative Examples were evaluated for filterability using a capsule filter DFA (manufactured by Nippon Pall Ltd., nylon pore size 0.45 μm, 2 inches). 16 kg of the composition was filtered under a flow rate of 400 ml/min and evaluated according to the following criteria.
"A": 16 kg were all filtered.
“B”: The flow rate became less than 400 mL/min after being filtered to 12 kg or more and less than 16 kg.
“C”: After being filtered to 8 kg or more and less than 12 kg, the flow rate became less than 400 mL/min.
"D": After being filtered to less than 8 kg, the flow rate was less than 400 mL/min.

<Composition stability over time (CM stability over time)>
The compositions of Examples and Comparative Examples were stored at 23°C for 30 days and then at 7°C for 9 months. Then, 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 type viscometer”) under the conditions of a rotation speed of 10 rpm and 23° C. The thickening rate was calculated more. The evaluation criteria are as follows.
(Thickness increase) = (Viscosity after aging)-(Viscosity immediately after preparation)/(Viscosity immediately after preparation)
"A": Thickening rate of less than 3% "B": Thickening rate of 3% to less than 5% "C": Thickening rate of 5% to less than 10% "D": Thickening rate of 10% or more

<Patterning property (resolution)>
Using the compositions of Examples and Comparative Examples, a coating film was formed on the image sensor device substrate by a spin coater. Then, the obtained coating film was prebaked at 100° C. for 2 minutes on a hot plate. Subsequently, the coating film that has been subjected to the above pre-baking treatment is exposed using an i-line exposure device (FPA, manufactured by Canon Inc.), and further developed to cover the outer peripheral portion of the light receiving portion on the substrate other than the dicing line and the electrode portion. Simultaneously with forming the light shielding film, 20 alignment marks having a line width of 20 μm were formed on the substrate.
The resolution was evaluated by observing the number of the formed alignment marks using an optical microscope.
"A": 20 marks were formed.
"B": 19 marks were formed.
"C": 18 marks were formed.
"D": There were 17 marks or less.

<Corrosion resistance of electrode>
Using the compositions of Examples and Comparative Examples, a coating film was formed on the image sensor device substrate by a spin coater. Next, the obtained device substrate after coating film formation was subjected to a prebaking treatment at 100° C. for 2 minutes on a hot plate. Subsequently, an i-line exposure device (FPA-3000+i5, manufactured by Canon Inc.) is used to expose the coating film that has been subjected to the above pre-baking treatment, and by further developing, a portion other than the dicing line and the electrode portion is formed on the outer peripheral portion of the light receiving portion on the substrate. A light-shielding film for coating was formed. Further, the obtained light-shielding film was subjected to heat treatment at 220° C. for 5 minutes using a hot plate (post-baking step).
The obtained wafer having a light-shielding film was stored for 3 days in an environment of a temperature of 110° C. and a humidity of 90% RH (HAST tester EHS-411M manufactured by Espec Corporation), and then a rust generation state of an electrode pattern was formed on the wafer. The thus-obtained 300 electrode pads were observed with an optical microscope (Olympus, trade name "LEXT OLS4500"), and the corrosion resistance of the electrodes was evaluated according to the following criteria.
"A": No change was observed "B": Electrode rust was 2 or less "C": Electrode rust was more than 2 and 10 or less "D": Electrode rust was more than 10

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 is 5:5 by mass ratio.

As shown in Tables 3 to 5, the content of chlorine atoms in the titanium nitride-containing particles is in the range of 0.001 to 0.3 mass% (in other words, 10 mass ppm to 3000 mass ppm). It was shown that the existence of such a film makes it possible to produce a cured film having excellent corrosion resistance of the electrode and excellent patterning property (resolution) (Example).
Further, when the content of chlorine atoms in the titanium nitride-containing particles exceeds 0.3 mass% (in other words, 3000 mass ppm), it is shown that the patterning property (resolution) and the anticorrosion property of the electrode are inferior. (Comparative example 1 and comparative example 2).
Further, it was shown that when the content of chlorine atoms in the titanium nitride-containing particles was less than 0.001 mass% (in other words, less than 10 mass ppm), the patterning property (resolution) was poor (comparison). Example 3, Comparative Example 4).

In addition, by comparison with Examples 17 to 21, the content of water is 0.1 to 1% by mass (preferably 0.1 to 0.8% by mass, and more preferably 0.1% by mass) with respect to the total mass of the composition. It was confirmed that in the case of 0.4% by mass), the patterning property (resolution) of the cured film and the anticorrosion property of the electrode material are excellent. Further, 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 stability of viscosity of the composition with time is more excellent. It was confirmed.
In addition, it was confirmed from the comparison between Example 26 and Example 27 that the patterning property (resolution) of the cured film was superior when D/P was 0.3 or less.
According to the comparison of Examples 26, 31 and 32, when the content of the titanium nitride-containing particles is 30 to 70 mass% with respect to the total solid content of the composition, the spectral property (good OD value), It was confirmed that the patterning property (resolution) and the anticorrosion property of the electrode were excellent.
Further, by comparison with Examples 6 to 9, when the specific surface area of the titanium nitride-containing particles determined by the BET method is 40 to 60 m ² /g, the spectral property (good OD value) and the patterning property (solution) It was confirmed that the image quality was superior. It was also confirmed that the filterability was excellent.
Further, by comparison with Examples 10 to 14, the diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particles was more than 42.8° and 43.5° when CuKα ray was used as the X-ray source. It was confirmed that when it was at most °, it was excellent in spectral property (good OD value) and patterning property (resolution).
In addition, it was confirmed from the comparison of Examples 12 to 15 that the titanium nitride-containing particles having an average primary particle diameter of 10 to 30 nm were more excellent in spectral properties (good OD value). It was also confirmed that the viscosity stability of the composition was also excellent. It was also confirmed that when the average primary particle diameter of the titanium nitride-containing particles is 10 nm or more, the viscosity stability of the composition is excellent.
Further, by comparing Example 12 and Example 16, in the shape of the primary particles of the titanium nitride-containing particles using a transmission electron microscope, when the spherical ratio is 60% by mass or more, the spectral property (good) is obtained. OD value) and patterning property (resolution). It was also confirmed that the composition had excellent filterability and viscosity stability over time.

  Evaluation was made in the same manner as in Example 1 except that the surfactant F-1 was not used. As a result of the evaluation, it was found that the same result as in Example 1 was obtained.

<Preparation of carbon black dispersion (CB dispersion)>
In the preparation of the above pigment dispersion, carbon black (trade name “Color Black S170”, manufactured by Degussa Co., average primary particle diameter 17 nm, BET specific surface area 200 m ² /g, gas black method was used instead of titanium nitride-containing particles. A carbon black dispersion was obtained by preparing a dispersion by the same method except that the carbon black manufactured by 1. was used.

  In the preparation of the composition of Example 1, titanium nitride-containing particles TiN-1 are contained instead of the pigment dispersion added so that the composition contains titanium nitride-containing particles TiN-1 at 19% by mass. A mixture of the pigment dispersion and the above CB dispersion [titanium nitride-containing 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 is 19% by mass. ] A composition was prepared in the same manner except that the above was used, and this was used for evaluation. As a result of the evaluation, it was found that the same light-shielding property as in Example 1 was obtained.

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

  In the preparation of the composition of Example 1, titanium nitride-containing particles TiN-1 are contained instead of the pigment dispersion added so that the titanium nitride-containing particles TiN-1 are contained in the composition in an amount of 19% by mass. A mixture of the pigment dispersion and the above PY dispersion [titanium nitride-containing particles in the composition TiN-1: 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. ] A composition was prepared in the same manner except that the above was used, and this was used for evaluation. As a result of the evaluation, it was found that the same light-shielding property as that of Example 1 was obtained and a film having a deep black tint was obtained.

Claims (32)

A composition containing titanium nitride-containing particles containing a chlorine atom ,
The content of the chlorine atoms in the titanium nitride-containing particles are, Ri 0.001 to 0.3% by mass,
The composition, wherein the solid content in the composition is 10 to 40% by mass . The composition according to claim 1 , wherein the titanium nitride-containing particles have an average primary particle diameter of 10 to 30 nm. Furthermore, the composition of Claim 1 or 2 containing 2 or more types of solvents. Further contains a dispersing agent composition according to any one of claims 1-3. The composition according to claim 4 , wherein the content ratio of the dispersant to the titanium nitride-containing particles is 0.3 or less in terms of mass ratio. Further, a polymerizable compound, composition according to any one of claims 1-5. Titanium nitride-containing particles containing a chlorine atom, and a polymerizable compound ,
The composition, wherein the content of the chlorine atom in the titanium nitride-containing particles is 0.001 to 0.3% by mass. The composition according to claim 7 , wherein the titanium nitride-containing particles have an average primary particle diameter of 10 to 30 nm. Furthermore, the composition of Claim 7 or 8 containing 2 or more types of solvents. Furthermore, the composition of any one of Claims 7-9 containing a dispersing agent. The composition according to claim 10 , wherein a content ratio of the dispersant to the titanium nitride-containing particles is 0.3 or less in a mass ratio. Titanium nitride-containing particles containing chlorine atoms, and containing a dispersant ,
The composition, wherein the content of the chlorine atom in the titanium nitride-containing particles is 0.001 to 0.3% by mass. The composition according to claim 12 , wherein a content ratio of the dispersant to the titanium nitride-containing particles is 0.3 or less in mass ratio. The composition according to claim 12 or 13 , wherein the titanium nitride-containing particles have an average primary particle diameter of 10 to 30 nm. Furthermore, the composition of any one of Claims 12-14 containing 2 or more types of solvents. Containing titanium nitride-containing particles containing a chlorine atom and two or more kinds of solvents ,
The composition, wherein the content of the chlorine atom in the titanium nitride-containing particles is 0.001 to 0.3% by mass. The composition according to claim 16 , wherein the titanium nitride-containing particles have an average primary particle diameter of 10 to 30 nm. Contains titanium nitride-containing particles containing chlorine atoms,
The content of the chlorine atom in the titanium nitride-containing particles is 0.001 to 0.3 mass% ,
The composition, wherein the titanium nitride-containing particles have an average primary particle diameter of 10 to 30 nm .   Contains titanium nitride-containing particles containing chlorine atoms,
  The composition according to any one of claims 1 to 18, wherein a content of the chlorine atom in the titanium nitride-containing particles is 0.001 mass% to 2000 mass ppm.   Contains titanium nitride-containing particles containing chlorine atoms,
  The composition according to any one of claims 1 to 19, wherein a content of the chlorine atom in the titanium nitride-containing particles is 0.001 to 0.15 mass%. Diffraction angle 2θ of peak derived from the (200) plane of the titanium nitride-containing particles, in a case of providing a CuKα ray as an X-ray source, is less than 42.8 ° Ultra 43.5 °, claim claim 1 21. The composition according to any one of 20 to 20 . The composition according to any one of claims 1 to 21, wherein the titanium nitride-containing particles have a specific surface area determined by the BET method of 40 to 60 m2/g. The photograph observation of the primary particle image of the said titanium nitride containing particle|grains using a transmission electron microscope WHEREIN: 60 or more out of 100 of the observation object are spherical shape. Composition. The composition according to any one of claims 1 to 23 , further comprising a polymerization initiator. The composition according to any one of claims 1 to 24 , wherein the content of the titanium nitride-containing particles is 30 to 70 mass% with respect to the total solid content of the composition. In addition, containing water,
The composition according to any one of claims 1 to 25 , wherein the content of the water is 0.1 to 1 mass% with respect to the total mass of the composition. Furthermore, containing a dispersant,
The composition according to any one of claims 1 to 26 , wherein the dispersant has at least one structure selected from the group consisting of polycaprolactone, polyvalerolactone, polymethyl acrylate and polymethyl methacrylate. object. Obtained with the compositions according to any of claims 1-27, the cured film. A color filter comprising the cured film according to claim 28 . A light-shielding film having the cured film according to claim 28 . A solid-state image sensor having the cured film according to claim 28 . An image display device comprising the cured film according to claim 28 .