WO2017169584A1

WO2017169584A1 - Composition, cured film, color filter, light-blocking film, solid-state imaging element and image display device

Info

Publication number: WO2017169584A1
Application number: PCT/JP2017/009177
Authority: WO
Inventors: 久保田　誠; 浜田　大輔
Original assignee: 富士フイルム株式会社
Priority date: 2016-03-31
Filing date: 2017-03-08
Publication date: 2017-10-05
Also published as: CN109073799A; TW201806853A; JPWO2017169584A1; CN113031398A; KR20180116354A; KR102160018B1; JP6698820B2; TWI790993B; CN109073799B

Abstract

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

Description

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

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

A solid-state imaging device is a photographic lens and a solid-state imaging device (hereinafter referred to as an “image sensor”) such as a CCD (charge coupled device) and a CMOS (complementary metal oxide semiconductor) disposed behind the photographic lens. 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 mobile phone with a camera, a smartphone, and the like.
In a solid-state imaging device, noise due to reflection of visible light may occur. Therefore, a predetermined light shielding film can be provided in the solid-state imaging device for the purpose of suppressing noise generation. As a composition for forming the light shielding film, a black composition containing a black pigment such as titanium black is used.

On the other hand, color filters disposed in a solid-state imaging device, a liquid crystal image device, and the like have R (red), G (green), and B (in order to improve contrast by preventing color mixing between colored pixels. A black matrix may be formed between each blue pixel. In addition, an image sensor peripheral light-shielding film (frame light-shielding film) is formed in the frame region of the color filter for the purpose of preventing light leakage from the light receiving portion of the solid-state imaging device.
A black composition containing a black pigment such as titanium black is also used in the composition for forming the black matrix. For example, Patent Document 1 states that “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 a light shielding material, and using CuKα rays as an X-ray source. A black resin composition for a resin black matrix having a diffraction angle 2θ of a peak derived from the (200) plane of the titanium nitride particles of 42.5 ° or more and 42.8 ° or less is disclosed. 1).

Japanese Patent No. 5136139

The cured film of the black composition containing titanium nitride particles (titanium nitride-containing particles) as described above is, for example, as a light shielding film of a constituent member of a solid-state imaging device, a black matrix of a color filter, or an image sensor peripheral light shielding film. When used, it may be used by being laminated on a substrate on which electrodes such as electrode patterns are arranged.
The inventors of the present invention produced a black composition containing titanium nitride particles (titanium nitride-containing particles) described in Patent Document 1, and used this to form an electrode on a substrate on which the electrode was placed. A cured film was formed so as to be coated and evaluated. As a result, it has been 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. Similarly, when forming a pattern-shaped cured film using the black composition, it has been clarified that the pattern resolution (patterning property) may not satisfy the desired requirements.

Therefore, an object of the present invention is to provide a composition capable of producing a cured film having excellent electrode corrosion resistance 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 imaging device, 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 the titanium nitride-containing particles to a predetermined numerical range. Completed.
That is, it has been found that the above object can be achieved by the following configuration.

(1) containing titanium nitride-containing particles containing chlorine atoms,
A 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 42.8 ° or more 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 determined by the BET method of 40 to 60 m ² / g.
(4) The composition according to any one of (1) to (3), wherein the titanium nitride-containing particles have an average primary particle size of 10 to 30 nm.
(5) In observation of 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), further comprising two or more solvents.
(7) The composition according to any one of (1) to (6), further comprising a dispersant.
(8) The composition according to (7), wherein a content ratio of the dispersant to the titanium nitride-containing particles is 0.3 or less by mass ratio.
(9) The composition according to any one of (1) to (8), further comprising a polymerizable compound.
(10) The composition according to any one of (1) to (9), further comprising a polymerization initiator.
(11) The composition according to any one of (1) to (10), wherein the solid content in the composition is 10 to 40% by mass.
(12) The composition according to any one of (1) to (11), wherein the content of the titanium nitride-containing particles is 30 to 70% by mass with respect to the total solid content of the composition.
(13) Furthermore, it contains water,
The composition according to any one of (1) to (12), wherein the water content is 0.1 to 1% by mass relative to the total mass of the composition.
(14) Furthermore, a dispersant is contained,
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 imaging device 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 anticorrosive properties of electrodes and excellent patterning properties. In addition, the present invention can provide a cured film, a color filter, a light shielding film, a solid-state imaging device, and an image display device.

The present invention will be described below.
In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has 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).
“Actinic light” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. . In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in the present specification includes not only exposure with a mercury lamp emission line spectrum, an excimer laser represented by far ultraviolet rays, X-rays, and EUV light, but also electron beams, ion beams, and the like. The exposure with the particle beam is also included in the exposure.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acrylic and methacryl, “(meth) acryloyl” represents acryloyl and methacryloyl, and “(meth) ) Acrylamide "refers to acrylamide and methacrylamide. In the present specification, “monomer” and “monomer” are synonymous. The monomer in the present invention is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.

[Composition]
The composition of the present invention contains titanium nitride-containing particles containing chlorine atoms, and the content of the chlorine atoms in the titanium nitride-containing particles is 0.001 to 0.3% by mass.
According to the composition of this invention, the cured film excellent in the anticorrosion property of the electrode and excellent in patterning property can be produced.
As a result of intensive studies, the inventors of the present invention used a black composition containing, as a pigment component, titanium nitride-containing particles having a chlorine atom content exceeding 0.3% by mass on a substrate on which an electrode is disposed. It was confirmed that when the light-shielding film was formed, hydrochloric acid was generated by the reaction of the chlorine atoms with moisture in the air depending on the use environment conditions, thereby causing deterioration of the electrode member.
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 resulting coating film is increased, and the patterning property is improved. We know that there is a tendency to decrease.
From the above viewpoint, by making the content of chlorine atoms in the titanium nitride-containing particles contained in the composition 0.001 to 0.3% by mass, the electrode has excellent anticorrosion properties and excellent patterning properties. A cured film can be formed.

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

Here, the method for causing the titanium nitride-containing particles to contain chlorine atoms is not particularly limited. As an example, a method of synthesizing titanium nitride-containing particles containing chlorine atoms by using titanium tetrachloride together with titanium powder and flowing ammonia gas as a carrier gas in the thermal plasma method described above can be given.
Further, when the content of chlorine atoms in the titanium nitride-containing particles is a predetermined amount or more, the particles are, for example, 100 to 300 ° C. (preferably 120 to 280 ° C., more preferably 120 to 250 ° C.) and 5 It is desirable to carry out 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.

The titanium powder material (titanium particles) and titanium tetrachloride used for the production of titanium nitride-containing particles are preferably of high purity. The titanium powder material and titanium tetrachloride are not particularly limited, but those having a purity of titanium element of 99.99% or more are preferable, and those of 99.999% or more are more preferably used.

The titanium powder material (titanium particles) and titanium tetrachloride used for the production of titanium nitride-containing particles may contain atoms other than titanium atoms. Examples of other atoms that can be contained in the titanium powder material include Fe atoms and Si atoms.
When the titanium powder material and titanium tetrachloride contain Fe atoms, the content of Fe atoms is preferably more than 0.001% by mass with respect to the total mass of the titanium powder material and titanium tetrachloride. Thereby, the patterning property of a 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 the titanium powder material and titanium tetrachloride. . Thereby, the corrosion resistance of the electrode by a cured film is more excellent (it can suppress more that a cured film corrodes an electrode). That is, the Fe powder contained in the titanium powder material and titanium tetrachloride used for the production of titanium nitride-containing particles is within the above range (over 0.001 mass, less than 0.4 mass%). The effect can be obtained more remarkably.
When the titanium powder material and titanium tetrachloride contain Si atoms, the Si atom content is preferably more than 0.002% by mass and less than 0.3% by mass with respect to the total mass of the titanium powder material. More preferably, the content is 0.01 to 0.15% by mass, and further preferably 0.02 to 0.1% by mass. When the content of Si atoms is more than 0.002% by 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 stabilized, and the titanium nitride-containing particles when the titanium nitride-containing particles are dispersed It is considered that the adsorbing property of the dispersant on the surface is improved, and the undispersed material of the titanium nitride-containing particles is reduced, thereby suppressing the generation of particles. That is, the effect of the present invention can be obtained more remarkably when the Si atom contained in the titanium powder material and titanium tetrachloride used for the production of titanium nitride-containing particles is within the above range.
The titanium powder material (titanium particles) and titanium tetrachloride used in the production of titanium nitride-containing particles preferably have a water content of less than 1% by mass with respect to the total mass of the titanium powder material. More preferably, it is less than 1 mass%, and it is still more preferable not to contain substantially. The effect of this invention can be acquired more notably because the water | moisture content in the titanium powder material and titanium tetrachloride used for manufacture of titanium nitride containing particle | grains exists in the said range.

The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 50 to 85% by mass and preferably 50 to 80% by mass with respect to the total mass of the titanium nitride-containing particles. More preferred is 50 to 75% by 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% by mass and preferably 20 to 45% by mass with respect to the total mass of the titanium nitride-containing particles. More preferred is 20 to 40% by mass. The nitrogen atom content 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 oxygen atom content 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% by mass with respect to the total mass of the titanium nitride-containing particles. Among these, the content is preferably 0.005 to 0.3% by mass, more preferably 0.01 to 0.3% by mass, still more preferably 0.1 to 0.3% by mass, From 0.15% by weight is particularly preferred. When the chlorine atom content is 0.001% by mass or more, the patterning property 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 may have a diffraction angle 2θ of a peak derived from the (200) plane of 42.8 ° or more 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 (eg, a black matrix) obtained using a composition containing titanium nitride-containing particles having such characteristics has an appropriate OD value and is excellent in patterning properties (resolution).

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 not more than 43.5 ° as described above, and is 42.85 to 43.3 °. Is more preferably 42.9 to 43.2 °.
Titanium nitride-containing particles contain titanium nitride (TiN) as a main component and are usually noticeable when oxygen is mixed during the synthesis and when the particle diameter is small, but due to oxidation of the particle surface, etc. A part of oxygen atoms may be contained.
However, a smaller amount of oxygen contained in the titanium nitride-containing particles is preferable because a higher OD value (optical density) can be obtained. Further, the titanium nitride-containing particles, preferably contains no TiO ₂ as an auxiliary component. When the titanium nitride-containing particles contain titanium oxide TiO ₂ as an accessory component, the peak derived from anatase TiO ₂ (101) as the strongest peak is in the vicinity of 2θ = 25.3 °, the rutile TiO ₂ ( 110) is observed in the vicinity of 2θ = 27.4 °. However, since TiO ₂ is white and causes a reduction in the light shielding properties of the black matrix, it is preferably reduced to such an 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 transmitted light of the cured film exhibits a blue to blue violet color having a peak wavelength of 475 nm or less, and has 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 and is preferably 40 to 60 m ² / g, more preferably 40 to 58 m ² / g, and 42 to 55 m ² / g. More preferably. By setting the specific surface area of the titanium nitride-containing particles to 40 to 60 m ² / g, the resulting cured film has an OD (optical density) value in a more appropriate range and is superior in patterning properties (resolution). Excellent filterability of things.

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. In addition, from the viewpoint of viscosity stability over time of the composition, the average primary particle diameter of the titanium nitride-containing particles is preferably 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, an apparatus according to JEM-2100F type field emission transmission electron microscope manufactured by JEOL). It can be determined from the photograph taken and refers to the number average particle size of primary particles. Specifically, a dispersion containing titanium nitride-containing particles is prepared by the method described in the examples, diluted with the same solvent as the dispersion so that the solid content is about 1% by mass, and dispersed on the carbon foil. A transmission electron microscope image of the titanium nitride-containing particles present on the carbon foil after dropping and drying the liquid is observed. The projected area of the primary particles of titanium nitride-containing particles is determined by the above apparatus, and the equivalent circle diameter is determined therefrom. The arithmetic average of the obtained equivalent circle diameter was defined as the primary particle diameter. More specifically, after measuring the primary particle size of 100 particles randomly selected to determine the average primary particle size, 80 particles excluding the maximum 10 particles and the minimum 10 particles are excluded. It is calculated | required by arithmetically averaging the primary particle diameter.
Further, in the photographic observation of the primary particle image using the transmission electron microscope described above, 60 or more (in other words, 60% or more) of titanium nitride-containing particles are spherical. Is preferred. When 60% or more of the titanium nitride-containing particles to be used are spherical, the obtained cured film has an OD (optical density) value in an appropriate range and is excellent in patterning properties (resolution). Moreover, 60% or more of the titanium nitride-containing particles to be used are spherical, so that the filterability and viscosity aging stability of the composition are excellent.
In the present invention, the term “spherical” means that the particles are not necessarily true spheres. For example, the particles are substantially spherical (the ratio of the minor axis / major axis in the two-dimensional figure when projected is 0.7 to 1). Degree) or a spheroid.

The content of 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. More preferably. When the content of the titanium nitride-containing particles is in the above numerical range, in addition to excellent spectral properties (good OD value), patterning properties (resolution) and anticorrosion properties of the electrodes are also excellent.
In addition, in this specification, solid content intends the component which comprises the cured film formed with a composition, and a solvent is not contained. For example, since the polymerizable compound described later is a component constituting the cured film, even a liquid (liquid) is included in the solid content.

<Dispersant>
The composition of the present invention preferably contains a dispersant. A dispersing agent contributes to the improvement of dispersibility of pigments, such as a titanium nitride content particle mentioned above. In this invention, a dispersing agent and the binder resin mentioned later are different components.
As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
Examples of the dispersant include polymer dispersants [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, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivatives.
The polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.

The polymer compound is adsorbed on the surface of the dispersion such as titanium nitride-containing particles and optionally used pigments, and acts to prevent re-aggregation of the dispersion. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to 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 can be promoted.

The polymer compound preferably has a structural unit having a graft chain. In this specification, “structural unit” is synonymous with “repeating unit”.
Since the polymer compound having a structural unit having such a graft chain has an affinity for a solvent by 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 a structural unit having a graft chain has an affinity with a polymerizable compound or other resin that can be used in combination. As a result, it becomes difficult to produce a residue by alkali development.
When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility of the pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to the pigment such as titanium nitride-containing particles decreases, and the dispersibility of the pigment or the like tends to decrease. For this reason, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and the number of atoms excluding hydrogen atoms. More preferred is 60-500.
Here, the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a 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. 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.
In order to improve the interaction between the graft chain and the solvent and thereby improve the dispersibility, the graft chain is made of 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.

Corresponding to the structural unit having a graft chain of the polymer compound, commercially available macromonomers suitably used for the synthesis of the polymer compound include AA-6 (trade name, Toa Gosei Co., Ltd.), AA-10 ( Product name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 (trade name, produced by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.) Co., Ltd.), AW-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei 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 Toa Gosei Co., Ltd.), Blemmer PP-100 (trade name, manufactured by NOF Corporation), Blemmer PP-500 ( Product name, NOF Corporation), BLEMMER PP-800 (trade name, NOF Corporation), BLEMMER PP-1000 (trade name, NOF Corporation), BLEMMER 55-PET-800 (product) Name, manufactured by NOF Corporation), BREMMER PME-4000 (trade name, manufactured by NOF Corporation), BREMMER PSE-400 (trade name, manufactured by NOF Corporation), Blemmer PSE-1300 (trade name, NOF Corporation, Bremer 43PAPE-600B (trade name, manufactured by NOF Corporation) and the like are used. Of these, AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.) AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), Blemmer PME-4000 (trade name, manufactured by NOF Corporation), etc. It is 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-opened structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure means a structure having a ring-opened structure of δ-valerolactone as a repeating unit.
Specific examples of the dispersant having a polycaprolactone structure include those in which j and k are 5 in the following formula (1) and the following formula (2). Specific examples of the dispersant having a polyvalerolactone structure include those in which j and k in the following formula (1) and the following formula (2) are 4.
Specific examples of the dispersant having a polymethyl acrylate structure include those in which X ⁵ in the following formula (4) is a hydrogen atom and R ⁴ is a methyl group. Further, specific examples of the dispersant having a polymethyl methacrylate 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 includes a structural unit represented by any one of the following formulas (1) to (4) as a structural unit having a graft chain, and includes the following formula (1A), the following formula (2A), It is more preferable to include a structural unit represented by any of the following formula (3A), the following formula (3B), and the following (4).

In the 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 the 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. 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 (the number of carbon atoms) from the viewpoint of synthesis restrictions. Are preferably each independently a hydrogen atom or a methyl group, more preferably a methyl group.

In the 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 (Y-1) to (Y-21) linking groups. . In the structures shown below, A and B mean binding sites with the left end group and the right end group in formulas (1) to (4), respectively. Of the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.

In the formulas (1) to (4), Z ¹ , Z ² , Z ³ , and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, and specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. 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 particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms. Of these, 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 the formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500.
In the formulas (1) and (2), j and k each independently represent an integer of 2 to 8. J and k in the formulas (1) and (2) are preferably integers of 4 to 6, and more preferably 5, from the viewpoint of dispersion stability and developability of the composition.

In the formula (3), R ³ represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ³ may be the same or different from each other.
In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure. R ⁴ preferably includes a hydrogen atom, an alkyl group, an aryl group, and 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 more 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 or different from each other.

In addition, the polymer compound may have a structural unit having a graft chain, which has two or more different structures. That is, the polymer compound molecule may contain structural units represented by formulas (1) to (4) having different structures, and n, m in formulas (1) to (4). , P, and q each represents an integer of 2 or more, in Formula (1) and Formula (2), j and k may contain structures different from each other in the side chain. 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.
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.

The structural unit represented by 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.

More preferably, the polymer compound 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 above formulas (1) to (4)) is 2 to 90% of the total mass of the polymer compound in terms of mass. It is preferably included in a range, and more preferably in a 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, not corresponding 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 (for example, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).

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

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

log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It 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.
When the logP value increases to a positive value across 0, the oil solubility increases. When the logP value increases to a negative value, the water solubility increases. There is a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for estimating aqueous properties.

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

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 An alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.) is represented.
R ¹ , R ² , and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. R ² and R ³ are particularly preferably a hydrogen atom.
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, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), divalent aromatic group (for example, arylene group) , Substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR ³¹ —, where R ³¹ Includes 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. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.

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

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. The heterocycle may be condensed with another heterocycle, aliphatic ring or aromatic ring. Further, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is a fatty acid Aromatic 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. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

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

The aliphatic group may have a cyclic structure or a branched structure. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -A 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 cyclic hydrocarbon rings, homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, and tricyclo [4.3.1.1 ^2,5 ] undecane rings , Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a perhydrophenalene ring is also included.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, 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.

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

The heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. The heterocycle may be condensed with another heterocycle, aliphatic ring or aromatic ring. Further, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is a fatty acid Aromatic 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.), an alkyl group having 1 to 6 carbon atoms (eg, Methyl group, ethyl group, propyl group, etc.), Z, or LZ. Here, L and Z are as defined above. R ⁴ , R ⁵ and R ⁶ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

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

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

In the polymer compound, the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably in a range of 20 to 80% with respect to 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 titanium nitride-containing particles.
Examples of the functional group capable of forming an interaction with a 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, the structural unit having an acid group, the structural unit having a basic group, or a coordinating group, respectively. It is preferable to have a structural unit having or a reactive structural unit.
In particular, when the polymer compound further has an alkali-soluble group such as a carboxylic acid group as the acid group, it is possible to impart developability for pattern formation by alkali development to the polymer compound.
That is, by introducing an alkali-soluble group into the polymer compound, the composition of the present invention has a polymer compound as a dispersant that contributes to dispersion of pigments such as titanium nitride-containing particles having alkali solubility. . A composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
Moreover, when a high molecular compound has a structural unit which has an acid group, it becomes easy for a high molecular compound to become compatible with a solvent, and it exists in the tendency for applicability | paintability to improve.
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, and the polymer compound stably disperses the pigment such as titanium nitride-containing particles, and the titanium nitride This is presumably because the viscosity of the polymer compound in which the pigment such as the contained particles is dispersed is low, and the polymer compound itself is easily dispersed stably.

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

Examples of the acid group that is a functional group capable of forming an interaction with a pigment such as titanium nitride-containing particles include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group. At least one 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 have high pigment dispersibility. In terms, 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 or more structural units having an acid group.
The polymer compound may or may not contain a structural unit having an acid group. However, when it is contained, the content of the structural unit having an acid group is based on the total mass of the polymer compound in terms of mass. Preferably, it is 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage of image strength due to alkali development.

Examples of the basic group which 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 group including an N atom. There are a ring, an amide group, and the like, and a preferable one is a tertiary amino group from the viewpoint of good adsorption power to pigments such as titanium nitride-containing particles and high dispersibility of the pigments. The polymer compound can have one or more of these basic groups.
The polymer compound may or may not contain a structural unit having a basic group, but when it is contained, the content of the structural unit having a basic group is calculated by mass conversion to 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 suppression of developability inhibition.

Examples of the coordinating group, which is a functional group capable of forming an interaction with a pigment such as titanium nitride-containing particles, and the reactive functional group include acetylacetoxy group, trialkoxysilyl group, isocyanate group, and acid anhydride And acid chlorides. Preferable one is an acetylacetoxy group in that the adsorbing power to the pigment such as titanium nitride-containing particles is good and the dispersibility of the pigment is high. The polymer compound may have one or more 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 when it is contained, 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 inhibition of developability inhibition with respect to the total mass of the polymer compound.

When the polymer compound in the present invention has a functional group capable of interacting with a pigment such as titanium nitride-containing particles in addition to the graft chain, the pigments such as various titanium nitride-containing particles as described above, It is only necessary to contain functional groups capable of forming an interaction, and how these functional groups are introduced is not particularly limited, but the polymer compounds are represented by the following general formulas (iv) to (vi). It is preferable to have one or more structural units selected from structural units derived from the monomer represented by:

In general formula (iv) to general formula (vi), R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number Represents an alkyl group of 1 to 6 (for example, methyl group, ethyl group, propyl group, etc.).
In general formula (iv) to general formula (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, more preferably Each independently represents a hydrogen atom or a methyl group. In general formula (iv), R ¹² and R ¹³ are each particularly preferably 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.
Y in the general formula (v) represents a methine group or a nitrogen atom.

In the general formulas (iv) to (v), L ₁ 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, , Arylene groups, and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino bonds (—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. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.

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

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle. Further, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ³² , where R ³² is a fatty acid Aromatic 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. L ₁ may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

In the general formula (iv) to general formula (vi), Z ₁ represents a functional group capable of forming an interaction with a pigment such as titanium nitride-containing particles in addition to the graft chain, and includes a carboxylic acid group and a tertiary group. An amino group is preferred, and a carboxylic acid group is more preferred.

In general formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom, a halogen atom (eg, 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.), - represents a _{Z 1} or _L 1 -Z _1,. Wherein _{L 1} and _{Z 1} has the same meaning as _{L 1} and _{Z 1} in the above, are the preferable examples. R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, 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 in which X ₁ is an oxygen atom or an imino group and Z ₁ is a carboxylic acid group is preferable.
In addition, as a 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.
Furthermore, 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, A compound in which Z is a carboxylic acid group is preferred.

The following are typical examples of monomers (compounds) represented by general formula (iv) to general formula (vi).
Examples of monomers 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) and succinic anhydride. , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and a phthalic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and a tetrahydroxyphthalic anhydride , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic anhydride, Acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and - hydroxyphenyl methacrylamide.

The content of structural units having functional groups capable of interacting with pigments such as titanium nitride-containing particles, the interaction with pigments such as titanium nitride-containing particles, dispersion stability, and permeability to developer From this viewpoint, it is preferably 0.05% by mass to 90% by mass, more preferably 1.0% by mass to 80% by mass, and still more preferably 10% by mass to 70% by mass with respect to the total mass of the polymer compound.

Furthermore, for the purpose of improving various performances such as image strength, the polymer compound is a structural unit having a graft chain, a hydrophobic structural unit, a titanium nitride-containing particle, etc., as long as the effects of the present invention are not impaired. Different from the structural unit having a functional group capable of interacting with the pigment, other structural unit having various functions (for example, a structural unit having a functional group having affinity with the dispersion medium used in the dispersion) ) May further be 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 or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less in terms of mass with respect to the total mass of the polymer compound. Especially preferably, it is 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 to 160 mgKOH / g, more preferably in the range of 10 mgKOH / g to 140 mgKOH / g, and still more preferably in the range of 20 mgKOH / g to 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 when forming a cured film is more effectively suppressed. Moreover, if the acid value of a high molecular compound is 10 mgKOH / g or more, alkali developability will become more favorable. Further, if the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of pigments such as titanium nitride-containing particles can be further suppressed, the number of coarse particles can be reduced, and the stability of the composition over time can be reduced. It can be improved.

In the present invention, the acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound. Moreover, the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound.

The weight average molecular weight of the polymer compound in the present invention is 4,000 as a polystyrene conversion value by a GPC (gel permeation chromatography) method from the viewpoint of pattern peeling inhibition during development and developability when forming a cured film. It is preferably 300 or more and 300 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. It is particularly preferred.
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 an eluent. ).

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 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 Kashiwagi Kasei Co., Ltd., “Disperbyk-101 (polyamideamine phosphate)” manufactured by BYK Chemie, 107 (carboxylic acid ester), and 110 (acid group). ), 111 (phosphate dispersing agent), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050 to 4010 to 4165 (polyurethane type), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyester) manufactured by EFKA Amide), 5765 (high molecular weight polycarboxylate), 622 (Fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”,“ Ajisper PB821, PB822, PB880, PB881 ”manufactured by Ajinomoto Fine Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd. “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester)” manufactured by Enomoto Kasei Co., Ltd. , DA-703-50, DA-705, DA-725 ”,“ Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) manufactured by Kao Corporation ) "," Homogenol L-18 (polymeric polycarboxylic acid) ", "Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "Acetamine 86 (stearylamine acetate)", "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative)" manufactured by Nippon Lubrizol Co., Ltd. 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer) ”,“ Nikkor T106 (Nikkor Chemicals) ” Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”, Kawano Fine Chemical Co., Ltd. Hinoact T-8000E, etc., Shin-Etsu Chemical Co., Ltd., Organosi Xan polymer KP341, “W001: cationic surfactant” manufactured by Yusho Co., Ltd., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl Nonionic surfactants such as ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA manufactured by Morishita Sangyo Co., Ltd.” -47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 "," Disperse Aid 6, D Polymer dispersing agents such as “Sparse Aid 8, Disperse Aid 15, Disperse Aid 9100”, “Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84 manufactured by ADEKA Corporation F87, P94, L101, P103, F108, L121, P-123 ”,“ Ionet (trade name) S-20 ”manufactured by Sanyo Kasei Co., Ltd., and the like. Further, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can also be used.
Commercially available amphoteric resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERB manufactured by BYK Chemie. 2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9976, Ajisper PB821, Azisper PB822, and Azisper PB881 manufactured by Ajinomoto Fine-Techno Co., Ltd.
These polymer compounds may be used alone or in combination of two or more.

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.

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

In the case where the composition contains a dispersant, the content of the dispersant is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, based on the total solid content of the composition.
A dispersing agent may be used individually by 1 type, and may be used together 2 or more types. When using 2 or more types together, it is preferable that a total amount becomes the said range.

<Binder resin>
The composition of the present invention preferably contains a binder resin.
As the binder resin, a linear organic polymer is preferably used. As such a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development. Among these, 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 that promotes at least one alkali solubility in a molecule (preferably a molecule having a (meth) acrylic copolymer or a styrene copolymer as the main chain). It can be suitably selected from alkali-soluble resins having a group to be used. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, (meth) acrylic resins, (meth) acrylamide resins, (meth) acrylic / (meth) acrylamide copolymer resins are preferred, and developability From the viewpoint of control, (meth) acrylic resins, (meth) acrylamide resins, and (meth) acryl / (meth) acrylamide copolymer resins are preferred.
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. Especially, what is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution is preferable, and an alkali-soluble resin having a structural unit derived from (meth) acrylic acid is more preferable. These acid groups may be used alone or in combination of two or more.

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-58-12777, JP-B-54-25957, Those described in Kaikai 54-92723, JP-A-59-53836, and JP-A-59-71048, ie, resins or acid anhydrides obtained by homopolymerizing or copolymerizing monomers having a carboxyl group Resins in which an acid anhydride unit is hydrolyzed, half-esterified or half-amidated by homopolymerizing a monomer having a monomer, and 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-carboxyl styrene. Examples of monomers having an acid anhydride include And maleic anhydride. Similarly, an acidic cellulose derivative having a carboxylic acid group in the side chain is also exemplified. In addition, 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 European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463 has film strength and developability. It is excellent in balance and is suitable.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon and polyether which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.

In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition polymerizable vinyl monomer as required] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid / necessary The other addition polymerizable vinyl monomer] copolymer is suitable because it is excellent in the balance of film strength, sensitivity, and developability.
Commercially available products include, for example, 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.

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

Moreover, 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 which has a graft chain is synonymous with the structural unit which has the graft chain which the dispersing agent mentioned above has, and its suitable 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. Preferably, the acid group is at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. More preferred is a carboxylic acid group.

The structural unit having an acid group preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulas (vii) to (ix).

In the general formulas (vii) to (ix), R ²¹ , R ²² , and R ²³ are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number Represents an alkyl group of 1 to 6 (for example, methyl group, ethyl group, propyl group, etc.).
In the general formula (vii) to the general formula (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, more preferably Each independently represents a hydrogen atom or a methyl group. In general formula (vii), R ²¹ and R ²³ are each particularly preferably 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.
Y in the general formula (viii) represents a methine group or a nitrogen atom.

In the general formulas (vii) to (ix), L ₂ 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, , Arylene groups, and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino bonds (—NR ⁴¹ ′ — Here, R ⁴¹ ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.

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

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle. One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle. Further, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R ⁴² , where R ⁴² represents a fatty acid Aromatic 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. L ₂ may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH ₂ CH ₂ ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

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

In general formula (ix), R ²⁴ , R ²⁵ , and R ²⁶ are each independently a hydrogen atom, a halogen atom (eg, 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.), - represents a _{Z 2} or _L 2 -Z _2,. Here _{L 2} and _{Z 2} has the same meaning as _{L 2} and _{Z 2} in the above, and preferred examples are also the same. R ²⁴ , R ²⁵ , and R ²⁶ 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 (vii), R ²¹ , R ²² , and R ²³ are each independently a hydrogen atom or a methyl group, and L ₂ is an alkylene group or an oxyalkylene structure. A compound in which X ₂ is an oxygen atom or an imino group and Z ₂ is a carboxylic acid group is preferable.
Further, 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.
Furthermore, 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 a structural unit having a graft chain described above, and the preferred acid value and weight average molecular weight are the same.

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

The content of the binder resin in the composition of the present invention is preferably 0.1 to 30% by mass and more preferably 0.3 to 25% by mass with respect to the total solid content of the composition.
Binder resin may be used individually by 1 type, and may be used together 2 or more types. When using 2 or more types together, it is preferable that a total amount becomes the said 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 preferable, 0.05 to 0.3 is more preferable, and 0.1 to 0.3 is more preferable. When the content ratio D / P is in the above range, the performance reproducibility of the dispersion is excellent, and the patterning property (resolution) of the cured film is also excellent.

<Polymerizable compound>
The composition of the present invention preferably contains a polymerizable compound.
The polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having 2 or more, further preferably 3 or more, and particularly preferably 5 or more. The upper limit is 15 or less, for example. 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 is preferably a monomer.
The molecular weight of the polymerizable compound is preferably 100 to 3000, and more preferably 250 to 1500.
The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, 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.), esters, amides, and multimers thereof. Preferred are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group and the like with a monofunctional or polyfunctional isocyanate or epoxy, the above unsaturated carboxylic acid A dehydration condensation reaction product of an ester or amide and a monofunctional or polyfunctional carboxylic acid is also preferably used. Reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, thiols, halogen groups, tosyloxy groups A reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as monofunctional or polyfunctional alcohols, amines or thiols is also suitable. Moreover, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like.
As these specific compounds, the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be suitably 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 JP2013-29760A and paragraphs 0254 to 0257 of JP2008-292970A can be referred to, the contents of which are incorporated herein.

The polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.). Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, manufactured as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are mediated by ethylene glycol or propylene glycol residues (eg, commercially available from Sartomer, SR454, SR499) ) Is preferred. These oligomer types can also be used. 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.
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. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. 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 preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

The polymerizable compound is also preferably a compound having a caprolactone structure.
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, Ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone be able to. Of these, compounds having a caprolactone structure represented by the following general formula (Z-1) are preferred.

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

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

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

Polymerizable compounds having a caprolactone structure are commercially available, for example, from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and DPCA-20 (m = 1 in the above formulas (Z-1) to (Z-3), Number of groups represented by (Z-2) = 2, a compound in which R ¹ is all hydrogen atoms), DPCA-30 (formula, m = 1, number of groups represented by formula (Z-2)) = 3, a compound in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (Z-2) = 6, a compound in which R ¹ is all hydrogen atoms) ), And DPCA-120 (a compound in which m = 2, the number of groups represented by formula (Z-2) = 6, and all R ¹ are 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 general formulas (Z-4) and (Z-5), each E independently represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O). —, Each independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
In general formula (Z-4), the total number of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40 .
In general formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60 .

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

The compounds represented by formula (Z-4) or 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 Xs are acryloyl groups, in the general formula (Z-5), a compound in which all six Xs are acryloyl groups, Among these, an embodiment in which at least one is a mixture with a compound having a hydrogen atom is preferable. With such a configuration, the developability can be further improved.

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

The compound represented by the general formula (Z-4) or (Z-5) is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. It can be synthesized from a step of bonding a ring-opening skeleton by reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a 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 a 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), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f), and among them, exemplary 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, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. 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 also suitable. is there. Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are disclosed. By using it, it is possible to obtain a composition excellent in the photosensitive speed.
Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

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, and even more preferably 10.60 or more.
In this specification, the SP value is determined by the Hoy method unless otherwise specified (HL Hoy Journal of Paining, 1970, Vol. 42, 76-118). The SP value is shown with the unit omitted, but the unit is cal ^1/2 cm ^−3/2 .

The composition also preferably has a polymerizable compound having a cardo skeleton from the viewpoint of reducing 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 represents an aryl group containing a benzene ring surrounded by a broken line. X ¹ to X ⁴ each independently represents 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 represents an integer of 1 to 5, and c and d each independently represents an integer of 0 to 4. R ¹ to R ⁴ each independently represents 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 which can be possessed. However, 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, X ¹ to X ⁴ and R ¹ to R ⁴ are each 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 by a broken line.

In the general formula (Q3), the aryl group containing a benzene ring surrounded by a broken line 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 or a naphthyl group) is 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 represents 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 is preferably an aliphatic group having a polymerizable group.
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 more preferable.
In the aliphatic group having a polymerizable group represented by X ¹ to X ⁴ , when the aliphatic group is substituted with a hetero atom, —NR— (R is a substituent), an oxygen atom, or a sulfur atom The non-adjacent —CH ₂ — in the aliphatic group is preferably substituted with an oxygen atom or a sulfur atom, and the non-adjacent —CH ₂ in the aliphatic group is preferred. More preferably,-is substituted with an oxygen atom. The aliphatic group having a polymerizable group represented by X ¹ to X ⁴ is preferably substituted at one or two sites by a hetero atom, more preferably substituted at one site by a hetero atom, Ar ¹¹ to Ar More preferably, one position adjacent to the aryl group containing a benzene ring surrounded by a broken line represented by ¹⁴ is substituted with a heteroatom.
As the polymerizable group contained in the aliphatic group having a polymerizable group represented by X ¹ to X ⁴ , a polymerizable group capable of radical polymerization or cationic polymerization (hereinafter, also referred to as a radical polymerizable group and a cationic polymerizable group, respectively) Is preferred.
As the radical polymerizable group, a generally known radical polymerizable group can be used, and a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization can be mentioned as a preferred one. Specifically, Examples thereof include a vinyl group and a (meth) acryloyloxy group. Among these, a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable.
As the cationic polymerizable group, a generally known cationic polymerizable group can be used. Specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, And a vinyloxy group etc. can be mentioned. Among 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 substituent contained in Ar ¹ to Ar ⁴ is preferably a radical polymerizable group.
Two or more of Ar ¹ ~ Ar ⁴ includes a substituent having a polymerizable ^group, preferably contains a substituent 2-4 of Ar 1 ~ Ar ⁴ has a polymerizable ^group, Ar 1 ~ Ar More preferably, 2 or 3 out of ⁴ contain a substituent having a polymerizable group, and more preferably 2 out of Ar ¹ to Ar ⁴ contain a substituent having a polymerizable group.
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, X ¹ to X ⁴ are each independently benzene surrounded by a broken line Even if it is substituted with a ring, it may be substituted with a ring other than the benzene ring surrounded by a broken line.

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

In the general formula (Q3), R ¹ to R ⁴ each independently represents a substituent. The substituent represented by R ¹ to R ⁴ is not particularly limited, and examples thereof include halogen atoms, halogenated alkyl groups, alkyl groups, alkenyl groups, acyl groups, hydroxyl groups, hydroxyalkyl groups, alkoxy groups, aryl groups, hetero groups An aryl group, an alicyclic group, etc. can be mentioned. The substituent represented by R ¹ to R ⁴ is preferably an alkyl group, an alkoxy group or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group. And more preferably 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 each 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 by a broken line.

In the general formula (Q3), 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 can each be a substituent that Ar ¹¹ to Ar ¹⁴ can have. The value obtained by subtracting a, b, c, or d from the number of.
e, f, g and h are each independently preferably 0 to 8, more preferably 0 to 2, and still more preferably 0.
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, e, f, g and h are preferably 0 or 1 , 0 is more preferable.

Examples of the compound represented by the 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 with respect to the total solid content of the composition. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, the upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
One type of polymerizable compound may be used alone, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.

<Polymerization initiator>
The composition of the present invention preferably contains a polymerization initiator.
There is no restriction | limiting in particular as a polymerization initiator, It can select suitably from well-known polymerization initiators, For example, what has photosensitivity (what is called a photoinitiator) is preferable.
When the composition of the present invention contains a photopolymerization initiator and the above-described polymerizable compound in addition to the titanium nitride-containing particles, the composition is cured by irradiation with actinic rays or radiation. Sometimes called.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, and the like. Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), a compound described in JP-A-62-258241, a compound described in JP-A-5-281728, a compound described in JP-A-5-34920, and U.S. Pat. No. 4,221,976. And the compounds described in the specification.

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, oniums A compound selected from the group consisting of a compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound and a derivative thereof, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound preferable.

More preferred are trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound, trihalomethyltriazine compound, α-aminoketone Particularly preferred is at least one compound selected from the group consisting of compounds, oxime compounds, triallylimidazole dimer, and benzophenone compounds.

In particular, when the composition of the present invention is used for the production of a light-shielding film of a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape, so that development is possible with no residue in the unexposed area. It is important that From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when a fine pattern is formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Therefore, in view of these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device. Further, the use of an oxime compound can improve the color transfer.
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, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone 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, a compound described in JP-A-2009-191179 in which an 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: both manufactured by BASF) can be used.

More preferred examples of the photopolymerization initiator include oxime compounds. In particular, an oxime initiator is preferable because it has high sensitivity and high polymerization efficiency, can be cured regardless of the color material concentration, and can be easily designed with a high color material concentration.
As specific examples of the oxime compound, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and a compound described in JP-A-2006-342166 can be used.
Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane Examples include -2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Examples include compounds described in 202-232, JP-A No. 2000-66385, JP-A No. 2000-80068, JP-T 2004-534797, and JP-A No. 2006-342166. It is done.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used. Also, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arkles NCI-831 and Adeka Arkles NCI-930 (made by ADEKA) can be used. N-1919 (manufactured by ADEKA) can also be used.

Further, as oxime compounds other than those described above, compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N-position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the dye moiety, ketoxime compounds described in International Patent Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are the same molecule The compounds described in US Pat. No. 7,556,910 and the compounds described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source may be used. .
Preferably, for example, paragraphs 0274 to 0275 of JP 2013-29760 A can be referred to, the contents of which are incorporated herein.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

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 nonmetallic atomic group.
Examples of the monovalent nonmetallic 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. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by 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 general 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-described substituents.
In the 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-described substituents.

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

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

In the 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 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 is a single bond or carbonyl group 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 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 to 4.

In the above formulas (1) and (2), R ¹ and R ² are preferably each independently a methyl group, ethyl group, n-propyl group, isopropyl, cyclohexyl group or 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 formula (1) and formula (2) include, for example, compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.

Specific examples of oxime compounds that are 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 also be used as a photopolymerization initiator.
Specific examples include OE-01 to OE-75 described in WO2015 / 036910.

Commercially available polymerization initiators are 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-acyloxime compounds (for example, Adekaoptomer N-1919, Adeka Arcles NCI-831, manufactured by ADEKA), Adeka Arcles NCI-930, IRGACURE-OXE03, IRGACURE -OXE04 etc. are mentioned, and these contents are It is incorporated in the book.

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 405 nm.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, more preferably from 5,000 to 200, from the viewpoint of sensitivity. More preferably, it is 1,000.
For the molar extinction coefficient of the compound, a known method can be used. For example, in a UV-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian), an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure.
You may use the photoinitiator used for this invention in combination of 2 or more type as needed.

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 relative to the total solid content in the composition, and is preferably 1 to 25% by mass. %, More preferably 1 to 10% by mass. The composition of the present invention may contain only one kind of polymerization initiator, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.

<Solvent>
The composition of the present invention preferably contains a solvent, and more preferably contains an organic solvent.
Examples of organic solvents 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 Nomethyl 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, Examples include, but are not limited to, dimethyl sulfoxide, γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate.

The composition of the present invention may contain one kind of organic solvent or two or more kinds of organic solvents, but the titanium nitride-containing particles of the composition of the present invention may be prepared during the preparation of the composition of the present invention. It is preferable to contain two or more kinds of organic solvents from the viewpoint that the 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, -Consists 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 It is preferable.

When the composition of the present invention contains an organic solvent, the content of the organic solvent is preferably 10 to 90% by mass and more preferably 60 to 90% by mass with respect to the total mass of the composition. preferable. When two or more types of organic solvents are included, the total amount is preferably within the above range.

<Water>
The composition of the present invention may contain water. Water may be intentionally added, or may be inevitably contained in the composition by adding each component contained in the composition of the present invention.
The water content is preferably 0.1 to 1% by mass, more preferably 0.1 to 0.8% by mass, and more preferably 0.1 to 0.4% by mass with respect to the total mass of the composition. More preferably, it is mass%. When the water content is within the above range, the patterning property (resolution) when a cured film is produced is excellent, and the corrosion resistance of the electrode material is also excellent. Moreover, by setting the water content to 0.1 to 1% by mass with respect to the total mass of the composition, the amount of particles in the composition can be further reduced, and the viscosity aging stability of the composition is also excellent. .

<Other ingredients>
In the composition of this invention, other components other than the component mentioned above may be contained.
Hereinafter, each component will be described in detail.

(Silane coupling agent)
A silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule. Note that a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form 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 number of carbon atoms is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
In order to improve the adhesion between the substrate and the cured film, 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). Includes silicon atoms (excluding silicon atoms to which hydrolyzable groups are bonded), alkylene groups substituted with silicon atoms, straight chain alkyl groups having 8 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms Desirably not.

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

The silane coupling agent preferably has one or more curable functional groups selected from the group consisting of a (meth) acryloyloxy group, an epoxy group, and an 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 is often 100 to 1000 from the viewpoint of handleability, and is preferably 270 or more and more preferably 270 to 1000 from the viewpoint that the effect of the present invention is more excellent.

One preferred embodiment of the silane coupling agent is a 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 preferred range is also as described above.
Lz represents a single bond or a divalent linking group. When Lz represents a divalent linking group, examples of the divalent linking group include an alkylene group which may be substituted with a halogen atom, an arylene group which may be substituted with a halogen atom, —NR ¹² —, —CONR ^{_{12 -, - CO -, -}} CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, and combinations thereof. Among them, at least one selected from the group consisting of an alkylene group which may be substituted with a halogen atom having 2 to 10 carbon atoms and an arylene group which may be substituted with 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 kind of group is preferable, an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms, —CO ₂ —, —O—, —CO—, —CONR ¹² —, or A group consisting of a combination of these groups is more preferred. 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 (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-trimethoxysilane (Trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (trade name manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-503), glycidoxyoctyltrimethoxysilane (trade name KBM manufactured by Shin-Etsu Chemical Co., Ltd.) -4803).

As another preferred embodiment of the silane coupling agent, 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 is provided. 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 be bonded to the following atoms and substituents. They may be the same atom, substituent 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 alkyl group, and / or an amino group that can be substituted with an aryl group, silyl Group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group, and the like. These substituents further include an amino group, a halogen atom, a sulfonamide group, a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an alkyl group and / or an aryl group. It may be substituted with an alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxyl group, a salt thereof, a sulfo group, or a salt thereof.
Note that 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 used as a substituent. It preferably has at least one organic group. The amino group structure may be present in the molecule in the form of a partial structure of a 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, or a combination 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. Group, alkoxycarbonyl group, carbonyloxy group, amide group, urea group, alkyleneoxy group ammonium group, alkylammonium group, carboxyl group, or a salt thereof, sulfo group and the like.
Moreover, it is preferable that the nitrogen atom is couple | bonded with the curable functional group through arbitrary organic coupling groups. Preferred examples of the organic linking group include the above-described 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 preferred range is also as described above.
The silane coupling agent Y only needs to have at least one curable functional group in one molecule, but it is also possible to adopt an embodiment having two or more curable functional groups, sensitivity, stability. From this viewpoint, 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-described ranges (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. More preferably, it is 0 to 6% by mass.

The composition of the present invention may contain one silane coupling agent or two or more silane coupling agents. When a composition contains 2 or more types of silane coupling agents, the sum should just be in the said range.

(UV absorber)
The composition of the present invention may contain an ultraviolet absorber. Thereby, the shape of a 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, compounds of paragraphs 0137 to 0142 (corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. .
In addition, a diethylamino-phenylsulfonyl ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) and the like are also preferably used.
Examples of the ultraviolet absorber include 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 when it is included, the content of the ultraviolet absorber is preferably 0.001 to 15% by mass relative 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 more preferable.

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

By including a fluorosurfactant in the composition of the present invention, liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and uniformity of coating thickness and liquid-saving properties 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 fluorosurfactant is applied, the interfacial tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is reduced. It improves and the applicability | paintability to a to-be-coated surface improves. For this reason, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

The fluorine content in the fluorosurfactant 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 coating film thickness and liquid-saving properties, and has good solubility in the composition.

Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC -101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) ), PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA). As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of JP-A No. 2015-117327 can also be used. A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
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 group or propyleneoxy group) (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.
Moreover, the fluoropolymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant. Specific examples thereof include compounds described in JP-A 2010-164965, paragraphs 0050 to 0090 and 0289 to 0295, such as MegaFac RS-101, RS-102, RS-718K, and RS- 72-K and the like.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl 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 Solsperse 20000 include (Nippon Lubrizol Co. tetrazole Co.) and the like. Further, Wako Pure Chemical Industries Ltd., NCW-101, NCW-1001 and, may also be used NCW-1002.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( 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 anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Co., Ltd.), and the like.

Examples of silicone-based surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, and BYK330 (above, manufactured by BYK Chemie).

Only one type of surfactant may be used, or two or more types may be combined. The content of the surfactant is preferably from 0.001 to 2.0% by mass, more preferably from 0.005 to 1.0% by mass, based on the total solid content of the composition of the present invention.

In addition to the above components, the following components may be further added to the composition of the present invention. Examples include sensitizers, co-sensitizers, cross-linking agents, curing accelerators, fillers, thermosetting accelerators, polymerization inhibitors, plasticizers, diluents, and oil sensitizers, and adhesion to the substrate surface. Accelerators and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.) You may add well-known additives, such as, as needed.
These components include, for example, paragraph numbers 0183 to 0228 of JP2012-003225A (corresponding <0237> to <0309> of US Patent Application Publication No. 2013/0034812) and JP2008-250074. Paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, paragraph numbers 0159 to 0184 in JP 2013-195480 A, and the like can be referred to, and the contents thereof are incorporated in this specification. .

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

It is preferable to use a pigment as the colorant. Thereby, it is 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 (a black organic pigment and a black inorganic pigment) is used as the pigment, it is easy to produce a film having a standard deviation of transmittance within the above range of 10% or less.

((Pigment))
Examples of the pigment include various conventionally known pigments.
Examples of 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, 72,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, 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, a zinc halide phthalocyanine pigment having an average number of halogen atoms in the molecule of 10 to 14, bromine atoms on average 8 to 12, and chlorine atoms on average 2 to 5 should be used. Is also possible. Specific examples include the compounds described in International Publication No. 2015/118720.
These organic pigments can be used alone or in various combinations in order to increase color purity.

Various known black pigments can be used as the black pigment. Examples thereof include carbon black and the following black metal-containing inorganic pigments. As the black metal-containing inorganic pigment, a metal oxide or metal containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag Nitrogen can be mentioned. These may be used alone or as a mixture of two or more. Moreover, you may prepare so that it may have desired light-shielding property by using in combination with the inorganic pigment of another hue further to a black pigment. 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, yellow lead , Zinc yellow (1 type of zinc yellow, 2 types of zinc yellow), ultramarine blue, prussian blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, victoria green, bitumen blue (Prussian blue) ), Vanadium zirconium blue, chrome tin pink, pottery red, salmon pink and the like. In particular, these black pigments and other inorganic pigments having other hues are used not only independently but also in combination with a plurality of types of pigments for the purpose of expressing light-shielding properties in a wide wavelength range from ultraviolet to infrared. Is possible.

The black pigment is preferably carbon black or titanium black, and titanium black is particularly preferable from the viewpoint of light-shielding properties in a wide wavelength range from ultraviolet to infrared. Titanium black is black particles having titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. Although not particularly limited, titanium oxynitride includes titanium oxynitride such as International Publication No. 2008/123097, JP-A 2009-58946, JP-A 2010-14848, JP-A 2010-97210, and JP-A 2011-2274670. Further, a mixture of titanium oxynitride and titanium carbide as disclosed in JP 2010-95716 can be used. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and can also be treated with a water-repellent substance as disclosed in JP-A-2007-302836. . Titanium black is a composite oxide such as Cu, Fe, Mn, V, Ni, etc., and one or more black pigments such as cobalt oxide, iron oxide, and carbon black for the purpose of adjusting dispersibility and colorability. You may contain in combination.

Titanium black can be produced by heating a mixture of titanium dioxide and titanium metal in a reducing atmosphere for reduction (Japanese Patent Laid-Open No. 49-5432), or ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, Japanese Patent Laid-Open No. JP-A-61-201610), and a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced 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 / More preferably, it is 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 Corporation), Tilack D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.

The above-mentioned black pigment preferably has an average primary particle diameter of 5 nm or more, and preferably 10 nm or more. From the same viewpoint, the upper limit is preferably 10 μm or less, more preferably 1 μm or less, and even more preferably 100 nm or less. The average primary particle diameter of the black pigment is a value measured by the following method. A mixed liquid containing a black pigment is diluted 80 times with propylene glycol monomethyl ether acetate, and the obtained diluted liquid is measured using a dynamic light scattering method. This measurement is an average particle diameter obtained by using Microtrack (trade name) UPA-EX150 manufactured by Nikkiso Co., Ltd.

Furthermore, it is also preferable to contain titanium black as a dispersion containing titanium black and Si atoms.
In this embodiment, titanium black is contained as a dispersion in the composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion 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 still more preferable.
Here, the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
In order to change the Si / Ti of the object to be dispersed (for example, 0.05 or more), the following means can be used.
First, a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.), whereby titanium black particles are mainly formed. 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 prepared by the plasma method can be suitably used because its particle size is smaller than commercially available titanium oxide fine particles (see the Journal of the Japan Institute of Metals Vol. 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 dispersing agent may be used for the dispersion of titanium oxide and silica particles. Examples of the dispersant include those described in the above-mentioned column of the dispersant.
The dispersion may be performed in a solvent. Examples of the solvent include water and organic solvents. What was demonstrated in the column of the above-mentioned organic solvent is mentioned.
Titanium black in which Si / Ti is adjusted to 0.05 or more, for example, can be obtained by, for example, the methods described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of JP-A-2008-266045. Can be produced.

The composition containing this dispersion by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a suitable range (for example, 0.05 or more). When a light shielding film is formed using an object, the residue derived from the composition outside the region where the light shielding film is formed is reduced. In addition, a residue contains the component derived from compositions, such as a titanium black particle and a resin component.
The reason why the residue is reduced is not yet clear, but the above-mentioned dispersed material tends to have a small particle size (for example, the particle size is 30 nm or less). By increasing the amount of components contained, the adsorptivity of the entire film with the underlying layer is reduced, and this is presumed to contribute to the improvement of the development removal property of the uncured composition (particularly titanium black) in the formation of the light-shielding film. Yes.
In addition, titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet light to infrared light. Therefore, the above-described dispersion containing titanium black and Si atoms (preferably Si / Ti is converted into mass) The light-shielding film formed by using a material having a thickness of 0.05 or more exhibits excellent light-shielding properties.
The content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A ).
Whether or not the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more for the dispersion to be contained in the light-shielding film obtained by curing the composition Is determined using the method (2) described in paragraph 0035 of JP2013-249417A.

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

Further, as the pigment, a tungsten compound and a metal boride can also be used.
Tungsten compounds and metal borides have high absorption for infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, they have high light shielding properties (shielding properties) for infrared rays) and absorption for visible light. It is a low infrared shielding material. For this reason, the photosensitive composition of this invention can form a pattern with high light-shielding property in an infrared region, and high translucency in a visible light region by containing a tungsten compound and / or a metal boride.
In addition, the tungsten compound and the metal boride have a small absorption even for light having a wavelength shorter than the visible range used for exposure of a high-pressure mercury lamp, KrF, ArF, or the like used for image formation.

Examples of the tungsten compound include a tungsten oxide compound, a tungsten boride compound, a tungsten sulfide compound, and the like, and a tungsten oxide compound represented by the following general formula (composition 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

As the metal of M, for example, alkali metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and the like can be mentioned, and an alkali metal is preferable. 1 type or 2 types or more may be sufficient as the metal of M.

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

When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, generation of an impurity phase in the tungsten compound can be more reliably avoided. it can.
When z / y is 2.2 or more, 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 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 by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding light scattering, the average primary particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average primary particle size of the tungsten fine particles is usually 1 nm or more.

Also, two or more tungsten compounds can be used.

Tungsten compounds are commercially available, but 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).
Further, 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.

In addition, 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 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 type or two or more types 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 by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding light scattering, the average primary particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average primary particle size of the metal boride fine particles is usually 1 nm or more.

Also, two or more metal borides can be used.

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

((dye))
Examples of the dye include, for example, JP-A No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, No. 2592207, and US Pat. No. 4,808,501. US Pat. No. 5,667,920, US Pat. No. 505950, US Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, and JP-A-6- The pigment | dye currently disclosed by 194828 gazette etc. can be used. When classified as chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used. 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 extender pigments as 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 can be used alone or in admixture of two or more. The amount of extender used is usually 0 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the colorant. In the present invention, the colorant and extender can be used with their surface modified with a polymer in some cases.

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

When the composition of the present invention contains a colorant, the content of the colorant is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, based on the total solid content of the composition, 35 More preferred is ˜60% by mass.

(Pigment derivative)
The composition of the present invention may contain a pigment derivative. Examples of the pigment derivative include a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group, or a phthalimidomethyl group.
Examples of the organic pigment for constituting the pigment derivative include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.
Moreover, as an acidic group which a pigment derivative has, a sulfonic acid group, a carboxylic acid group, and its quaternary ammonium base are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is especially preferable. The basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.
Specific examples of the pigment derivative include the following compounds. In addition, the descriptions in paragraphs 0162 to 0183 of JP2011-252065 A can be referred to, and the contents thereof are incorporated in this 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 and more preferably 3 to 20% by mass with respect to the total mass of the colorant. The composition of the present invention may contain only one type of pigment derivative or two or more types of pigment derivatives. When two or more types are included, 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-described 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 substances or reducing defects. Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, a filter made of fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon, polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP), and the like can be given. Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
The pore size of the filter is suitably 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 still more preferably 0.3 to 0.0 μm. 7 μm. By setting it within this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filtration clogging of the pigment.
When using 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 filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are 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. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
As the second filter, a filter formed of the same material as the first filter described above can be used. The pore size of the second filter is suitably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, 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. The light shielding property of a cured film improves more because the solid content of a composition is 10 mass% or more. Moreover, when the solid content of the composition is 40% by mass or less, the viscosity stability over time of the composition becomes better.

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

When used as a light shielding film around the image sensor, the thickness of the light shielding film is not particularly limited, but from the viewpoint of obtaining the effect of the present invention more effectively, the film thickness after drying is 0.2 μm or more and 50 μm or less. Is preferably 0.5 μm or more and 30 μm or less, and more preferably 0.7 μm or more and 20 μm or less. Further, 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 obtaining the effect of the present invention more effectively. 1 mm or more and 3.5 mm or less are more preferable.

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

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

Specifically, the composition of the present invention is applied on a substrate directly or via another layer to form a composition layer (composition layer forming step), and exposed through a predetermined mask pattern. By curing only the composition layer portion irradiated with light (exposure process) and developing with a developer (development process), 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 on a substrate to form a composition layer (coating film).

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

As the coating method of the composition of the present invention on the substrate, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied.

In producing a color filter having a light shielding film around the image sensor, the coating thickness of the composition is preferably 0.35 μm or more and 2.0 μm or less from the viewpoint of resolution and developability, and 0.40 μm or more and 1. 5 μm or less is more preferable.

The composition coated on the substrate is usually dried at 70 ° C. or higher and 110 ° C. or lower for 2 minutes or longer and 4 minutes or shorter. Thereby, a 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, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation with actinic rays or radiation. In particular, ultraviolet rays such as g-line, h-line and i-line are preferably used, and a high-pressure mercury lamp is more preferable. The 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, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part (the coating film part irradiated with light) remains.
As the developer, when producing a color filter having a light shielding film around the image sensor, an organic alkali developer that does not cause damage to the underlying circuit or the like is desirable. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.

Examples of the alkaline aqueous solution include an inorganic developer and an organic developer. As the inorganic developer, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate having a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. %, An alkaline aqueous solution dissolved so as to be%. Examples of the organic developer 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 can be added to the alkaline aqueous solution. In the case where a developer composed 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 and a shower developing method can be used.

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

[Color filter, light shielding film]
The cured film formed using the composition of the present invention is a pixel black matrix of a color filter or an image sensor peripheral light shielding film (frame light shielding film) as described above, or in an image display device or 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 a solid-state imaging device such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal Oxide Semiconductor), and is particularly suitable for a high-resolution CCD or CMOS that exceeds 1 million pixels. It is. The color filter can be used by being disposed, for example, between a light receiving portion of each pixel constituting a CCD or CMOS and a microlens for collecting light. In addition, the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape. The partition in this case preferably has a low refractive index for each color pixel. Examples of the image pickup device having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A.
If the color filter of this invention has the said cured film, the form will not be specifically limited.
In the color filter, the cured film can be suitably used, for example, as a pixel black matrix of the color filter or an image sensor peripheral light shielding film (frame light shielding film) as described above.

(Light shielding film)
The light shielding film is formed and used on various members in an image display device or a sensor module (for example, an infrared light cut filter, an outer peripheral portion of a solid-state imaging device, an outer peripheral portion of a wafer level lens, a back surface of a solid-state imaging device, etc.). it can.
Moreover, it is good also as an infrared light cut filter with a light shielding film by forming a light shielding film in at least one part on the surface of an infrared light cut filter.
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 thickness is an average thickness, and is a value obtained by measuring the thickness of any five 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 the light of 400 to 700 nm incident on the light shielding film at an incident angle of 5 ° and measuring the reflectance with a spectrometer UV4100 (trade name) manufactured by Hitachi High Technology.

[Solid-state image sensor]
The solid-state imaging device of the present invention includes the 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 the solid-state imaging device includes the cured film and functions as a solid-state imaging device.

The substrate has a plurality of photodiodes that constitute a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon, etc., and the photodiodes receive light on the transfer electrodes. A light-shielding film having an opening only in the part, 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 part, and a color filter on the device protective film It is the composition which has.
Further, the light source has a condensing means (for example, a microlens, etc., the same shall apply hereinafter) on the device protection layer and below the color filter (on the side close to the substrate), and a constitution having a light condensing means on the color filter. May be. In addition, the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape. The partition in this case preferably has a low refractive index for each color pixel. Examples of the image pickup apparatus having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A.

(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 the definition of display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Industrial Books Co., Ltd.) Issued in the first year). The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.

When the color filter of the present invention is applied to a liquid crystal display device, the form is not particularly limited.
Below, the aspect in the case of applying the color filter of this invention to a liquid crystal display device is explained in full 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 in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the color filter of the present invention is a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), and a STN (Super). -Twist Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), and R-OCB (Reflective Opt).
In addition, the color filter in the present invention can be used for 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 resistance to the peeling liquid, in addition to the normal required characteristics as described above. Sometimes. Since the color filter of the present invention is excellent in light resistance and the like, a COA type liquid crystal display device having high resolution and excellent long-term durability can be provided. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-technology and latest trends in the market-(issued in 2001 by Toray Research Center Research Division)".

The liquid crystal display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee 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. Regarding these components, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
Regarding backlighting, SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Yukiaki Yagi), etc. Are listed.

The cured film of the present invention is a portable device such as a personal computer, a tablet, a mobile phone, a smartphone, or a digital camera; an office automation (OA) device such as a multifunction printer or a scanner; a monitoring camera, a barcode reader, a cash automatic Industrial equipment such as personal identification using ATMs, high-speed cameras, or face image authentication; in-vehicle camera equipment; medical camera equipment such as endoscopes, capsule endoscopes, or catheters; Optics used in 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 astronomy or deep space targets Light shielding member or light shielding layer of filter or module It can be used. Furthermore, the cured film of the present invention can be used for an antireflection member or an antireflection layer of the optical filter or module.

Moreover, the cured film of this invention can be used also for uses, such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). Although it does not specifically limit, In addition to the optical filter or optical film used for micro LED or micro OLED, it is used suitably with respect to the member which provides 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.

Moreover, the cured film of this invention can be used also for uses, such as a quantum dot display. Although it does not specifically limit, In addition to the optical filter and optical film which are used for a quantum dot display, it uses suitably with respect to the member which provides a light-shielding function and an antireflection function.
Examples of quantum dot displays include U.S. Patent Application Publication No. 2013/0335677, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, and U.S. Patent Application Publication No. 2014/0035960. Those described are mentioned.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

Hereinafter, the present invention will be described in detail using examples. However, the present invention is not limited to this. Unless otherwise specified, “part” and “%” are based on mass.

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

<Titanium nitride-containing particles>
As titanium nitride-containing particles, 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 according to the black composite fine particle production apparatus described 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 the plasma gas supply source mixes argon gas 50 L / min and nitrogen 50 L / min as plasma gas. A gas was supplied to generate an argon-nitrogen thermal plasma flame in the plasma torch. Moreover, 10 L / min carrier gas was supplied from the spray gas supply source of the material supply apparatus.
Further, titanium tetrachloride (liquid) as the particle raw material 1, liquid ammonia (manufactured by Ube Industries) as the particle raw material 2, and Ti powder particles (manufactured by Toho Tech Co., “TC-200”) as the particle raw material 3 are carrier gases. Along with argon gas, it was supplied into a thermal plasma flame in a plasma torch, evaporated in the thermal plasma flame, and highly dispersed in a 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 a gas supplied into the chamber by the gas supply device. The flow rate in the chamber at this time was 5 m / sec, and the supply amount was 1000 L / min. The pressure in the cyclone was 50 kPa, and the supply speed 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 labo kiln L / K manufactured by Narabashi Corporation as a firing furnace. Specifically, heat treatment was performed at 240 ° C. for 0.2 hours while supplying nitrogen as an atmosphere gas to the baking furnace at 100 mL / min.
In this way, titanium nitride-containing particles TiN-1 were obtained.

The obtained titanium nitride-containing particles TiN-1 were measured for the content of titanium (Ti) atoms and chlorine (Cl) atoms by ICP emission spectroscopy. For the ICP emission spectroscopic analysis, an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.
The nitrogen atom content 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.
For the titanium nitride-containing particles TiN-2 to TiN-19 described later, the contents of Ti atoms, Cl atoms, and nitrogen atoms were measured in the same manner as the titanium nitride-containing particles TiN-1. The remaining amount in each particle is an impurity such as oxygen or metal element derived from an oxide present in the particle.
The results are shown in Tables 1 and 2.

X-ray diffraction of titanium nitride-containing particles TiN-1 was measured by a wide-angle X-ray diffraction method (trade name “RU-200R” manufactured by Rigaku Corporation) with a powder sample placed in an aluminum standard sample holder. As measurement conditions, the X-ray source is CuKα ray, the output is 50 kV / 200 mA, the slit system is 1 ° -1 ° -0.15 mm-0.45 mm, the measurement step (2θ) is 0.02 °, and the scan speed is It was 2 ° / min.
And the diffraction angle (2 (theta)) of the peak originating in this TiN (200) surface was measured. The crystallite size constituting the particles was determined from the half width of this peak using Scherrer's equation. The results are shown in Table 1.
For the following titanium nitride-containing particles TiN-2 to TiN-19, the diffraction angle 2θ and the crystallite size were measured in the same manner as the titanium nitride-containing particles TiN-1. The results are shown in Tables 1 and 2.

The average primary particle size of the titanium nitride-containing particles TiN-1 was measured using a transmission electron microscope (TEM) according to the method described above. In addition, when the shape of the particles was observed simultaneously with the above measurement, it was confirmed that 60 or more of the 100 titanium nitride-containing particles to be observed were spherical. These results are shown in Table 1. In addition, regarding the particle shape observation evaluation, when 60% or more of the measurement target is spherical, it is indicated as “spherical” in the table. When the number of spherical particles was less than 60% of the measurement target, it was indicated in the table as “spherical less than 60%”. In the table, “cube” indicates that the number of cubic particles is 60% or more of the measurement target. Note that the cube is not limited to the one visually recognized as a cube, and the polyhedron whose corners are visually recognized was measured as a cube.
For the following titanium nitride-containing particles TiN-2 to TiN-19, the average primary particle diameter was measured and the shape was observed by the same method as for titanium nitride-containing particles TiN-1. The results are shown in Tables 1 and 2.

The specific surface area of the titanium nitride-containing particles TiN-1 uses a Nippon Bell Co., Ltd. precision fully automatic gas adsorption apparatus ( "BELSORP" 36), after vacuum degassing at 100 ° C., the temperature of liquid nitrogen of the _{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 in the same manner as the titanium nitride-containing particles TiN-1.
The results are shown in Tables 1 and 2.

(Titanium nitride-containing particles TiN-2)
The same as the titanium nitride-containing particles TiN-1, except that the particle raw materials 1 to 3 used for the production of the titanium nitride-containing particles TiN-1 particles, the flow rate ratio, 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)
The same as the titanium nitride-containing particles TiN-1, except that the particle raw materials 1 to 3 used for the production of the titanium nitride-containing particles TiN-1 particles, the flow rate ratio, 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)
The same as the titanium nitride-containing particles TiN-1, except that the particle raw materials 1 to 3 used for the production of the titanium nitride-containing particles TiN-1 particles, the flow rate ratio, 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)
The same as the titanium nitride-containing particles TiN-1, except that the particle raw materials 1 to 3 used for the production of the titanium nitride-containing particles TiN-1 particles, the flow rate ratio, 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 except that the particle raw materials 1 to 3 used in the production of the titanium nitride-containing particles TiN-1 particles, the flow rate ratio, the heat treatment conditions, and the flow rate in the chamber are as shown in Table 1. In the same manner as in Example 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 changed as shown in Table 1.

(Titanium nitride-containing particles TiN-8)
Titanium nitride-containing particles TiN-1 except that the particle raw materials 1 to 3 used in the production of the titanium nitride-containing particles TiN-1 particles, the flow rate ratio, the heat treatment conditions, and the flow rate in the chamber are as shown in Table 1. In the same manner as in Example 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 changed as shown in Table 1.

(Titanium nitride-containing particles TiN-10)
The same as the titanium nitride-containing particles TiN-1, except that the particle raw materials 1 to 3 used for the production of the titanium nitride-containing particles TiN-1 particles, the flow rate ratio, 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)
The same as the titanium nitride-containing particles TiN-1, except that the particle raw materials 1 to 3 used for the production of the titanium nitride-containing particles TiN-1 particles, the flow rate ratio thereof, and the heat treatment conditions were as shown in Table 2. Titanium nitride-containing particles TiN-11 were produced. Note that the particle raw material 3 was not used in TiN-11.

(Titanium nitride-containing particles TiN-12)
The same as the titanium nitride-containing particles TiN-1, except that the particle raw materials 1 to 3 used for the production of the titanium nitride-containing particles TiN-1 particles, the flow rate ratio 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)
The same as the titanium nitride-containing particles TiN-1, except that the particle raw materials 1 to 3 used for the production of the titanium nitride-containing particles TiN-1 particles, the flow rate ratio 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)
The same as the titanium nitride-containing particles TiN-1, except that the particle raw materials 1 to 3 used for the production of the titanium nitride-containing particles TiN-1 particles, the flow rate ratio 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)
The same as the titanium nitride-containing particles TiN-1, except that the particle raw materials 1 to 3 used for the production of the titanium nitride-containing particles TiN-1 particles, the flow rate ratio 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 titanium nitride containing particles TiN-1 particles were produced 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 TiN-1 particles and the flow ratios thereof were as shown in Table 2. Material-containing particles TiN-17 were produced.

(Titanium nitride-containing particles TiN-18)
Titanium nitride containing titanium nitride containing particles TiN-1 particles were produced 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 TiN-1 particles and the flow ratios thereof were as shown in Table 2. Material-containing particles TiN-18 were produced.

(Titanium nitride-containing particles TiN-19)
The same as the titanium nitride-containing particles TiN-1, except that the particle raw materials 1 to 3 used for the production of the titanium nitride-containing particles TiN-1 particles, the flow rate ratio 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, except for the titanium nitride-containing particles TiN-11, TiN-12, TiN-13, and TiN-14, the heat treatment temperature is 240 ° C.

(Table 1)

(Table 2)

<Dispersant>
Dispersants A to E having the following structures were used as the dispersants. In the dispersants A, B, and D, the numerical value described in each structural unit intends the mass% of each structural unit with respect to all the structural units. In the dispersant C, the numerical values (a to e) described in each structural unit intend the molar ratio of each structural unit to all structural units, and x and y intend the number of linkages. Further, in the dispersant E, the numerical value described in the linking group linked to Z is intended to be 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, made 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)
OXE-03: Irgacure OXE03 (trade name, manufactured by BASF Japan)
・ 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 The above-mentioned distilled butyl acetate and distilled cyclopentanone are commercially available butyl acetate And what distilled and refine | purified cyclopentanone was used.

<Polymerization inhibitor>
・ P-Methoxyphenol

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

<Preparation of pigment dispersion>
First, titanium nitride-containing particles, a dispersant, and a solvent were mixed for 15 minutes with a stirrer (EUROSTAR manufactured by IKA) to obtain a dispersion. Next, the obtained dispersion was subjected to a dispersion treatment under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises Co., Ltd. to obtain a pigment dispersion.
(Distribution condition)
・ Bead diameter: 0.05mm, (YTZ manufactured by Nikkato)
・ Bead filling rate: 65% by volume
・ Mill peripheral speed: 10m / sec
・ Separator peripheral speed: 13m / s
・ Amount of liquid mixture to be dispersed: 15kg
・ Circulating flow rate (pump supply amount): 90 kg / hour
・ Processing liquid temperature: 19-21 ℃
・ Cooling water: Water ・ Processing time: 22 hours

<Preparation of composition>
Next, the pigment dispersion, binder resin, polymerizable compound, polymerization initiator and solvent were mixed and stirred to obtain the compositions of Examples and Comparative Examples shown in Tables 3 to 5 below. Tables 3 to 5 show the contents (% by mass) of the respective components contained in the compositions of Examples and Comparative Examples.
In addition, the ratio of the dispersant to the titanium nitride-containing particles ((mass ratio) D / P), the solid content concentration (mass%) in the composition, the moisture content in the composition (mass%, the measurement method is shown below. Each composition was prepared so that the pigment concentration (% by mass) in the solid content would be the ratio shown in each Example and Comparative Example in Tables 3-5.

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

[Evaluation test]
The following evaluation tests were performed for the compositions of the examples and comparative examples.

<Outgas>
The frame for color filters was produced using each composition of an Example and a comparative example.
Specifically, the compositions of Examples and Comparative Examples were spin-coated on a semiconductor substrate configured with an 8-inch substrate assuming an image sensor so that the film thickness after pre-baking was 1.5 μm. A coating film was formed. Subsequently, a binary mask capable of forming a light-shielding film having a width of 250 μm and a length of 200 μm is arranged on the outer periphery of a width of 720 μm and a length of 520 μm, and exposure (exposure) is performed using an i-line exposure apparatus (FPA-3000 + i5, manufactured by Canon). Further development was carried out after a quantity of 500 mJ / cm ² ).
The obtained semiconductor substrate having a plurality of frames for the color filter is cut out to a size of 10 mm × 10 mm, and the amount of Cl in the outgas is detected by temperature programmed 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 evaluated according to the following criteria. Went. The degree of vacuum during the measurement was 1 × 10 ⁻⁷ Torr or less.
“A”: In 1 L of outgas, Cl amount is 10 ppm or less “B”: In 1 L of outgas, Cl amount is more than 10 ppm and 50 ppm or less “C”: In 1 L of outgas, Cl amount is more than 50 ppm and 100 ppm or less “D”: In 1 L of outgas , Cl content exceeds 100ppm

<Number of particles>
A sample solution in which the above composition was diluted 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 determined by a flow type particle image analyzer (trade name “FPIA-3000”, Malvern). ).

<OD value>
A film was formed by spin-coating the compositions of Examples and Comparative Examples on a 0.7 mm thick, 10 cm square glass plate (EagleXG, Corning) at a rotation speed of 1.0 μm. A dry film was obtained by heat treatment at 100 ° C. for 2 min on the plate. The obtained substrate was measured for OD with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies), the lowest OD value was measured in the wavelength region from 400 nm to 1200 nm, and 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>
About the composition of an Example and a comparative example, filterability evaluation was performed using the capsule filter DFA (Nippon Pole company make, nylon hole diameter 0.45 micrometer, 2 inches). In addition, 16 kg of the composition was filtered under the condition of a flow rate of 400 ml / min, and evaluated according to the following criteria.
“A”: All 16 kg was filtered.
“B”: After being filtered to 12 kg or more and less than 16 kg, the flow rate was less than 400 mL / min.
“C”: After being filtered to 8 kg or more and less than 12 kg, the flow rate was less than 400 mL / min.
“D”: After filtration to less than 8 kg, the flow rate was less than 400 mL / min.

<Composition aging viscosity stability (CM aging stability)>
The compositions of Examples and Comparative Examples were stored at 23 ° C. for 30 days and then stored at 7 ° C. for 9 months. Thereafter, the viscosity of each composition before and after storage was measured using an E-type viscometer (trade name “R85 type viscometer” manufactured by Toki Sangyo Co., Ltd.) under the conditions of 10 rpm and 23 ° C. The viscosity increase rate was calculated. The evaluation criteria are as follows.
(Thickening rate) = (viscosity after aging)-(viscosity immediately after preparation) / (viscosity immediately after preparation)
“A”: Thickening rate less than 3% “B”: Thickening rate of 3% or more and less than 5% “C”: Thickening rate of 5% or more and less than 10% “D”: Thickening rate of 10% or more

<Patternability (resolution)>
Using the compositions of Examples and Comparative Examples, a coating film was formed on the image sensor device substrate with a spin coater. Next, the obtained coating film was pre-baked at 100 ° C. for 2 minutes on a hot plate. Subsequently, the coating film that has been subjected to the pre-baking process is exposed using an i-line exposure apparatus (FPA, manufactured by Canon Inc.), and further developed to cover the outer periphery of the light receiving part on the substrate except for the dicing line and the electrode part. Simultaneously with the formation of 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 alignment marks formed using an optical microscope.
“A”: 20 marks were formed.
“B”: 19 marks were formed.
“C”: 18 marks were formed.
“D”: There were 17 or fewer marks.

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

The evaluation results of the above evaluation tests are shown in Tables 3 to 5.
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 within the range of 0.001 to 0.3 mass% (in other words, 10 mass ppm to 3000 mass ppm). As a result, it was shown that a cured film excellent in the anticorrosive property of the electrode and excellent in patterning property (resolution) can be produced (Example).
In addition, when the content of chlorine atoms in the titanium nitride-containing particles exceeds 0.3% by mass (in other words, 3000 ppm by mass), it indicates that the patterning property (resolution) and the anticorrosion property of the electrode are inferior. (Comparative Example 1 and Comparative Example 2).
Moreover, when the content of chlorine atoms in the titanium nitride-containing particles was less than 0.001% by mass (in other words, less than 10 ppm by mass), it was shown that the patterning property (resolution) was inferior (comparison). Example 3 and Comparative Example 4).

Further, by comparison with Examples 17 to 21, the water content is 0.1 to 1% by mass (preferably 0.1 to 0.8% by mass, more preferably 0.1% by mass based on the total mass of the composition). It was confirmed that the cured film was excellent in patterning property (resolution) and anticorrosion property of the electrode material. Moreover, by setting the water content to 0.1 to 1% by mass with respect to the total mass of the composition, the amount of particles in the composition can be further reduced, and the viscosity aging stability of the composition is also excellent. It was confirmed.
Further, by comparing Example 26 and Example 27, it was confirmed that when D / P was 0.3 or less, the cured film was more excellent in patternability (resolution).
By comparison with Examples 26, 31 and 32, when the content of titanium nitride-containing particles is 30 to 70% by mass with respect to the total solid content of the composition, spectral properties (good OD value), It was confirmed that the patterning property (resolution) and the corrosion resistance of the electrode were excellent.
Further, in 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. Moreover, it was confirmed that the filterability is also excellent.
Further, in comparison with Examples 10 to 14, when the diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particles is CuKα ray as an X-ray source, it exceeds 42.8 ° and 43.5 °. It was confirmed that the film was excellent in spectroscopic property (good OD value) and patterning property (resolution) when the temperature was not more than 0 °.
Further, by comparison with Examples 12 to 15, it was confirmed that when the average primary particle diameter of the titanium nitride-containing particles was 10 to 30 nm, the spectral properties (good OD value) were excellent. It was also confirmed that the composition was excellent in viscosity aging stability. Moreover, it was 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, when the ratio of the spherical shape is 60% by mass or more in the shape of the primary particles using a transmission electron microscope of the titanium nitride-containing particles, the spectral properties (good) OD value) and patterning properties (resolution) were confirmed to be excellent. It was also confirmed that the composition was excellent in filterability and viscosity aging stability.

Evaluation was conducted 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 pigment dispersion, carbon black (trade name “Color Black S170”, manufactured by Degussa, average primary particle diameter of 17 nm, BET specific surface area of 200 m ² / g, gas black method, instead of titanium nitride-containing particles, was used. A carbon black dispersion was obtained by the same method except that carbon black produced by the above method was used.

In the preparation of the composition of Example 1, titanium nitride-containing particles TiN-1 are contained in place of the pigment dispersion added to contain 19% by mass of titanium nitride-containing particles TiN-1 in the composition. Mixture of pigment dispersion and CB dispersion described above [titanium nitride-containing particles TiN-1 in composition: carbon black of 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. The composition was prepared in the same manner except that was used, and evaluated using this composition. 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 titanium nitride-containing particles. A dispersion was prepared to obtain a chromatic pigment dispersion (PY dispersion).

In the preparation of the composition of Example 1, titanium nitride-containing particles TiN-1 are contained in place of the pigment dispersion added to contain 19% by mass of titanium nitride-containing particles TiN-1 in the composition. Mixture of pigment dispersion and the above PY dispersion [titanium nitride-containing particles TiN-1 in the composition: Pigment Yellow 150 in the composition = 17: 2 (mass ratio). The total content of titanium nitride-containing particles TiN-1 and Pigment Yellow 150 in the composition is 19% by mass. The composition was prepared in the same manner except that was used, and evaluated using this composition. As a result of the evaluation, it was found that the same light shielding property as in Example 1 was obtained, and a darker film was obtained.

Claims

Containing titanium nitride-containing particles containing chlorine atoms,
A 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 peak diffraction angle 2θ derived from the (200) plane of the titanium nitride-containing particles is greater than 42.8 ° and 43.5 ° or less when CuKα rays are used as an X-ray source. Composition.
The composition according to claim 1 or 2, wherein the titanium nitride-containing particles have a specific surface area determined by a BET method of 40 to 60 m 2 / g.
The composition according to any one of claims 1 to 3, wherein the titanium nitride-containing particles have an average primary particle diameter of 10 to 30 nm.
5. In photographic observation of a primary particle image of the titanium nitride-containing particles using a transmission electron microscope, 60 or more of 100 observation objects are spherical. Composition.
Furthermore, the composition according to any one of claims 1 to 5, further comprising two or more solvents.
The composition according to any one of claims 1 to 6, further comprising a dispersant.
The composition according to claim 7, wherein a content ratio of the dispersant to the titanium nitride-containing particles is 0.3 or less by mass ratio.
The composition according to any one of claims 1 to 8, further comprising a polymerizable compound.
The composition according to any one of claims 1 to 9, further comprising a polymerization initiator.
The composition according to any one of claims 1 to 10, wherein a solid content in the composition is 10 to 40% by mass.
The composition according to any one of claims 1 to 11, wherein a content of the titanium nitride-containing particles is 30 to 70 mass% with respect to a total solid content of the composition.
In addition, it contains water
The composition according to any one of claims 1 to 12, wherein a content of the water is 0.1 to 1% by mass with respect to a total mass of the composition.
In addition, it contains a dispersant,
The composition according to any one of claims 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.
A cured film obtained using the composition according to any one of claims 1 to 14.
A color filter having the cured film according to claim 15.
A light-shielding film having the cured film according to claim 15.
A solid-state imaging device having the cured film according to claim 15.
An image display device comprising the cured film according to claim 15.