KR20180116354A - Composition, a cured film, a color filter, a light-shielding film, a solid-state image pickup device and an image display device - Google Patents

Abstract

A composition capable of producing a cured film having excellent anticorrosion property and excellent patterning property is provided. A cured film, a color filter, a light shielding film, a solid-state image pickup device, and an image display device are also provided. The composition contains titanium nitride-containing particles containing a chlorine atom, and the content of the chlorine atoms in the titanium nitride-containing particles is 0.001 to 0.3 mass%.

Description

Composition, a cured film, a color filter, a light-shielding film, a solid-state image pickup device and an image display device

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

The solid-state imaging device includes a photographing lens, a solid-state imaging device (hereinafter also referred to as an "image sensor") such as a CCD (charge-coupled device) and a CMOS (complementary metal oxide semiconductor) And a circuit board on which the solid-state imaging device is mounted. This solid-state imaging device is mounted on a digital camera, a camera-equipped mobile phone, a smart phone, or the like.

In the solid-state imaging device, noise due to reflection of visible light may occur. Therefore, for the purpose of suppressing the generation of noise, a predetermined light-shielding film is provided in the solid-state imaging device. As a composition for forming a light-shielding film, a black composition containing a black pigment such as titanium black is used.

On the other hand, a color filter disposed in a solid-state image pickup device, a liquid crystal imaging device, and the like is provided between each pixel of R (red), G (green), and B (blue) for the purpose of preventing color mixing of light between colored pixels, There is a case where a black matrix is formed. In addition, in the color filter, a shielding film (frame shielding film) around the image sensor is formed in the frame region for the purpose of preventing light leakage of the light receiving portion of the solid-state image pickup device.

A black composition containing a black pigment such as titanium black is also used for the composition for forming the black matrix described above. For example, Patent Document 1 discloses a black resin composition for a resin black matrix containing at least a light-shielding material, a resin and a solvent, and at least titanium nitride particles as a light-shielding material, And the diffraction angle 2? Of the peak derived from the (200) plane of the nitride particle is not less than 42.5 占 and not more than 42.8 占 "(Claim 1).

Patent Document 1: Japanese Patent Publication No. 5136139

When the cured film of the black composition containing the titanium nitride particles (titanium nitride-containing particles) as described above is used, for example, as a light shielding film of a constituent member of a solid-state image sensor or a black matrix of a color filter or a light shielding film around an image sensor, May be stacked on the substrate on which the electrodes are arranged.

The present inventors prepared a black composition containing the titanium nitride particles (titanium nitride-containing particles) described in Patent Document 1, and formed a cured film so as to cover the electrodes on the substrate on which the electrodes were arranged, . As a result, depending on the type of the titanium nitride particles (titanium nitride-containing particles), it was found that rusting or the like occurred in a region contacting the light-shielding film of the electrode, that is, the electrode was corroded. It has also been found that when the patterned cured film is similarly formed using the black composition, the resolution of the pattern (patternability) may not satisfy the desired requirements.

Accordingly, it is an object of the present invention to provide a composition capable of producing a cured film having excellent anticorrosion property and excellent patterning property. It is also an object of the present invention to provide a cured film, a color filter, a light-shielding film, a solid-state image pickup device and an image display device.

The present inventors have intensively studied in order to achieve the above object, and as a result, they found that the above problems can be solved by adjusting the content of chlorine atoms in titanium nitride-containing particles to a predetermined numerical value range, and completed the present invention.

That is, it has been found that the above object can be achieved by the following constitution.

(1) A titanium nitride-containing particle containing a chlorine atom,

Wherein the content of the chlorine atoms in the titanium nitride-containing particles is 0.001 to 0.3 mass%.

(2) The composition according to (1), wherein the diffraction angle 2? Of the peak originating from the (200) plane of the titanium nitride-containing particle is 42.8 占 to 43.5 占 when the CuK? Ray is an X-ray source.

(3) The composition according to (1) or (2), wherein the titanium nitride-containing particles have a specific surface area of 40 to 60 m ² / g as determined by the BET method.

(4) The composition according to any one of (1) to (3), wherein the titanium nitride-containing particles have an average primary particle diameter of 10 to 30 nm.

(5) In the photographing of the primary particles 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 out of 100 of the objects to be observed are spherical.

(6) The composition according to any one of (1) to (5), further containing two or more kinds of solvents.

(7) The composition according to any one of (1) to (6), further comprising a dispersant.

(8) The composition according to (7), wherein the content ratio of the dispersant to the titanium nitride-containing particles is 0.3 or less by mass.

(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 containing 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 mass% with respect to the total solid content of the composition.

(13) A composition containing more water,

The composition according to any one of (1) to (12), wherein the water content is 0.1 to 1% by mass with respect to the total mass of the composition.

(14) The composition according to any one of

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, methyl polyacrylate and methyl polymethacrylate.

(15) A cured film obtained by using the composition according to any one of (1) to (14).

(16) A color filter having the cured film described in (15).

(17) A light-shielding film having the cured film according to (15).

(18) A solid-state imaging device having the cured film described in (15).

(19) An image display device having the cured film described in (15).

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

Hereinafter, the present invention will be described.

In the present specification, the numerical range indicated by using "~ " means a range including numerical values written before and after" ~ "as a lower limit value and an upper limit value.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term " actinic ray "or" radiation " in the present specification means, for example, a line spectrum of a mercury lamp, far ultraviolet ray represented by an excimer laser, extreme ultraviolet ray (EUV light), X ray and electron ray. In the present invention, light means an actinic ray or radiation. In the present specification, the term "exposure" means not only exposure using deep-line spectra of mercury lamps, deep ultraviolet rays represented by excimer lasers, X-rays, EUV light, etc., but also imaging with particle lines such as electron beams and ion beams Are included in the exposure.

As used herein, "(meth) acrylate" refers to acrylate and methacrylate, "(meth) acryl" refers to acrylic and methacrylic, "(meth) acryloyl" Methacryloyl ", and "(meth) acrylamide" represents acrylamide and methacrylamide. In the present specification, the terms "monomer" and "monomer" are synonyms. 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 means a group involved in the polymerization reaction.

[Composition]

The composition of the present invention contains titanium nitride-containing particles containing a chlorine atom, and the content of the chlorine atoms in the titanium nitride-containing particles is 0.001 to 0.3 mass%.

According to the composition of the present invention, it is possible to produce a cured film having excellent anticorrosion property of electrodes and excellent patterning property.

As a result of intensive studies, the present inventors have found that when a light-shielding film is formed on a substrate on which electrodes are arranged by using a black composition containing titanium nitride-containing particles having a content of chlorine atoms of more than 0.3 mass% as a pigment component, It has been confirmed that depending on the use environment conditions, the chlorine atom reacts with moisture or the like in the air to generate hydrochloric acid, thereby deteriorating 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 mass% as a pigment component is used, the optical density (OD) of the obtained coating film is increased and the patterning property tends to be lowered.

From the above viewpoint, the content of chlorine atoms in the titania nitride-containing particles contained in the composition is 0.001 to 0.3% by mass, whereby a cured film having excellent anticorrosion property and excellent patterning property can be formed.

≪ Titanium nitride-containing particles containing chlorine atoms >

For producing the titanium nitride-containing particles, a gas phase reaction method is generally used, and specific examples thereof include an electric furnace method and a thermal plasma method. Among these methods, the thermal plasma method is preferable because of the low content of impurities, easy alignment of the particle diameter, and high productivity.

Examples of the method of generating the thermal plasma include a DC arc discharge, a polyphase arc discharge, a high frequency (RF) plasma, a hybrid plasma, and the like, and a high frequency plasma in which impurities are rarely mixed from the electrode is preferable. As a specific method for producing the titanium nitride-containing particles by the thermal plasma method, for example, a titanium powder is evaporated by a high-frequency thermal plasma to introduce nitrogen into the apparatus as a carrier gas, and the titanium powder is nitrided in the cooling process, Containing particles are synthesized. The thermal plasma method is not limited to the above.

Titanium nitride-containing particles can be obtained by thermal plasma method, so that the diffraction angle 2? Of the peak derived from the (200) plane (details will be described later) when the CuK? Ray is an X- It can be easily adjusted to the range of 43.5 DEG or less.

Here, the method of containing the titanium atom-containing particles in the chlorine atom is not particularly limited. As an example, a method of synthesizing titanium nitride-containing particles containing chlorine atoms by using titanium tetrachloride in combination with titanium powder and flowing ammonia gas as a carrier gas in the thermal plasma method described above is an example.

When the content of the chlorine atoms in the titanium nitride-containing particles is a predetermined amount or more, the particles are heated at a temperature of, for example, 100 to 300 占 폚 (preferably 120 to 280 占 폚, more preferably 120 to 250 占 폚) It is preferable to carry out heat treatment for 72 hours (preferably 3 to 48 hours, more preferably 3 to 36 hours). By carrying out the heat treatment, the content of chlorine atoms contained in the titanium nitride-containing particles can be reduced and adjusted to a predetermined amount.

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

Titanium powder materials (titanium particles) and titanium tetrachloride used for producing titanium nitride-containing particles sometimes contain atoms other than titanium atoms. Other atoms that may be included in the titanium powder material include, for example, Fe atoms and Si atoms.

When the titanium powder material and the titanium tetrachloride contain Fe atoms, the content of Fe atoms is preferably more than 0.001 mass% with respect to the total mass of the titanium powder material and the titanium tetrachloride. As a result, the patterning property of the cured film is more excellent. When the titanium powder material and the titanium tetrachloride contain Fe atoms, the content of Fe atoms is preferably less than 0.4 mass% with respect to the total mass of the titanium powder material and the titanium tetrachloride. As a result, the corrosion resistance of the electrode by the cured film is more excellent (the cured film can further suppress corrosion of the electrode). That is, when the titanium atoms contained in the titanium powder material and the titanium tetrachloride used in the production of the titanium nitride-containing particles are within the above range (more than 0.001 mass% and less than 0.4 mass%), the effect of the present invention can be obtained more remarkably.

When the titanium powder material and the titanium tetrachloride contain Si atoms, the content of Si atoms is preferably more than 0.002 mass% and less than 0.3 mass% with respect to the total mass of the titanium powder material, more preferably 0.01 to 0.15 mass% , More preferably from 0.02 to 0.1 mass%. When the Si atom content is more than 0.002 mass%, the patterning property of the cured film is further improved. When the Si atom content is less than 0.3% by mass, the polarity of the outermost layer of the obtained titanium nitride-containing particles is stabilized, the adsorption of the dispersant to the titanium nitride-containing particles at the time of dispersing the titanium nitride- It is considered that there is an effect of suppressing particle generation by reducing the fine dispersion of the titanium nitride-containing particles. That is, if the titanium atoms contained in the titanium powder material and the titanium tetrachloride used for the production of the titanium nitride-containing particles are within the above-mentioned range, the effect of the present invention can be obtained more remarkably.

The amount of water in the titanium powder material (titanium particle) and the titanium tetrachloride used for producing the titanium nitride-containing particles is preferably less than 1% by mass, more preferably less than 0.1% by mass based on the total mass of the titanium powder material , And it is more preferable that it does not substantially contain it. When the moisture content in the titanium powder material and the titanium tetrachloride used in the production of the titanium nitride-containing particles is within the above range, the effect of the present invention can be obtained more remarkably.

The content of the titanium atom (Ti atom) in the titanium nitride-containing particles is preferably 50 to 85 mass%, more preferably 50 to 80 mass%, and more preferably 50 to 75 mass%, based on the total mass of the titanium nitride- % Is more preferable. 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 the nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 20 to 50 mass%, more preferably 20 to 45 mass%, and more preferably 20 to 40 mass%, based on the total mass of the titanium nitride- % Is more preferable. The content of nitrogen atoms can be analyzed by inert gas fusion-thermal conductivity method.

The content of oxygen atoms in the titanium nitride-containing particles is preferably 12 mass% or less, and more preferably 8 mass% or less, with respect to the total mass of the titanium nitride-containing particles. The content of oxygen atoms can be analyzed by an inert gas melting-infrared absorption method.

The content of chlorine atoms in the titanium nitride-containing particles is 0.001 to 0.3 mass% with respect to the total mass of the titanium nitride-containing particles. Among them, the content is preferably 0.005 to 0.3 mass%, more preferably 0.01 to 0.3 mass%, even more preferably 0.1 to 0.3 mass%, particularly preferably 0.1 to 0.15 mass%. When the content of the chlorine atom is 0.001 mass% or more, the patterning property of the cured film is excellent. When the content of the chlorine atom is 0.3 mass% or less, the patterning property of the cured film is excellent and the cushioning property of the electrode is excellent.

Here, the content of chlorine atoms in the titanium nitride-containing particles is measured by ICP emission spectroscopy.

It is preferable that the titanium nitride-containing particles have a diffraction angle 2? Of the peak derived from the (200) plane when the X-ray diffraction spectrum is measured with the CuK? Ray as the X-ray source being more than 42.8 degrees and not more than 43.5 degrees. The cured film (for example, a black matrix or the like) obtained by using the composition containing the titanium nitride-containing particles having such characteristics has an appropriate OD value and is superior in patterning property (resolution).

As described above, the diffraction angle 2 &thetas; of the peak originating from the (200) plane of the titanium nitride-containing particles is preferably 42.8 DEG to 43.5 DEG, more preferably 42.85 to 43.3 DEG, still more preferably 42.9 to 43.2 DEG Do.

Titanium nitride-containing particles include titanium nitride (TiN) as a main component, and are usually remarkable when oxygen is mixed in the composition and when the particle diameter is small. However, the titanium nitride-containing particles contain some oxygen atoms do.

However, it is preferable that the amount of oxygen contained in the titanium nitride-containing particles is small because an OD value (optical density) higher than that is obtained. It is preferable that the titanium nitride-containing particles do not contain TiO ₂ as a subcomponent. When titanium nitride TiO ₂ as a subcomponent contains titanium nitride-containing particles, a peak derived from anatase-type TiO ₂ (101) as a peak having the strongest intensity is derived from rutile TiO ₂ (110) in the vicinity of 2? = 25.3 占Peak appears near 2? = 27.4 °. However, since TiO ₂ is white and causes a deterioration in the light shielding property of the black matrix, it is preferable that TiO ₂ is reduced to such an extent that it can not be observed as a peak.

The crystallite size constituting the titanium nitride-containing particles can be obtained from the half width of the X-ray diffraction peak, and is calculated using the Scherr equation.

The crystallite size is preferably 20 nm or more, and more preferably 20 to 50 nm. When a black matrix is formed by using titanium nitride-containing particles having a crystallite size of 20 nm or more, the transmitted light of the cured film has a peak wavelength of 475 nm or less and exhibits a bluish purple color. Thus, a black matrix having high light shielding and ultraviolet 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 even more preferably 42 to 55 m ² / g . By setting the specific surface area of the titanium nitride-containing particles to 40 to 60 m ² / g, the obtained cured film has a more appropriate range of OD (optical density) value, and is superior in patterning property (resolution) Do.

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 even more preferably 10 to 20 nm. By setting the average primary particle diameter of the titanium nitride-containing particles to 10 to 30 nm, the OD (optical density) value of the obtained cured film is in a suitable range. From the viewpoint of viscosity stability over time, it is preferable that the average primary particle size of the titanium nitride-containing particles is 10 nm or more.

In the present invention, the average primary particle diameter of the titanium nitride-containing particles is measured by observing the particles with a transmission electron microscope (for example, a device based on a field emission transmission electron microscope of JEM-2100F type manufactured by JEOL Ltd.) It can be obtained from the photograph and refers to the number average particle diameter of the primary particles. Specifically, a dispersion containing titanium nitride-containing particles was prepared by the method described in the examples, and the dispersion was diluted with the same solvent as that of the dispersion so that the solid content became about 1 mass%, the dispersion was dropped on the carbon foil, The transmission electron microscope image of the titanium nitride-containing particles present on the carbon foil is observed. The projection area of the primary particles of the titanium nitride-containing particles is determined by the above apparatus, and the circle-equivalent diameter is obtained therefrom. The arithmetic mean of the obtained circle equivalent diameters was defined as the primary particle diameter. More specifically, in order to obtain the average primary particle diameter, the primary particle diameter was measured for 100 randomly selected particles, and then the primary particle diameter of 80 particles excluding the maximum 10 sides and the minimum 10 particles was arithmetically averaged Is obtained.

It is preferable that 60% or more (in other words, 60% or more) of the 100 out of 100 objects to be observed are spherical in the photographic observation of the primary particle image using the transmission electron microscope described above. When 60% or more of the titanium nitride-containing particles used is spherical, the obtained cured film has an OD (optical density) value in a suitable range and is superior in patterning property (resolution). Further, when at least 60% of the titanium nitride-containing particles used are spherical, the composition has excellent filterability and viscosity stability over time.

In the present invention, the term "spherical" in the present invention does not necessarily mean a true sphere. For example, it may be a substantially spherical shape (a short diameter / long diameter in a two- (Diameter ratio) of about 0.7 to 1) or a spheroid.

The content of the titanium nitride-containing particles is preferably 30 to 70 mass%, more preferably 40 to 68 mass%, and even more preferably 42 to 65 mass% with respect to the total solid content of the composition. When the content of the titanium nitride-containing particles is in the above-mentioned range, the film has excellent spectroscopic properties (good OD value), excellent patterning property (resolution) and excellent corrosion resistance of the electrode.

In the present specification, the solid content means a component constituting the cured film formed by the composition, and does not include a solvent. For example, since a polymerizable compound to be described later is a component constituting a cured film, it is included in a solid matter even if it is a liquid (liquid phase).

<Dispersant>

The composition of the present invention preferably contains a dispersant. The dispersant contributes to the improvement of the dispersibility of the pigment such as the titanium nitride-containing particles described above. In the present invention, the dispersant and the binder resin to be described later are different components.

As the dispersing agent, for example, a known pigment dispersing agent can be suitably selected and used. Among them, a polymer compound is preferable.

Examples of the dispersant include polymer dispersants such as polyamide amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethane, modified polyester, modified poly (meth) acrylate, Acrylic copolymer, naphthalenesulfonic acid-formalin condensate], polyoxyethylene alkylphosphoric acid ester, polyoxyethylene alkylamine, and pigment derivative.

From the structure, the polymer compound can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a block polymer.

The polymer compound is adsorbed on the surface of the titanium nitride-containing particles and the pigment dispersion such as a pigment to be used according to the purpose, and functions to prevent re-aggregation of the pigment dispersion. For this reason, end-modified polymers, graft polymers, and block polymers having anchor sites to the pigment surface are preferred.

On the other hand, by modifying the surface of the titanium nitride-containing particles, the adsorption of the polymer compound to the titanium nitride-containing particles can be promoted.

The polymer compound preferably has a structural unit having a graft chain. Also, in this specification, the term "structural unit" is synonymous with "repeating unit".

Such a polymer compound having a structural unit having a graft chain is excellent in dispersibility of a pigment such as titanium nitride-containing particles and dispersion stability after aging because it has affinity with a solvent by a graft chain. Also, due to the presence of the graft chain, the polymer compound having a structural unit having a graft chain has affinity with a polymerizable compound or other usable resin or the like. As a result, it becomes difficult to generate residues by the alkali phenomenon.

As the graft chain becomes longer, the effect of three-dimensional repulsion increases, and the dispersibility of the pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorption force to the pigment such as titanium nitride-containing particles decreases, and the dispersibility of the pigment tends to be lowered. Therefore, the number of atoms other than hydrogen atoms in the graft chain is preferably 40 to 10,000, more preferably 50 to 2000 atoms excluding hydrogen atoms, and more preferably 60 to 500 atoms other than hydrogen atoms .

Here, the graft chain indicates from the base of the main chain of the copolymer (the atom binding to the main chain in the group branched from the main chain) to the end of the group branched from the main chain.

The graft chain preferably has a polymer structure. Examples of such a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acryl structure), a polyester structure, , A polyurea structure, a polyamide structure, and a polyether structure.

In order to improve the interactivity of the graft chain and the solvent and thereby increase the dispersibility, the graft chain is preferably a graft having at least one member selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure 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 suitably used.

Examples of commercially available macromonomers that are suitably used for the synthesis of high molecular compounds corresponding to structural units having a graft chain possessed by the polymer compound include AA-6 (trade name, manufactured by Doagosei Co., Ltd.), AA-10 6 (trade name, manufactured by Toagosei Co., Ltd.), AW-6 (trade name, manufactured by Toagosei Co., Ltd.) AY-714 (trade name, manufactured by Toagosei Co., Ltd.), AY-707 (trade name, manufactured by Toagosei Co., Ltd.) AK-32 (trade name, manufactured by Toagosei Co., Ltd.), BLEMMER PP-100 (trade name, manufactured by Toagosei Co., Ltd.) (Trade name, manufactured by Nichiyu Corporation), Blemmer PP-500 (trade name, manufactured by Nichiyu Corporation), Blemmer PP-800 (trade name, manufactured by Nichiyu Corporation) (Trade name, manufactured by Nichiyu Corporation), Blemmer 55-PET-800 (trade name, manufactured by Nichiyu Corporation), Blemmer PME-4000 ), Blemmer PSE-400 (trade name, manufactured by Nichiyu Corporation), Blemmer PSE-1300 (trade name, manufactured by Nichiyu Corporation), Blemmer 43PAPE-600B . Of these, preferred are AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (trade name, manufactured by Toagosei Co., Ltd.), AB- 6 (trade name, manufactured by Toagosei Co., Ltd.), AN-6 (trade name, manufactured by Doagosei Co., Ltd.) and BLEMMER PME-4000 (trade name, manufactured by Nichiyu Corporation).

The dispersing agent preferably has at least one structure selected from the group consisting of polycaprolactone, polyvalerolactone, methyl polyacrylate and methyl polymethacrylate. Further, it is more preferable to use two or more of these structures in combination.

Here, the polycaprolactone structure refers to a structure having a structure in which? -Caprolactone is replaced by a repeating unit. The polyvalero lactone structure refers to a structure having a structure in which? -Valerolactone is replaced as a repeating unit.

Specific examples of the dispersant having a polycaprolactone structure include those in which j and k in the following formulas (1) and (2) are 5. Specific examples of the dispersant having a polyvalero lactone structure include those wherein j and k in the following formulas (1) and (2) are 4.

As specific examples of the dispersant having a methyl polyacrylate structure, X ⁵ in the following formula (4) is a hydrogen atom and R ⁴ is a methyl group. Specific examples of the dispersant having a polymethylmethacrylate structure include those in which X ⁵ in the following formula (4) is a methyl group and R ⁴ is a methyl group.

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

[Chemical Formula 1]

In the formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH 2. 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 preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (in terms of synthetic limitations) , A hydrogen atom or a methyl group, more preferably a methyl group.

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

(2)

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, but specific examples thereof include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkyl thioether group, an aryl thioether group, a heteroaryl thioether group, . Among them, as an organic group represented by Z ¹ , Z ² , Z ³ and Z ⁴ , from the viewpoint of improving the dispersibility, it is preferable to have a steric repulsion effect, and each independently an alkyl group or an alkoxy group having 5 to 24 carbon atoms Among them, branched alkyl groups having 5 to 24 carbon atoms, cyclic alkyl groups having 5 to 24 carbon atoms, and alkoxy groups having 5 to 24 carbon atoms are particularly preferable. The alkyl group contained in the alkoxy group may be any of linear, branched and 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 an integer of 4 to 6 and more preferably 5 in view of dispersion stability and developability of the composition.

In the formula (3), R ³ represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, plural R ³ may be the same or different.

In formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, 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, and a straight chain alkyl group having 1 to 20 carbon atoms More preferably a straight chain alkyl group having 1 to 6 carbon atoms. When q is 2 to 500 in the formula (4), a plurality of X ⁵ and R ⁴ existing in the graft copolymer may be the same or different.

The polymer compound may have a structural unit having a graft chain having two or more different structures. That is, the polymer molecule may contain structural units represented by formulas (1) to (4) having different structures from each other, and n, m, p, and In the formulas (1) and (2), j and k may be different from each other in the side chain, and in the formulas (3) and (4) R ³ , R ⁴ and X ⁵ present in plural groups may be the same or different.

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.

(3)

Formula (1A) of the, X ^1, Y ^1, Z ¹ and n is ¹ and X, Y ^1, Z ¹ and n and the consent of the formula (1), are also the same preferable range. In the formula ^{(2A), X 2, Y} 2, Z 2 and m is ^2, and X, Y ^2, Z ² and m and consent of the formula (2) are also the same preferable range.

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

[Chemical Formula 4]

In the formula (3A) or ^{(3B), X 3, Y} 3, Z 3 , and p is ^3, and X, Y ^3, Z ^3, and p and consent of the formula (3) it is also the same preferable range.

It is more preferable that the polymer compound has a structural unit represented by formula (1A) as a structural unit having a graft chain.

In the polymer compound, a structural unit having a graft chain (for example, a structural unit represented by the above formulas (1) to (4)) is preferably in the range of 2 to 90% , And it is more preferable that it is contained in the range of 5 to 30%. When the structural unit having a graft chain is contained within this range, the dispersibility of the titanium nitride-containing particles is high, and the developability in forming the cured film is good.

The polymer compound preferably has a hydrophobic structural unit that is different from the structural unit having a graft chain (i.e., does not correspond to a 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, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group, etc.).

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

The ClogP value is a value calculated by the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides the value of "computed logP" calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of the compound and estimates the logP value of the compound by dividing the chemical structure into partial structures (fragments) and summing the assigned logP contributions for the fragments. The details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v 4.82 is used.

A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds., P. 295, Pergamon Press, 1990 C. Hansch & A. J. Leo. Substituent Constants for Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306,1993.

log P means a common logarithm of the partition coefficient P and is a physical property value showing quantitatively how an organic compound is distributed in an equilibrium of a two-phase system of oil (generally 1-octanol) and water, Is expressed by the following equation.

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 value of logP is increased to 0 on the positive side, the oil solubility is increased and when the negative value is increased, the water solubility is increased. The water solubility of the organic compound is negatively correlated with that of the organic compound. And is widely used as a parameter for evaluating the hydrophilicity.

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

[Chemical Formula 5]

In the above formulas (i) to (iii), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine or bromine) (For example, methyl group, ethyl group, propyl group, etc.).

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. It is particularly preferable that R ² and R ³ are hydrogen atoms.

X represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.

L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkenylene group, a substituted alkenylene group), a divalent aromatic group (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR ³¹ -, where R is a substituted or unsubstituted aryl group), a divalent heterocyclic group, ³¹ represents 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 carbon number of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, and even more preferably from 1 to 10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group.

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

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocycle may be condensed with another heterocycle, an aliphatic ring or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent, a halogen atom, a hydroxyl group, an oxo group (= O), Im oxo group (= S), imino group (= NH), a substituted imino group (= NR ^32, where R ³² be an aliphatic group, An aromatic group or a heterocyclic group), an aliphatic group, an aromatic group, and a heterocyclic group.

L is preferably a divalent linking group containing a single bond, an alkylene group or 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 repeating oxyalkylene structures. As the polyoxyalkylene structure, a polyoxyethylene structure or a polyoxypropylene structure is preferable. The polyoxyethylene structure is represented by - (OCH ₂ CH ₂ ) n-, and n is preferably an integer of 2 or more, more preferably an integer of 2 to 10.

Examples of Z include an aliphatic group (e.g., alkyl group, substituted alkyl group, unsaturated alkyl group, substituted unsaturated alkyl group), aromatic group (e.g., aryl group, substituted aryl group, arylene group, substituted arylene group) . &Lt; / RTI &gt; These groups include an oxygen atom (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR ³¹ -, wherein R ³¹ represents an aliphatic group, ), Or a carbonyl group (-CO-).

The aliphatic group may have a cyclic structure or a branched structure. The carbon number of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, and even more preferably from 1 to 10. Examples of the cyclic hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenylene group, a biphenyl group, and a 4-cyclohexylphenyl group. Examples of the cyclic hydrocarbon group include a cyclic hydrocarbon group and a cyclic hydrocarbon group, do. As the bridged cyclic hydrocarbon ring, there may be mentioned, for example, pinene, bonene, nopine, novone, and bicyclooctane ring (bicyclo [2.2.2] octanoic 2 recalled cyclic hydrocarbons, such as heptane ring, etc.), homo blade Dane, adamantane, tricyclo [5.2.1.0 ^2,6] de cane, such as, and tricyclo [4.3.1.1 ^2,5] undecane ring Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane, and perhydro-1,4-methano-5,8-methanonaphthalene ring, And the like. Examples of the bridged cyclic hydrocarbon ring include condensed cyclic hydrocarbon rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroanenaphthene, perhydrofluorene, perhydroindene, And a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a hydroperylene ring are condensed.

The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group. Provided that the aliphatic group does not have an acid group as a substituent.

The carbon number of the aromatic group is preferably from 6 to 20, more preferably from 6 to 15, and even more preferably from 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. Provided that the aromatic group does not have an acid group as a substituent.

The heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocycle may be condensed with another heterocycle, an aliphatic ring or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent, a halogen atom, a hydroxyl group, an oxo group (= O), Im oxo group (= S), imino group (= NH), a substituted imino group (= NR ^32, where R ³² be an aliphatic group, An aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group. Provided that the heterocyclic group does not have an acid group as a substituent.

R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine or bromine), an alkyl group having 1 to 6 carbon atoms (for example, For example, a methyl group, an ethyl group, a propyl group, etc.), Z, or LZ. Wherein L and Z are the same as those in the above. As R ⁴ , R ⁵ , and R ⁶ , a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom is more preferable.

In the present invention, as the monomer represented by the general formula (i), R ¹ , R ² , and R ³ are each a hydrogen atom or a methyl group, L is a single bond or a divalent linking group containing an alkylene group or an oxyalkylene structure , X is an oxygen atom or an imino group, and Z is an aliphatic group, a heterocyclic group or an aromatic group.

As the monomer represented by the general formula (ii), a compound wherein R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable. As the monomer represented by the general formula (iii), a compound wherein R ⁴ , R ⁵ , and R ⁶ are each a hydrogen atom or a methyl group and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable.

Examples of representative compounds represented by the formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrene, and the like.

As a representative example of the compounds represented by formulas (i) to (iii), reference can be made to the compounds described in paragraphs 0089 to 0093 of JP-A-2013-249417, the contents of which are incorporated herein by reference.

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

The polymer compound can introduce a functional group capable of forming an interaction with a pigment such as a titanium nitride-containing particle or the like. Here, the polymer compound preferably further has a structural unit having a functional group capable of forming an interaction with a pigment such as a titanium nitride-containing particle.

Examples of the functional group capable of forming an interaction with the pigment such as the titanium nitride-containing particles include an acid group, a basic group, a coordinating group, and a functional group having reactivity.

When the polymer compound has an acid group, a basic group, a coordinating group, or a functional group having reactivity, it is preferable that the polymer compound has a structural unit having an acid group, a structural unit having a basic group, a structural unit having a coordinating group, desirable.

In particular, the polymer compound has an alkali-soluble group such as a carboxylic acid group as an acid group, so that the developability for forming a pattern by an alkali development can be imparted to the polymer compound.

That is, by introducing an alkali-soluble group into the polymer compound, the composition of the present invention has alkali-solubility in the polymer compound as a dispersing agent contributing to the dispersion of the pigment such as titanium nitride-containing particles. Such a composition containing a polymer compound is excellent in the light shielding property of the exposed portion and improves the alkali developability of the unexposed portion.

Further, when the polymer compound has a structural unit having an acid group, the polymer compound tends to be easily compatible with the solvent, and the coating property tends to be improved.

This is because the acid group in the structural unit having an acid group is likely to interact with the pigment such as the titanium nitride-containing particles, and the polymer compound stably disperses the pigment such as the titanium nitride-containing particles and the pigment such as the titanium nitride- The viscosity of the polymer compound dispersed therein is low, and the polymer compound itself is likely to be stably dispersed.

However, the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the structural unit having the graft chain described above or may be another structural unit, but the structural unit having an alkali-soluble group as an acid group is not limited to the above- (I.e., does not correspond to the hydrophobic structural unit described above).

Examples of the acid group which is a functional group capable of forming an interaction with the pigment such as titanium nitride-containing particles include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and preferably a carboxylic acid group, And a phosphoric acid group. Particularly preferred is a carboxylic acid group in view of good adsorption ability to pigments such as titanium nitride-containing particles and high pigment dispersibility.

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 content of the structural unit having an acid group is preferably 5 to 80% by mass, based on the total mass of the polymer compound, of the structural unit having an acid group, , And more preferably 10 to 60% from the viewpoint of suppressing the damage of the image caused by the alkali development.

Examples of the basic group that is a functional group capable of forming an interaction with a pigment such as a titanium nitride-containing particle include a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, And is preferably a tertiary amino group because of its good adsorptivity to pigments such as titanium nitride-containing particles and also high dispersibility of pigments. The polymer compound may have one or more of these basic groups.

The polymer compound may or may not contain a structural unit having a basic group, but when contained, the content of the structural unit having a basic group is preferably 0.01% to 50% % Or less, and more preferably from 0.01% or more and 30% or less from the viewpoint of inhibiting developability.

Examples of the coordinating group which is a functional group capable of forming an interaction with the pigment such as titanium nitride-containing particles and the reactive functional group include, for example, an acetyl acetoxy group, a trialkoxysilyl group, an isocyanate group, And acid chlorides. Preferred is an acetyl acetoxy group in view of good adsorption ability to pigments such as titanium nitride-containing particles and high dispersibility of pigments. 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 contained, the content of these structural units is preferably in the range of , Preferably not less than 10% and not more than 80%, and more preferably not less than 20% and not more than 60% from the viewpoint of suppressing development inhibition.

In the case where the polymer compound in the present invention has functional groups capable of forming an interaction with a pigment such as titanium nitride-containing particles in addition to the graft chain, it is preferable that the interaction with pigments such as various titanium nitride- And the functional groups are not specifically limited. However, the polymer compound is preferably a polymer comprising a structural unit derived from a monomer represented by the following general formulas (iv) to (vi) It is preferable to have the above structural units.

[Chemical Formula 6]

In the general formulas (iv) to (vi), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, , Or an alkyl group having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, etc.).

In the general formulas (iv) to (vi), R ¹¹ , R ¹² and R ¹³ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Is independently a hydrogen atom or a methyl group. In the formula (iv), it is particularly preferable that R ¹² and R ¹³ are each a hydrogen atom.

X ₁ in the general formula (iv) represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.

In the general formula (v), Y represents a methoxy group or a nitrogen atom.

L ₁ in formulas (iv) to (v) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkenylene group, and a substituted alkenylene group) (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR ³¹ '), a substituted or unsubstituted arylene group -, wherein R ³¹ 'is 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 carbon number of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, and even more preferably from 1 to 10. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group and a heterocyclic group.

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

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocycle may be condensed with at least one of another heterocycle, an aliphatic ring or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent, a halogen atom, a hydroxyl group, an oxo group (= O), Im oxo group (= S), imino group (= NH), a substituted imino group (= NR ^32, where R ³² be an aliphatic group, An aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

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

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

In the formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) An alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), -Z ₁ , or L ₁ -Z ₁ . Here, L ₁ and Z ₁ is, and L ₁ and Z ₁ and copper in the above, the same preferable examples. R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

In the present invention, it is preferable that as the monomer represented by the general formula (iv), R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group, L ₁ is a divalent linking group containing an alkylene group or an oxyalkylene structure , X ₁ is an oxygen atom or an imino group, and Z ₁ is a carboxylic acid group.

As the monomer represented by the general formula (v), a compound wherein R ¹¹ is a hydrogen atom or a methyl group, L ¹ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is a meta-group is preferable.

As the monomer represented by formula (vi), it is preferable that R ¹⁴ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom or a methyl group, L ₁ is a single bond or an alkylene group, and Z is a carboxylic acid group.

Representative examples of the monomers (compounds) represented by the general formulas (iv) to (vi) are shown below.

Examples of the monomer include a reaction product of a methacrylic acid, a crotonic acid, an isocrotonic acid, a compound having an addition polymerizable double bond and a hydroxyl group in a 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 and a phthalic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in a molecule and a tetrahydrophthalic anhydride, a compound having an addition polymerizable double bond and a hydroxyl group in the molecule, A reaction product of trimellitic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule with pyromellitic anhydride, a reaction product of acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, Phenol, and 4-hydroxyphenylmethacrylamide, and the like.

The content of the structural unit having a functional group capable of forming an interaction with the pigment such as titanium nitride-containing particles is preferably in the range of from 0.1 to 10 parts by mass, more preferably from 10 to 30 parts by mass, from the viewpoint of the interaction with the pigment such as titanium nitride- Is preferably from 0.05% by mass to 90% by mass, more preferably from 1.0% by mass to 80% by mass, and still more preferably from 10% by mass to 70% by mass.

In order to improve all the performance such as the image strength, the polymer compound may contain a pigment such as a structural unit having a graft chain, a hydrophobic structural unit and a titanium nitride-containing particle, (For example, a structural unit having a functional group having affinity with a dispersion medium used in a dispersion) different from the structural unit having a functional group capable of forming an interaction .

Examples of such another structural unit include a structural unit derived from a radically polymerizable compound selected from acrylonitrile, methacrylonitrile, 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 with respect to the total mass of the polymer compound in terms of mass, , 10% or more and 60% or less. When the content is within the above range, sufficient pattern formation property is maintained.

The acid value of the polymer compound is preferably in the range of 0 mgKOH / g or more and 160 mgKOH / g or less, more preferably 10 mgKOH / g or more and 140 mgKOH / g or less, still more preferably 20 mgKOH / g or more and 120 mgKOH / g or less Range.

When the acid value of the polymer compound is 160 mgKOH / g or less, the pattern peeling at the time of development when the cured film is formed is more effectively suppressed. When the acid value of the polymer compound is 10 mgKOH / g or more, the alkali developability is better. When the acid value of the polymer compound is 20 mgKOH / g or more, the sedimentation of the pigment such as titanium nitride-containing particles can be further suppressed, the number of coarse particles can be further reduced, and the stability over time of the composition can be further improved have.

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

The weight average molecular weight of the polymer compound in the present invention is preferably from 4,000 to 300,000 as a polystyrene reduced value by the GPC (Gel Permeation Chromatography) method, from the viewpoint of pattern peel suppression at the time of development and developability at the time of forming a cured film More preferably 5,000 or more and 200,000 or less, still more preferably 6,000 or more and 100,000 or less, particularly preferably 10,000 or more and 50,000 or less.

The GPC method was carried out by using TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) as a column and THF (tetrahydrofuran) as an eluent, using HLC-8020GPC (manufactured by TOSOH CORPORATION) Furans).

The polymer compound can be synthesized on the basis of known methods. Examples of the solvent used in synthesizing the polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, Methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propylacetate, N, N-dimethylethanolamine, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, toluene, 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 usable in the present invention include "DA-7301" manufactured by Goosumoto Kasei Co., Ltd., "Disperbyk-101 (polyamide amine phosphate)", BYKChemie Quot ;, "BYK-P104, P105 " (high molecular weight unsaturated poly (ethylene oxide)), 111 (phosphate dispersant), 130 (polyamide), 161,162,163,164,165,166,170,190 (Block copolymers), 4400 to 4402 (modified polyacrylate), 5010 (polyester amide), 5765 (polybutylene terephthalate), EFKA4047, 4050 to 4010 to 4165 (polyurethane resin), EFKA4330 to 4340 6750 (azo pigment derivative) "manufactured by Ajinomoto Fine Techno Co., Ltd.," Ajisper PB821, PB822, PB880, PB881 "manufactured by Ajinomoto Fine Techno Co., Quot; Fluorene TG-710 (Yreetain Oligomer) ", "Polyflur No. 50E, No. 300 (acrylic copolymer)" 703-50, DA-705, DA-725 ", manufactured by Kao Corporation, " Diparon KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid) &Quot; Homogenol L-18 (Polymeric Polycarboxylic Acid) ", "Emulgen 920 ", " Dermol RN, N (Naphthalenesulfonic acid-formaldehyde polycondensate) , "930, 935, 985 (polyoxyethylene nonylphenyl ether)", "acetamin 86 (stearylamine acetate)", Nippon Rubisol Co., 28,000, 32000, 38500 (graft copolymer) "manufactured by Nikko Chemicals Co., Ltd.," manufactured by Nippon Kayaku Co., (Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ", manufactured by Shin-Etsu Chemical Co., Ltd., and Hinoact T-8000E manufactured by Kawaken Fine Chemicals Co., , Oganosil COOPIN POLYMER KP341, "W001: cationic surfactant" manufactured by YUSHO CO., LTD., Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, Nonionic surface active agents such as polyoxyethylene nonylphenyl ether, polyethylene glycol diolate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic surface active agents such as "W004, W005, W017" EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 ", manufactured by Morishita Sangyo Co., Ltd., "EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, F38, L42, L44, L61, L64, F68, L72, P95, F77, and F77, manufactured by ADEKA Co., (Trade name) S-20 "manufactured by Sanyo Chemical Industries, Ltd., and the like, There. In addition, Acrybee FFS-6752, Acrybee FFS-187, Acricheter RD-F8, and Cyclamer P may be used.

Examples of commercially available bisphenol resins include DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK- DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajisper PB821, Ajisper PB822 and Ajisper PB881 manufactured by Ajinomoto Fine Techno.

These polymer compounds may be used alone or in combination of two or more.

As specific examples of the polymer compound, reference can be made to the polymer compounds described in paragraphs 0127 to 0129 of Japanese Laid-Open Patent Publication No. 2013-249417, the contents of which are incorporated herein by reference.

As the dispersant, graft copolymers of the above-mentioned polymer compounds and paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 of US2011 / 0124824) of Japanese Laid-Open Patent Publication No. 2010-106268 can be used, And is incorporated herein by reference.

In addition to the above, a polymer compound comprising a constituent component having a side chain structure in which an acidic group of a compound of the paragraphs 0028 to 0084 (corresponding to paragraphs 0075 to 0133 of US2011 / 0279759) of JP-A No. 2011-153283 is bonded via a linking group , The contents of which are expressly incorporated herein by reference.

In the case where the composition contains a dispersant, the content of the dispersant is preferably from 0.1 to 50 mass%, more preferably from 0.5 to 30 mass%, based on the total solid content of the composition.

The dispersant may be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total amount is in the above range.

<Binder Resin>

The composition of the present invention preferably contains a binder resin.

As the binder resin, it is preferable to use a linear organic polymer. As such a linear organic polymer, any known one can be used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline development. Among them, an alkali-soluble resin (a resin having a group capable of promoting alkali solubility) is particularly preferable as the binder resin.

As the binder resin, it is preferable to use, as the linear organic polymer, an alkali-soluble resin having at least one group capable of promoting alkali solubility in a molecule (preferably, a (meth) acrylic copolymer or a molecule having a styrene- . From the viewpoint of heat resistance, a polyhydroxystyrene resin, a polysiloxane resin, a (meth) acrylic resin, a (meth) acrylamide resin and a (meth) acrylic / (meth) acrylamide copolymer resin are preferable, From the viewpoint of control, (meth) acrylic resins, (meth) acrylamide resins and (meth) acrylic / (meth) acrylamide copolymer resins are preferable.

Examples of the group capable of promoting alkali solubility (hereinafter also referred to as acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Among them, those soluble in an organic solvent and capable of being developed by a weakly alkaline aqueous solution are preferable, and an alkali-soluble resin having a structural unit derived from (meth) acrylic acid is more preferable. These acid groups may be only one kind, or two or more kinds.

As the binder resin, for example, a radical polymer having a carboxylic acid group in its side chain, for example, Japanese Patent Application Laid-open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Application Laid-Open Nos. 54-25957, 54-92723, 59-53836, and 59-71048, that is, monomers having a carboxyl group A resin in which an acid anhydride unit is hydrolyzed, half-esterified or half-aminated, or an epoxy acrylate in which an epoxy resin is modified with an unsaturated monocarboxylic acid or an acid anhydride, etc. . Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxy styrene. Examples of the monomer having an acid anhydride include maleic anhydride, . An acidic cellulose derivative having a carboxylic acid group in the side chain may also be mentioned as an example. In addition, a polymer obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group is useful.

The acetal-modified polyvinyl alcohol-based binder resin having an acid group described in each publication of European Patent Publication No. 993966, European Patent Publication No. 1204000, and Japanese Unexamined Patent Publication No. 2001-318463 is excellent in film strength and developability It is suitable because of its excellent balance.

In addition, as the water-soluble linear organic polymer, polyvinylpyrrolidone, polyethylene oxide and the like are useful. In addition, in order to increase the strength of the cured coating, alcohol-soluble nylon and a polyether which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.

Particularly preferred among these are (benzyl (meth) acrylate / (meth) acrylic acid / optionally addition polymerizable vinyl monomer) copolymer and [allyl (meth) acrylate / (meth) acrylic acid / Addition polymerizable vinyl monomer] copolymer is suitable because it has excellent balance of film strength, sensitivity, and developability.

Examples of commercially available products include commercially available products such as ACRYBASE FF-187, FF-426 (manufactured by Fujikura Chemical Industry Co., Ltd.), ARC Liqueur RD-F8 (manufactured by Nippon Shokubai Co., (ACA) 230AA, and the like.

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

As the binder resin, 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).

The definition of the structural unit having a graft chain is the same as that of the structural unit having the graft chain of the above-mentioned dispersant, and the preferable range is also the same.

Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and preferably at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, and more preferably a carboxylic acid group.

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

(7)

In the general formulas (vii) to (ix), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom) , Or an alkyl group having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, etc.).

In the general formulas (vii) to (ix), R ²¹ , R ²² and R ²³ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably, Is independently a hydrogen atom or a methyl group. In the general formula (vii), it is particularly preferable that R ²¹ and R ²³ are each a hydrogen atom.

X ₂ in the general formula (vii) represents an oxygen atom (-O-) or an imino group (-NH-), preferably an oxygen atom.

In the general formula (viii), Y represents a methoxy group or a nitrogen atom.

L ₂ in formulas (vii) to (ix) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkenylene group, and a substituted alkenylene group) (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR ⁴¹ '), a substituted or unsubstituted arylene group -, wherein R ⁴¹ 'is 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 carbon number of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, and even more preferably from 1 to 10. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group and a heterocyclic group.

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

The divalent heterocyclic group preferably has a 5-membered ring or a 6-membered ring as a heterocyclic ring. The heterocycle may be condensed with at least one of another heterocycle, an aliphatic ring or an aromatic ring. The heterocyclic group may have a substituent. Examples of the substituent, a halogen atom, a hydroxyl group, an oxo group (= O), Im oxo group (= S), imino group (= NH), a substituted imino group (= NR ^42, where R ⁴² is an aliphatic group, An aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

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

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

In the general formula (ix), R ²⁴ , R ²⁵ and R ²⁶ each independently represent a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom) An alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), -Z ₂ , or L ₂ -Z ₂ . Here, L ₂ and Z ₂ are, and L ₂ and Z ₂ as agreed in the above, the same preferable examples. R ²⁴ , R ²⁵ , and R ²⁶ are each independently 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 a divalent linking group , X ₂ is an oxygen atom or an imino group, and Z ₂ is a carboxylic acid group.

As the monomer represented by the general formula (vii), a compound in which R ²¹ is a hydrogen atom or a methyl group, L ₂ is an alkylene group, Z ₂ is a carboxylic acid group, and Y is a meta-group is preferable.

As the monomer represented by the general formula (ix), a compound wherein R ²⁴ , R ²⁵ , and R ²⁶ are each independently a hydrogen atom or a methyl group and Z ₂ is a carboxylic acid group is preferable.

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

The binder resin may contain one or more structural units having an acid group.

The content of the structural unit having an acid group is preferably from 5 to 95%, in terms of mass, relative to the total mass of the binder resin, more preferably from 10 to 10%, from the viewpoint of suppressing the damage of the image strength due to alkali development To 90%.

The content of the binder resin in the composition of the present invention is preferably 0.1 to 30 mass%, more preferably 0.3 to 25 mass%, based on the total solid content of the composition.

The binder resin may be used alone or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total amount is in the above range.

In the composition of the present invention, the content ratio of the dispersant to the titanium nitride-containing particles (the mass ratio of the dispersant / titanium nitride-containing particles (hereinafter also referred to as "D / P")) is preferably 0.3 or less, , More preferably from 0.1 to 0.3. When the content ratio D / P is within the above range, not only the performance reproducibility of the dispersion is excellent, but also the patterning property (resolution) of the cured film is excellent.

<Polymerizable compound>

The composition of the present invention preferably contains a polymerizable compound.

The polymerizable compound is preferably a compound having at least one group having an ethylenically unsaturated bond, more preferably at least two compounds, more preferably at least three, and particularly preferably at least five. The upper limit is, for example, 15 or less. Examples of the group having an ethylenic unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.

The polymerizable compound may be any of chemical forms such as, for example, a monomer, a prepolymer, an oligomer, a mixture thereof and a multimer thereof, and a monomer is preferable.

The molecular weight of the polymerizable compound is preferably 100 to 3000, more preferably 250 to 1500.

The polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functional groups, and more preferably a (meth) acrylate compound having 3 to 6 functional groups.

Examples of monomers and prepolymers include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and oligomers thereof , Preferably an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound, and oligomers thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group or a mercapto group with a monofunctional or multifunctional isocyanate or an epoxide, an unsaturated carboxylic acid ester or an amide And a dehydration condensation reaction product with a monofunctional or multifunctional carboxylic acid are suitably used. The unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group may be reacted with monofunctional or polyfunctional alcohols, amines, reaction products with thiols, halogen group, tosyloxy group, etc. Unsaturated carboxylic acid esters or amides having a salting-out substituent and mono- or polyfunctional alcohols, amines and thiols are also suitable. It is also possible to use a group of compounds substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an ally ether or the like in place of the above unsaturated carboxylic acid.

As specific compounds thereof, the compounds described in paragraphs [0095] to [0108] of JP-A No. 2009-288705 can be suitably used in the present invention.

In the present invention, as the polymerizable compound, a compound having at least one group having an ethylenic unsaturated bond and having a boiling point of 100 캜 or more at normal pressure is also preferable. As an example thereof, reference may be made to the compounds described in paragraphs 0227 and 027 of Japanese Patent Application Laid-Open No. 2013-29760 and Japanese Patent Application Laid-Open No. 2008-292970, the contents of which are incorporated herein by reference.

As the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330, Nippon Kayaku Kabushiki Kaisha) and dipentaerythritol tetraacrylate (KAYARAD D-320, Nippon Kayaku Co., Ltd., (KAYARAD D-310 manufactured by Nippon Kayaku Kabushiki Kaisha), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; Nippon Kayaku Kabushiki Kaisha), dipentaerythritol penta A-DPH-12E manufactured by Shin-Nakamura Kagaku Co., Ltd.), and a structure in which the (meth) acryloyl group intervenes between the ethylene glycol residue or the propylene glycol residue (for example, SR454, SR499, which are commercially available from Mitsubishi Chemical Corporation) are preferred. These oligomer types can also be used. NK Ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Kagaku Co., Ltd.) and KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) 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 aliphatic polyhydroxy compound and an ester of an unsaturated carboxylic acid are preferable, and a polymerizable compound having an acid group by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a nonaromatic carboxylic acid anhydride More preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co.,

The acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH / g, and more preferably from 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 terms of production and handling. Further, the photopolymerization performance is good and the curability is excellent.

The polymerizable compound is also a preferred embodiment of the 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, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta (Meth) acrylic acid and? -Caprolactone obtained by esterifying a polyhydric alcohol such as trimethylol propane, trimethylol propane, trimethylol propane, trimethylol propane, trimethylol propane, trimethylol propane, (Meth) acrylate. Among them, a compound having a caprolactone structure represented by the following general formula (Z-1) is preferable.

[Chemical Formula 8]

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

[Chemical Formula 9]

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

[Chemical formula 10]

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

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

The polymerizable compound may be a compound represented by the following general formula (Z-4) or (Z-5).

(11)

In the general formulas (Z-4) and (Z-5), E is each independently - ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) -, y represents an integer independently from 0 to 10, and X represents, independently of each other, a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.

In the general formula (Z-4), the sum of the (meth) acryloyl groups is 3 or 4, m is independently an integer of 0 to 10, and the sum of m is an integer of 0 to 40.

In the general formula (Z-5), the sum of the (meth) acryloyl groups is 5 or 6, and each n independently represents an integer of 0 to 10, and the sum of n is an integer of 0 to 60.

In the general formula (Z-4), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

The sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and still more preferably an integer of 4 to 8.

In the general formula (Z-5), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.

The sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.

- ((CH ₂ ) _y CH ₂ O) - or - ((CH ₂ ) _y CH (CH ₃ ) O) - in the general formula (Z-4) or the general formula (Z- Side is bonded to X is preferable.

The compounds represented by the general formula (Z-4) or (Z-5) may be used singly or in combination of two or more. Particularly, in the compound represented by the general formula (Z-5) in which all of the six X's are acryloyl groups, in the compound represented by the general formula (Z-5) And a compound in which at least one is a hydrogen atom is preferable. With such a configuration, the developability can be further improved.

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

The compound represented by the general formula (Z-4) or the general formula (Z-5) can be produced by subjecting pentaerythritol or dipentaerythritol, which is a conventionally known process, to a ring opening skeleton And a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride to the terminal hydroxyl group of the ring opening skeleton. Each process is a well-known process, and a person skilled in the art can easily synthesize a compound represented by formula (Z-4) or (Z-5).

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

Specifically, the compounds represented by the following formulas (a) to (f) are exemplified, and among them, the exemplified compounds (a), (b), (e), and (f) are preferable.

[Chemical Formula 12]

[Chemical Formula 13]

Examples of commercially available products of the polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains of Satomar Co., DPCA-60, which is a hexafunctional acrylate having six pentylene oxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains, and the like.

Examples of the polymerizable compound include those described in JP-A-48-41708, JP-A-51-37193, JP-A-2-32293, and JP-A-2-16765 Such as urethane acrylates described in JP-A-58-49860, JP-A-56-17654, JP-A-62-39417, and JP-A-62-39418 Yutein compounds having an ethylene oxide skeleton are also suitable. In addition, the 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 A composition having a very high photosensitive speed can be obtained.

(Commercially available from Shin-Nakamura Kagaku), DPHA-40H (manufactured by Nippon Kayaku), UA-306H, UA-306T (manufactured by Sanyo Chemical Industries, Ltd.) , UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.).

The polymerizable compound used in the present invention preferably has a SP (dissolution parameter) value of 9.50 or more, more preferably 10.40 or more, and even more preferably 10.60 or more.

In this specification, the SP value is obtained by the Hoy method (HL Hoy Journal of Painting, 1970, Vol. 42, 76-118) unless otherwise specified. The SP value is shown by omitting the unit, but its unit is cal ^1/2 cm ^-3/2 .

It is also preferable that the composition 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.

In general formula (Q3)

[Chemical Formula 14]

In the general formula (Q3), Ar ¹¹ to Ar ¹⁴ each independently represent an aryl group including a benzene ring surrounded by a broken line. X ¹ to X ⁴ each independently represent a substituent having a polymerizable group, and the carbon atom in the substituent may be substituted by a heteroatom. a and b each independently represent an integer of 1 to 5; and c and d each independently represent an integer of 0 to 4; R ¹ ~ R ⁴ each independently represent a substituent, e, f, g and h each independently represent an integer of 0 or more, e, the upper limit of f, g and h are in the Ar ¹¹ ~ Ar ¹⁴ may have, respectively A, b, c or d from the number of substituents. When Ar ¹¹ to Ar ¹⁴ each independently represent a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, X ¹ to X ⁴ and R ¹ to R ⁴ are each independently a benzene ring surrounded by a dashed line Or may be substituted with a ring other than a benzene ring surrounded by a broken line.

In the general formula (Q3), the aryl group containing a benzene ring surrounded by the 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 , Naphthyl group), and more preferably a phenyl group (benzene ring surrounded by a broken line).

In the general formula (Q3), X ¹ to X ⁴ each independently represent a substituent having a polymerizable group, and the carbon atom in the substituent may be substituted by a heteroatom. 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, more preferably an alkylene group having 2 to 10 carbon atoms , And more preferably an alkylene group having 2 to 5 carbon atoms.

In the aliphatic group having a polymerizable group represented by X ¹ to X ⁴ , when the aliphatic group is substituted by a heteroatom, it is preferably a group substituted by -NR- (R is a substituent), an oxygen atom, or a sulfur atom preferably, -CH ₂ non-adjacent of said aliphatic group - is more preferable, which is substituted with an oxygen atom or a sulfur atom, and, -CH ₂ non-adjacent of said aliphatic group - is more preferred that the optionally substituted oxygen atom. The aliphatic group having a polymerizable group represented by X ¹ to X ⁴ is preferably substituted by 1 to 2 substituents selected from a hetero atom, more preferably one substituent by a heteroatom, and Ar ¹¹ to Ar ¹⁴ It is more preferable that one adjacent to the aryl group including the benzene ring surrounded by the broken line is substituted by a hetero atom.

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 preferable.

As the radical polymerizing group, there can be used generally known radically polymerizing groups, and suitable ones include polymerizable groups having radically polymerizable ethylenically unsaturated bonds, and specific examples thereof include a vinyl group, a (meth) acryloyloxy group and the like . Among them, a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable.

As the cationic polymerizable group, generally known cationic polymerizable groups can be used. Specific examples thereof include aliphatic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spiroorthoesters groups, and vinyloxy groups . Among them, an alicyclic ether or vinyloxy group is preferable, and an epoxy group, oxetanyl group, or vinyloxy group is particularly preferable.

The polymerizable group of the substituent group contained in Ar ¹ to Ar ⁴ is preferably a radical polymerizable group.

Ar ¹ ~ Ar least two of ^{the four} comprises a substituent having a polymerizable group, Ar ¹ ~ Ar may include a substituent having a ^42-4 dog polymerization of the penis and, Ar ¹ ~ Ar ⁴ of 2 or 3 More preferably a substituent having a polymerizable group, and more preferably two of Ar ¹ to Ar ⁴ include a substituent having a polymerizable group.

When Ar ¹¹ to Ar ¹⁴ each independently represent a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, X ¹ to X ⁴ may each independently be substituted with a benzene ring surrounded by a broken line, May be substituted by a ring other than a benzene ring.

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

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

In the general formula (Q3), R ¹ to R ⁴ each independently represent a substituent. The substituent represented by R ¹ to R ⁴ is not particularly limited and examples thereof include a halogen atom, a halogenated alkyl group, an alkyl group, an alkenyl group, an acyl group, a hydroxyl group, a hydroxyalkyl group, an alkoxy group, Groups, and vicinal groups. 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, more preferably a methyl group, More preferable.

In the general formula (Q3), when Ar ¹¹ to Ar ¹⁴ each independently represent a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, R ¹ to R ⁴ are each independently a benzene ring surrounded by a dashed line Or may be substituted with a ring other than a benzene ring surrounded by a broken line.

In the above general formula (Q3), e, f, g and h each independently represents an integer of 0 or more, e, f, g and the upper limit value of h is a from a number of substituents that Ar ¹¹ ~ Ar ¹⁴ may have, respectively , b, c, or d.

e, f, g and h are each independently preferably 0 to 8, more preferably 0 to 2, still more preferably 0.

When Ar ¹¹ to Ar ¹⁴ each independently represent a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, e, f, g and h are preferably 0 or 1, and more preferably 0 .

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, the compounds described in JP-A-2010-254732 can also be suitably used.

In the case where the composition of the present invention contains a polymerizable compound, the content of the polymerizable compound is preferably from 0.1 to 40 mass% with respect to the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, for example, and further preferably 1% by mass or more. The upper limit is more preferably 30 mass% or less, for example, and still more preferably 20 mass% or less.

The polymerizable compounds may be used singly or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total amount is in the above range.

<Polymerization Initiator>

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

The polymerization initiator is not particularly limited and can be appropriately selected from known polymerization initiators, and for example, those having photosensitivity (so-called photopolymerization initiator) are preferable.

The composition of the present invention is sometimes referred to as a "photosensitive composition" in that it contains a photopolymerization initiator and the aforementioned polymerizable compound in addition to the titanium nitride-containing particles, because it cures upon irradiation with an actinic ray or radiation.

The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have photosensitivity to a visible ray from an ultraviolet ray region. In addition, it may be an activator that generates an active radical by generating some action with a photosensitized sensitizer, or may be an initiator that initiates cationic polymerization depending on the type of the 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 acylphosphine compounds such as halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, oxadiazole skeletons, etc.), acylphosphine oxides and the like, Oxime compounds such as imidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones. As the halogenated hydrocarbon compound having a triazine skeleton, for example, Wakabayashi et al., Bull. Chem. Soc. Compounds described in GB-A-5313428, compounds described in German Patent Publication No. 3337024, compounds described in J. Org., &Lt; RTI ID = 0.0 &gt; . Chem .; 29, 1527 (1964), compounds described in JP-A-62-58241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, and Compounds described in U.S. Patent No. 4212976, and the like.

From the viewpoint of exposure sensitivity, it is also possible to use a trihalomethyltriazine compound, a benzyldimethylketal compound, an? -Hydroxyketone compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, Oxime compounds, triallyl imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, And a 3-aryl-substituted coumarin compound.

More preferably, it is a trihalomethyltriazine compound, an? -Amino ketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a triallylimidazole dimer, an onium compound, a benzophenone compound or an acetophenone compound , At least one compound selected from the group consisting of a trihalomethyltriazine compound, an? -Amino ketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound is particularly preferable.

Particularly, when the composition of the present invention is used for the production of a light-shielding film of a solid-state image sensor, it is necessary to form a fine pattern in a sharp shape, so that it is important that the composition is cured and developed without residue on the unexposed portion. From this viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. Particularly, in the case of forming a fine pattern in a solid-state image pickup device, stepper exposure is used for curing exposure, but this exposure device may be damaged by halogen, and the addition amount of the photopolymerization initiator also needs to be suppressed to a low level, Taking these points into consideration, it is particularly preferable to use an oxime compound as a photopolymerization initiator in order to form a fine pattern such as a solid-state imaging element. In addition, by using an oxime compound, the colorimetricity can be further improved.

As specific examples of the photopolymerization initiator, reference can be made, for example, to paragraphs 0265 to 0268 of JP-A-2013-29760, the contents of which are incorporated herein by reference.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be suitably used. More specifically, for example, the aminoacetophenone initiator disclosed in Japanese Patent Application Laid-Open No. 10-291969 or the acylphosphine initiator disclosed in Japanese Patent No. 4225898 may be used.

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (all trade names, manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, commercially available IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (all trade names, manufactured by BASF) can be used. As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 in which the absorption wavelength is matched to a long-wavelength light source such as 365 nm or 405 nm can be used.

As the acylphosphine-based initiator, commercially available IRGACURE-819 and DAROCUR-TPO (all trade names, all manufactured by BASF) can be used.

The photopolymerization initiator is more preferably an oxime compound. In particular, the oxime-based initiator is preferable because it has high sensitivity, high polymerization efficiency, can be cured irrespective of the coloring material concentration, and can be easily designed with high coloring density.

Specific examples of the oxime compounds include compounds described in JP 2001-233842 A, compounds described in JP-A 2000-80068, and compounds described in JP 2006-342166 A.

Examples of oxime compounds that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan- , 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino- 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

J. C. S. Perkin II (1979) pp. Pp. 1653-1660, J. C. S. Perkin II (1979) pp. Pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-A 2004-534797, JP-A 2006-342166, etc. .

IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are suitably used in commercial products. ADEKA ACKNES NCI-831 and ADEKA ACKLS NCI-930 (manufactured by ADEKA), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.) Can also be used. N-1919 (manufactured by ADEKA) can also be used.

As oxime compounds other than the above-mentioned materials, compounds described in Japanese Unexamined Patent Publication No. 2009-519904 in which oxime is linked to carbazole N, compounds described in U.S. Patent No. 7626957 in which a hetero substituent is introduced into a benzophenone moiety, Compounds disclosed in Japanese Unexamined Patent Application Publication Nos. 2002-15025 and 2009-292039 where nitro groups are introduced, ketoxime compounds described in International Patent Publication No. 2009-131189, triazine skeleton and oxime skeleton in the same molecule And compounds described in Japanese Patent Application Laid-Open No. 2009-221114 having a maximum absorption at 405 nm and good sensitivity to a g-ray light source may be used.

Preferably, for example, reference is made to paragraphs 0274 to 0275 of JP-A-2013-29760, the contents of which are incorporated herein by reference.

Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). Further, the N-O bond of the oxime may be an oxime compound of the (E) form, an oxime compound of the (Z) form, or a mixture of the form (E) and the form (Z).

[Chemical Formula 15]

In the general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metallic atomic group.

Examples of the monovalent nonmetal 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. These groups may have one or more substituents. The substituent described above may be substituted with another substituent.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

In the 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. As the substituent, the above-mentioned substituent can be exemplified.

In the general formula (OX-1), as the divalent organic group represented by A, an alkylene group, a cycloalkylene group or an alkane-ylene group having 1 to 12 carbon atoms is preferable. These groups may have one or more substituents. As the substituent, the above-mentioned substituent can be exemplified.

In the present invention, it is also possible to use an oxime compound having a fluorine atom as a photopolymerization initiator. Specific examples of the fluorine atom-containing oxime compounds include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471 (C-3), and the like. The contents of which are incorporated herein by reference.

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

[Chemical Formula 16]

In formula (1), R ¹ and R ² each independently represent an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms in the case of an aryl group, R ¹ and R ² is a phenyl group, and combine with the phenyl group together form a group fluorene, R ³ and R ⁴ are, each independently, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, having a carbon number of 6 An aryl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a single bond or a carbonyl group.

In the formula ^{(2), R 1, R} 2, R 3 and R ^4, R ^1, in the formula (1) R ^2, R ³ and R ⁴ with the consent and, 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 , A halogen atom or a hydroxyl group, and 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, 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 each independently preferably a methyl group, ethyl group, n-propyl group, isopropyl group, 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 the formulas (1) and (2) include the compounds described in paragraphs 0076 to 0079 of JP-A No. 2014-137466. The contents of which are incorporated herein by reference.

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

[Chemical Formula 17]

The present invention can also use an oxime compound having a benzofuran skeleton as a photopolymerization initiator.

Specific examples thereof include OE-01 to OE-75 described in WO2015 / 036910.

The commercially available polymerization initiator is not particularly limited, but IRGACURE OXE01 (1.2-octene ion, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)]) , IRGACURE OXE02 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime) Methyl) thioxanthene-9-one, O-acyloxime compounds (for example, ADEKA OPTOMER N-1919 and ADEKA ACKLS NCI-831 manufactured by ADEKA), ADEKA ACKLS NCI-930, IRGACURE- OXE03, IRGACURE-OXE04, and the like, all of which are incorporated herein by reference.

The oxime compound preferably has a maximum absorption wavelength in a wavelength range of 350 nm to 500 nm, more preferably a maximum absorption wavelength in a wavelength range of 360 nm to 480 nm, and particularly preferably a high absorbance at 365 nm and 405 nm.

The oxime compound preferably has a molar extinction coefficient at 365 nm or 405 nm of 1,000 to 300,000, more preferably 2,000 to 300,000, and still more preferably 5,000 to 200,000 from the viewpoint of sensitivity.

The molar extinction coefficient of the compound can be measured by a known method. For example, it is preferable that the molar extinction coefficient is measured at a concentration of 0.01 g / L by using an ultraviolet visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent .

The photopolymerization initiator used in the present invention may be used in combination of two or more as necessary.

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

<Solvent>

The composition of the present invention preferably contains a solvent, and more preferably contains an organic solvent.

Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethylether, ethylene glycol monoethylether, ethylene Propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate , Ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether Propyleneglycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethylsulfoxide, gamma -butyrolactone, ethyl acetate , Butyl acetate, methyl lactate, and ethyl lactate, but are not limited thereto.

The composition of the present invention may contain one kind of organic solvent or two or more kinds of organic solvents but it is preferable that the composition of the present invention can suppress the fluctuation of the particle size of the titanium nitride- It is preferable to contain two or more kinds of organic solvents.

When two or more organic solvents are contained, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, - methyl methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol monomethylether, ethyl 3-ethoxypropionate and propylene glycol It is preferably composed of two or more kinds selected from the group consisting of colmonomethyl ether acetate.

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

<Water>

The composition of the present invention may contain water. The water may be intentionally added, or may be inevitably contained in the composition by adding each component contained in the composition of the present invention.

The content of water is preferably 0.1 to 1 mass%, more preferably 0.1 to 0.8 mass%, and even more preferably 0.1 to 0.4 mass% with respect to the total mass of the composition. When the content of water is within the above range, the patterning property (resolution) of the cured film is excellent, and the corrosion resistance of the electrode material is excellent. By adjusting the content of water 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 stability of the composition over time is also excellent.

<Other Ingredients>

The composition of the present invention may contain other components than the above-mentioned components.

Hereinafter, each component will be described in detail.

(Silane coupling agent)

The silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule. The hydrolyzable group such as an alkoxy group is bonded to a silicon atom.

The hydrolyzable group means a substituent which is directly connected to a silicon atom and capable of generating 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 carbon atoms, the number of carbon atoms thereof is preferably 6 or less, more preferably 4 or less. Particularly, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.

In order to improve adhesion between the substrate and the cured film, it is preferable that the silane coupling agent does not contain a fluorine atom and a silicon atom (provided that the silicon atom bonded to the hydrolyzable group is excluded), and a fluorine atom, a silicon atom But excluding the silicon atom bonded to the hydrolyzable group), an alkylene group substituted with a silicon atom, a straight chain alkyl group having a carbon number of 8 or more, and a branched alkyl group having a carbon number of 3 or more.

The silane coupling agent preferably has a group represented by the following formula (Z). * Indicates the binding position.

(Z) * -Si- (R _Z1 ) ₃

In the formula (Z), R _Z1 represents a hydrolyzable group and its definition is as described above.

The silane coupling agent preferably has at least one curable functional group selected from the group consisting of a (meth) acryloyloxy group, an epoxy group, and an oxetane group. The curable functional group may be directly bonded to a silicon atom, or may be bonded to a silicon atom through a linking group.

In addition, examples of the favorable mode of the curable functional group contained in the silane coupling agent include a radical polymerizable group.

The molecular weight of the silane coupling agent is not particularly limited and is usually from 100 to 1000 in view of handleability, and is preferably 270 or more, and more preferably from 270 to 1000, from the viewpoint of more excellent effects of the present invention.

One preferred embodiment of the silane coupling agent is the silane coupling agent X represented by the formula (W).

(W) ???????? R _Z2 -Lz-Si- (R _Z1 ) ₃ ?????

R _z1 represents a hydrolyzable group, and the definitions are as described above.

R _z2 represents a curable functional group, the definitions are as described above, and the suitable ranges are 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 by a halogen atom, an arylene group which may be substituted by a halogen atom, -NR ¹² -, -CONR ¹² -, -CO-, -CO ₂ -, SO ₂ NR ¹² -, -O-, -S-, -SO ₂ -, and combinations thereof. Among these, a carbon number of 2 to 10 hydrogen atoms are substituted and at least one selected from an alkylene group and a halogen atom is the group consisting of an arylene which may be substituted, and having 6 to 12 which may be of the species, or those groups -NR ¹² -, A group formed by combination with at least one group selected from the group consisting of -CONR ¹² -, -CO-, -CO ₂ -, SO ₂ NR ¹² -, -O-, -S-, and SO ₂ - , An alkylene group which may be substituted with a halogen atom having 2 to 10 carbon atoms, -CO ₂ -, -O-, -CO-, -CONR ¹² -, or a group formed by a combination of these groups. Here, R ¹² represents a hydrogen atom or a methyl group.

Examples of the silane coupling agent X include N -? - aminoethyl -? - aminopropyl-methyldimethoxysilane (trade name: KBM-602 manufactured by Shin-Etsu Chemical Co., Trimethoxysilane (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (KBE- Aminopropyltrimethoxysilane (trade name KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyltriethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyl Trimethoxysilane (trade name KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) and glycidoxy-octyltrimethoxysilane (KBM-4803, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

Other suitable examples of the silane coupling agent include a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule and a hydrolyzable group bonded to a silicon atom.

The silane coupling agent Y may have at least one silicon atom in the molecule, and the silicon atom may be bonded to the following atoms or substituents. They can be the same atom, substitution or different. The substituent is preferably a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an amino group which may be substituted with an alkyl group and / or an aryl group, An alkoxy group having 1 to 20 carbon atoms, and an aryloxy group. These substituents may also be substituted with at least one substituent selected from the group consisting of a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group which may be substituted with an alkyl group and / An amide group, an urea group, an ammonium group, an alkylammonium group, a carboxyl group, or a salt thereof, a sulfo group, or a salt thereof.

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 preferably has at least one nitrogen atom in the molecule and the nitrogen atom is present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom has at least one organic group as a substituent desirable. The structure of the amino group may be in the form of a partial structure of a nitrogen-containing heterocycle, or may exist as a substituted amino group such as aniline.

Examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and combinations thereof. These substituents may further have a substituent and examples of the substituent which 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, a sulfonamido group, An amide group, an urea group, an alkyleneoxy group, an ammonium group, an alkylammonium group, a carboxyl group or a salt thereof, and a sulfo group.

The nitrogen atom is preferably bonded to the curable functional group through an arbitrary organic linking group. Preferable examples of the organic linking group include substituents that can be introduced into the above-mentioned nitrogen atom and the organic group bonded thereto.

The definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferable range thereof is as described above.

The silane coupling agent Y may contain at least one curable functional group in one molecule, but it may also have two or more curable functional groups. From the viewpoints of sensitivity and stability, it is preferable to have 2 to 20 curable functional groups , More preferably from 4 to 15, and most preferably from 6 to 10 curable functional groups in the molecule.

The molecular weight of the silane coupling agent X and the silane coupling agent Y is not particularly limited, but may be the above-mentioned range (preferably not less than 270).

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

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

(Ultraviolet absorber)

The composition of the present invention may contain an ultraviolet absorber. As a result, the shape of the pattern can be made better (finer).

As the ultraviolet absorber, salicylate, benzophenone, benzotriazole, substituted acrylonitrile and triazine 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 Japanese Laid-Open Patent Publication No. 2012-068418 may be used and the contents thereof may be used and are included in this specification .

In addition, a diethylamino-phenyl sulfonyl ultraviolet absorber (trade name: UV-503, manufactured by Daitogagaku Co., Ltd.) is suitably used.

Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP-A No. 2012-32556.

The composition of the present invention may or may not contain an ultraviolet absorber, but if included, the content of the ultraviolet absorber is preferably 0.001 to 15 mass%, more preferably 0.01 to 10 mass%, based on the total solid content of the composition , More preferably from 0.1 to 5 mass%.

(Surfactants)

The composition of the present invention may contain various surfactants in order to further improve the applicability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used.

By containing the fluorine-containing surfactant in the composition of the present invention, the liquid properties (particularly, the fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and the liquid-storing property can be further improved . That is, in the case of forming a film by using a coating liquid to which a composition containing a fluorine-containing surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is lowered and the wettability to the surface to be coated is improved, . This makes it possible to more suitably form a film having a uniform thickness with a small thickness deviation.

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

Examples of the fluorine-based surfactant include Megapak F171, Dong F172, Dong F173, Dong F176, Dong F177, Dong F141, Dong F142, Dong F143, Dong F144, Dong R30, Dong F437, Dong F475, Dong F479, Dong F482 (Manufactured by Sumitomo 3M Co., Ltd.), Surflon S-382, Copper SC-422 (manufactured by DIC Corporation), Fluorad FC430, Copper FC431, Copper FC171 (Manufactured by Asahi Glass Co., Ltd.), SC-103, SC-104, SC-105, SC-1068, SC-381, PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA). As the fluorochemical surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A No. 2015-117327 may be used. As the fluorine-based surfactant, a block polymer may be used. Specific examples thereof include the compounds described in Japanese Laid-Open Patent Publication No. 2011-89090.

The fluorine-containing surfactant is preferably a fluorine-containing surfactant having two or more (preferably five or more) repeating units derived from a (meth) acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group and a propyleneoxy group) ) Acrylate compounds, and the following compounds are also exemplified as the fluorinated surfactants used in the present invention.

[Chemical Formula 18]

The weight average molecular weight of the compound is preferably from 3,000 to 50,000, for example, 14,000.

A fluorine-containing polymer having an ethylenic unsaturated group in its side chain may also be used as a fluorine-containing surfactant. Specific examples thereof include compounds described in Japanese Laid-Open Patent Publication No. 2010-164965, paragraphs 0050 to 0090 and paragraphs 0289 to 0295, such as Megapark RS-101, RS-102, RS-718K and RS-72-K And the like.

Specific examples of the nonionic surfactants include glycerol, trimethylol propane, trimethylol ethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerin ethoxylate and the like), polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol diallylate, polyethylene glycol Diestearate and consumptive fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, NCW-101, NCW-1001, and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. may also be used.

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.) Acrylic acid type (co) polymer Polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusoh Co., Ltd.).

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusoh Corp.) and Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.).

Examples of silicone based surfactants include TORAY silicone DC3PA, TORAY silicone SH7PA, TORAY silicone DC11PA, TORAY silicone SH21PA, TORAY silicone SH28PA, TORAY silicone SH29PA, TORAY silicone SH30PA, TORAY silicone SH8400 (manufactured by Toray Dow Corning Co., ), TSF-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (manufactured by Momentive Performance Materials Co., Ltd.), KP341, KF6001 and KF6002 (all manufactured by Shin-Etsu Silicones Co., , BYK307, BYK323, and BYK330 (manufactured by Big Chemie).

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

In addition to the above components, the following components may be further added to the composition of the present invention. Examples of the additives include sensitizers, notarization agents, crosslinking agents, curing accelerators, fillers, thermal curing accelerators, polymerization inhibitors, plasticizers, diluents and sensitizers. For example, known additives such as conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, flavors, surface tension adjusting agents and chain transfer agents may be added as needed.

These components are described in, for example, Japanese Patent Laid-Open Publication No. 2012-003225, paragraphs 0183 to 0228 (corresponding to U.S. Patent Application Publication No. 2013/0034812 <0237> to <0309>), Reference numerals 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, and paragraphs 0159 to 0184 of Japanese Patent Laid-Open Publication No. 2013-195480, all of which are incorporated herein by reference.

(coloring agent)

The composition of the present invention may use a colorant other than the above-mentioned titanium nitride-containing particles (hereinafter, simply referred to as "colorant"). The colorant is used, for example, for adjusting the chromaticity of the composition, and it is possible to replace part of the titanium nitride with a colorant within a range in which the OD value is not lowered. Examples of such colorants include pigments (black organic pigments, organic pigments of chromatic organic pigments and inorganic pigments), and dyes.

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

((Pigment))

As the pigment, various conventionally known pigments can be mentioned.

Examples of chromatic organic pigments include the following. However, the present invention is not limited thereto.

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, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 172, 173, 174, 175, 169, 170, 171, 172, 173, 174, 148, 150, 151, 152, 153, 154, 155, 156, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213,

CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 73,

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 81: 2, 81: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 175, 176, 177, 178, 179, 170, 176, 168, 169, 170, 171, 172, 175, 176, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,

C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc.,

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc.,

CI Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66,

As the green pigment, it is also possible to use a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms in the molecule, an average of 8 to 12 bromine atoms, and an average chlorine atom of 2 to 5. Specific examples include the compounds described in International Publication No. 2015/118720.

These organic pigments can be used singly or in various combinations in order to enhance color purity.

As the black pigment, various known black pigments can be used. For example, carbon black and the following black metal-containing inorganic pigments can be mentioned. Examples of the black metal-containing inorganic pigment include metal oxides and metal nitrates containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, . These may be used alone or as a mixture of two or more. The black pigment may be further combined with inorganic pigments of different colors to have desired light-shielding properties. Examples of specific inorganic pigments that can be used in combination include zinc oxide, zinc white, ritofone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite, podium, iron oxide, , Prussian Blue (Ferrocyanide Iron Carlyle), Zircon Gray, Praseodymium Yellow, Chromium Titanium Yellow, Chromium Green, Peacock, Victoria Green, Prussian Blue (Prussian Blue), Zinc Sulfur (Zinc Sulfur One, Zinc Sulfur Two) Blue), vanadium zirconium blue, chromium tin pink, manganese pink, and salmon pink. In particular, for the purpose of exhibiting light shielding properties in a wide wavelength range from ultraviolet rays to infrared rays, it is possible to use these black pigments and inorganic pigments having different hues not only singly but also by mixing a plurality of kinds of pigments.

As the black pigment, carbon black and titanium black are preferable, and titanium black is particularly preferable from the viewpoint of having a light shielding property in a broad wavelength range from ultraviolet rays to infrared rays. Titanium black is a black particle having a titanium atom. Preferably titanium oxide or titanium oxynitride. Although not particularly limited, examples of titanium oxynitride include those disclosed in International Publication Nos. 2008/123097, 2009-58946, 2010-14848, 2010-97210, and Japanese Patent Application Laid-Open No. 2011-2274670 The same titanium oxynitride, or a mixture of titanium oxynitride and titanium carbide such as Japanese Laid-Open Patent Publication No. 2010-95716. The surface of the titanium black particles can be modified as needed for the purpose of improving dispersibility and inhibiting cohesiveness. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide and zirconium oxide, and treatment with a water repellent substance as shown in Japanese Patent Application Laid-Open No. 2007-302836 is also possible. Titanium black may contain one or more kinds of black pigments such as composite oxides of Cu, Fe, Mn, V and Ni, cobalt oxide, iron oxide and carbon black for the purpose of adjusting dispersibility, do.

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

The specific surface area of titanium black is not particularly limited, BET (Brunauer, Emmett, Teller ) method a value of 5m ² / g and more than preferably 150m ² / g or less, 20m ² / g more than 120m ² / g or less measured by More preferable.

Examples of commercially available products of 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 (Manufactured by Kasei Corporation).

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

It is also preferable that titanium black be contained as a pigment dispersion containing titanium black and Si atoms.

In this embodiment, the titanium black is contained as a dispersoid in the composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersoid is preferably 0.05 or more in terms of mass, more preferably 0.05 to 0.5 More preferably 0.07 to 0.4.

Here, the above-described dispersed body includes both of the titanium black in the primary particle state and the aggregate (secondary particle) state.

In order to change the Si / Ti of the object to be dispersed (for example, to be 0.05 or more), the following means can be used.

First, titanium oxide and silica particles are dispersed using a dispersing machine to obtain a dispersion, and the dispersion is subjected to a reduction treatment at a high temperature (for example, 850 to 1000 ° C) to obtain titanium black particles as a main component and Si and Ti And the like can be obtained. The reduction treatment may be performed in an atmosphere of a reducing gas such as ammonia.

Examples of the titanium oxide include TTO-51N (trade name, manufactured by Ishihara Sangyo Co., Ltd.) and the like.

The titanium oxide produced by the plasma method can be suitably used because the particle size thereof is smaller than that of commercially available titanium dioxide fine particles (see Journal of the Japanese Institute of Metals 63 (1) (1999) 74-81).

Examples of commercial products of silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name: Ebonic).

A dispersion agent may be used for the dispersion of the titanium oxide and the silica particles. As the dispersant, those described in the section of the above-mentioned dispersant can be mentioned.

The above dispersion may be performed in a solvent. Examples of the solvent include water and organic solvents. Include those described in the column of the above-mentioned organic solvent.

Titanium black whose Si / Ti is adjusted to 0.05 or more, for example, can be produced by a method described in, for example, Japanese Patent Application Laid-Open No. 2008-266045, paragraph [0016] and paragraphs [0016] to [0021] .

(Si / Ti) ratio of Si atoms and Ti atoms in a target containing titanium black and Si atoms to a suitable range (for example, 0.05 or more), a light shielding film is formed by using a composition containing this object The residues derived from the composition outside the formation region of the light-shielding film are reduced. In addition, the residue includes a component derived from a composition such as titanium black particles, a resin component and the like.

The reason why the residue is reduced is still unclear. However, the above-described dispersed body tends to become a small particle size (for example, the particle size is 30 nm or less), and the component containing Si atoms of the dispersed body increases, It is presumed that the adsorption of the film to the underlying film is reduced and this contributes to the improvement of the developing ability of the uncured composition (particularly, titanium black) in the formation of the light-shielding film.

In addition, titanium black is excellent in light shielding property against light in a wavelength range over a wide range from ultraviolet light to infrared light. Therefore, titanium black and an object to be dispersed including Si atoms (preferably Si / Shielding film formed by using a light shielding film having a thickness of 0.05 or more)

Further, the content ratio (Si / Ti) of Si atoms and Ti atoms in the target dispersion can be measured by using the method (1-1) or the method (1-2) described in paragraph 0033 of Japanese Laid-Open Patent Publication No. 2013-249417 .

In order to determine whether or not the content ratio (Si / Ti) of Si atoms and Ti atoms in the object to be dispersed in the object to be dispersed contained in the light shielding film obtained by curing the composition is 0.05 or more, JP-A- (2) as described in paragraph [0035] of this Article.

In the pigment dispersion containing titanium black and Si atoms, the above-mentioned titanium black can be used.

In this dispersion, a composite oxide of Cu, Fe, Mn, V, Ni, etc., cobalt oxide, iron oxide, carbon black, aniline black or the like is mixed with titanium black for the purpose of adjusting the dispersibility, Or one or more black pigments may be used in combination as a pigment dispersion.

In this case, it is preferable that 50% by mass or more of the entire dispersoid is occupied by the to-be-dispersed body made of titanium black.

In this dispersion, it is also possible to use other coloring agents (such as organic pigments and dyes) together with titanium black in combination with the purpose, as long as the effect of the present invention is not impaired for the purpose of adjusting the light shielding property do.

Hereinafter, a material used for introducing Si atoms into the object to be dispersed will be described. When a Si atom is introduced into the object to be dispersed, a Si-containing substance such as silica may be used.

Examples of usable silica include precipitated silica, fumed silica, colloidal silica, synthetic silica and the like, and these may be appropriately selected and used.

In addition, since the particle diameter of the silica particles is smaller than the film thickness when the light shielding film is formed, the silica particles are preferably used as the silica particles because of better light shielding properties. Further, as an example of the particulate type silica, there may be mentioned, for example, the silica described in paragraph 0039 of Japanese Laid-Open Patent Publication No. 2013-249417, the contents of which are incorporated herein.

As the pigment, a tungsten compound and a metal boride can also be used.

Tungsten compounds and metal borides are infrared shielding materials that have high absorption (that is, high shielding property against infrared rays) for infrared rays (light having a wavelength of about 800 to 1,200 nm) and low absorption for visible light. Thus, the photosensitive composition of the present invention contains a tungsten compound and / or a metal boride, thereby forming a pattern having a high light shielding property in an infrared region and a high light transmittance in a visible light region.

Further, the tungsten compound and the metal boride are less likely to absorb light even for short-wavelength light used for exposure, such as high-pressure mercury lamps, KrF, and ArF used for image formation.

Examples of the tungsten compound include a tungsten oxide compound, a tungsten boride compound, and a tungsten sulphide compound, and a tungsten oxide compound represented by the following 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?

2.2? Z / y? 3.0

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

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

When z / y is 2.2 or more, the chemical stability as a material can be further improved. When the ratio z / y 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 , and Ba _0.33 WO ₃ , and Cs _0.33 WO ₃ or Rb _0.33 WO ₃ , And Cs _0.33 WO ₃ is more preferable.

The tungsten compound is preferably a fine particle. 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 falls within this range, the tungsten fine particles are less likely to block visible light due to light scattering, so that the light transmittance in the visible light region can be more surely obtained. From the viewpoint of avoiding light scattering, the smaller the average primary particle diameter is, the better, but the average primary particle diameter of the tungsten fine particles is usually 1 nm or more for ease of handling at the time of production.

It is also possible to use two or more kinds of tungsten compounds.

When the tungsten compound is, for example, a tungsten oxide compound, the tungsten oxide compound can be obtained by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere Patent Publication No. 4096205).

The tungsten oxide-based compound is also available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Ginkgo Co., Ltd.

Examples of the metal boride include LaB ₆ , PrB ₆ , NdB ₆ , CeB ₆ , YB ₆ , TiB ₂ , boride, zirconium (ZrB _2), boride, hafnium (HfB _2), boride, vanadium (VB _2), boride, tantalum (TaB _2), boride, chromium (CrB, CrB _2), boride, molybdenum (MoB _2, Mo ₂ B ₅ , MoB), tungsten boride (W ₂ B ₅ ), and the like, and it is preferable to use lanthanum boride (LaB ₆ ).

The metal boride is preferably fine particles. The average primary particle size of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and most preferably 100 nm or less. When the average particle diameter is in this range, the light transmittance in the visible light region can be more surely ensured because the metal boride fine particles are less likely to block visible light due to light scattering. From the viewpoint of avoiding light scattering, the smaller the average primary particle size is, the better, but the average primary particle size of the metal boride fine particles is usually 1 nm or more for ease of handling at the time of production and so on.

It is also possible to use two or more metal borides.

The metal boride is available as a commercially available product and is also available as a dispersion of metal boride fine particles such as KHF-07AH manufactured by Sumitomo Ginkgo Kogyo Co., Ltd.

((dyes))

As the dyes, for example, Japanese Unexamined Patent Publication No. 64-90403, Japanese Unexamined Patent Publication No. 64-91102, Japanese Unexamined Patent Publication No. 1-94301, Japanese Unexamined Patent Publication No. 6-11614, Japanese Patent No. 2592207 , U.S. Patent No. 4808501, U.S. Patent No. 5667920, U.S. Patent No. 5,05950, U.S. Patent No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A- 6-51115, 6-194828 and the like can be used. As a chemical structure, it is possible to use a pyrazole compound, a pyromethene compound, an anilino compound, a triphenylmethane compound, an anthraquinone compound, a benzilidene compound, an oxolin compound, a pyrazolotriazoazo compound, A cyanine compound, a phenothiazine compound, a pyrrolopyrazolequamethane compound, and the like can be used. As the dye, a dye multimer may be used. Examples of the pigment multimer include the compounds described in JP-A-2011-213925 and JP-A-2013-041097.

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

The colorants may be used alone or in combination of two or more. As the coloring agent, colored organic pigments such as red, blue, yellow, green, and purple may be contained. When a light-shielding pigment (concretely, 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 mass% with respect to the light-shielding pigment. From the viewpoint of adjusting the color tone, it is preferable to use a red pigment and a light-shielding pigment in combination, and although not particularly limited, Pigment Red 254 is preferably used as the red pigment. From the viewpoint of enhancing light shielding property, it is preferable to use a yellow pigment and a light-shielding pigment in combination, and there is no particular limitation, but 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 mass%, more preferably 30 to 70 mass%, and more preferably 35 to 60 mass%, based on the total solid content of the composition desirable.

(Pigment derivative)

The composition of the present invention may contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the organic pigment is substituted with an acidic group, a basic group, or a phthalimide methyl group.

Examples of the organic pigments for constituting the pigment derivative include pigments such as diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perynone pigments, , Thioindigo pigments, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, trene pigments, metal complex pigments, and the like.

The acid group of the pigment derivative is preferably a sulfonic acid group, a carboxylic acid group or a quaternary ammonium salt group thereof, more preferably a carboxylic acid group or a sulfonic acid group, and particularly preferably a sulfonic acid group. As the basic group of the pigment derivative, an amino group is preferable, and a tertiary amino group is particularly preferable.

Specific examples of the pigment derivative include the following compounds. Reference may also be made to paragraphs 0162 to 0183 of Japanese Laid-Open Patent Publication No. 2011-252065, the contents of which are incorporated herein by reference.

[Chemical Formula 19]

When the composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably from 1 to 30 mass%, more preferably from 3 to 20 mass%, based on the total mass of the colorant. The composition of the present invention may contain only one kind of pigment derivative or two or more kinds thereof. When two or more kinds are included, the total amount is preferably in the above range.

&Lt; Preparation method of composition >

The composition of the present invention can be prepared by mixing the above-mentioned various components by a known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet grinder, a wet disperser).

The composition of the present invention is preferably filtered with a filter for the purpose of removing foreign matters or reducing defects. The filter is not particularly limited as long as it is conventionally used for filtration and the like. For example, a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, a polyolefin resin (including high density, ultrahigh molecular weight) such as polyethylene and polypropylene (PP) . Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.

The pore diameter of the filter is preferably about 0.1 to 7.0 mu m, preferably about 0.2 to 2.5 mu m, more preferably about 0.2 to 1.5 mu m, and still more preferably 0.3 mu m to 0.7 mu m. By setting this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing clogging of the pigment.

When using a filter, other filters may be combined. At this time, the filtering using the first filter may be performed once, or may be performed two or more times. When filtering is performed two or more times in combination with other filters, it is preferable that the hole diameters of the second and subsequent times are equal to or larger than the hole diameters of the first filtering. The first filter having different pore diameters may be combined within the above-described range. The hole diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, there may be selected, for example, various filters provided by Nippon Oil Corporation, Advantech Toyokawa Co., Ltd., Nippon Integrity Corporation (formerly Nihon Micro-Roller Corporation) or Kitsch Microfilter .

The second filter may be formed of the same material as the first filter described above. The pore diameter of the second filter is suitably about 0.2 to 10.0 mu m, preferably about 0.2 to 7.0 mu m, and more preferably about 0.3 to 6.0 mu m.

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

[Coating film (light-shielding film)]

The cured film of the present invention is obtained by using the above-mentioned composition.

The cured film preferably has a surface uneven structure. By doing so, the reflectance of the light-shielding film or the light-shielding film having the light-shielding film can be reduced. The concavo-convex structure may have a concavo-convex structure on the surface of the light-shielding film itself, or another layer may be provided on the light-shielding film to provide the concavo-convex structure. The shape of the surface relief structure is not particularly limited, but it is preferable that the surface roughness is in the range of 0.55 μm or more and 1.5 μm or less.

The reflectance of the light-shielding film is preferably 5% or less, more preferably 3% or less, and particularly preferably 2% or less.

The method for producing the surface relief structure is not particularly limited, but a method including an organic filler or an inorganic filler in a light-shielding film or other layers, a lithography method using an exposure process, an etching method, a sputtering method, a nano-imprinting method or the like The surface of the light-shielding film or other layers may be roughened.

As a method of reducing the reflectance of the cured film, a method of providing a low refractive index layer on the light-shielding film, a method of providing a plurality of layers (for example, high refractive index layers) having different refractive indexes, For example, a method of forming a low optical density layer and a high optical density layer described in JP-A-2015-1654.

In the cured film of the present invention, the above-mentioned titanium nitride-containing particles are mainly included. The cured film of the present invention is suitably used as a light shielding film, and specifically, it is suitably used as a light shielding film (frame 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 a light shielding film around the image sensor, a light shielding film around the image sensor is formed on the color filter and applied to a CCD image sensor or a CMOS image sensor. That is, the above-described cured film can be formed in a region in contact with the frame region of the CCD image sensor or the CMOS image sensor of the color filter.

The color filter having the light shielding film around the image sensor of the present invention is formed using the above-described composition (particularly, the above-described photosensitive composition). The light shielding film around the image sensor obtained using the composition of the present invention is excellent in patterning property and anti-corrosiveness of the electrode.

When used as a light shielding film around the image sensor, the film thickness of the light shielding film is not particularly limited, but from the viewpoint of more effectively obtaining the effect of the present invention, the film thickness after drying is preferably 0.2 탆 or more and 50 탆 or less, Or less, more preferably 0.7 m or more and 20 m or less. From the viewpoint of more effectively obtaining the effect of the present invention, the size of the light-shielding film (length of one side) is preferably from 0.001 mm to 5 mm, more preferably from 0.05 mm to 4 mm, More preferable.

&Lt; Process for producing a cured film &

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

The process for producing a patterned cured film of the present invention comprises a step of applying a composition of the present invention onto a substrate to form a composition layer (coating film) (hereinafter referred to as a "composition layer forming step" (Hereinafter abbreviated as " exposure step " as appropriate) and a step of developing a composition layer after exposure to form a patterned cured film (hereinafter referred to as " And a control unit.

Specifically, the composition of the present invention is applied directly or through a different layer on a substrate to form a composition layer (composition layer forming step), and exposed through a predetermined mask pattern to form only the light irradiated composition layer portion (Curing process) and developing with a developing solution (developing process), a patterned cured film composed of pixels can be formed.

Hereinafter, each process will be described.

(Composition layer forming step)

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

As the substrate, for example, an alkali-free glass, a soda glass, a Pyrex (registered trademark) glass, a quartz glass, a transparent conductive film adhered thereto, a photoelectric conversion element substrate (E.g., a silicon substrate), a CCD (Charge Coupled Device) substrate, and a CMOS (Complementary Metal-Oxide Semiconductor) substrate.

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 surface of the substrate.

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

When manufacturing a color filter having a light shielding film around the image sensor, the coating film thickness of the composition is preferably from 0.35 μm to 2.0 μm, more preferably from 0.40 μm to 1.5 μm from the viewpoints of resolution and developability.

The composition applied on the substrate is generally dried at 70 DEG C or higher and 110 DEG C or lower for about 2 minutes to 4 minutes or less. Thus, a composition layer can be formed.

(Exposure step)

In the exposure step, the composition layer (coating film) formed in the composition layer forming step is exposed through a mask to cure only the irradiated coated film portion.

The exposure is preferably performed by irradiation with an actinic ray or radiation, and 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 is 5 ~ 1500mJ / cm ² are preferred and more preferably 10 ~ 1000mJ / cm ^2.

(Developing step)

Subsequent to the exposure step, an alkali developing treatment (development step) is performed to elute the unirradiated portion in the exposure step into an aqueous alkali solution. As a result, only the photo-cured portion (coated film portion irradiated with light) remains.

When a color filter having a light shielding film around the image sensor is manufactured, an organic alkali developing solution which does not cause any damages to the underlying circuit or the like is preferable. The developing temperature is usually 20 to 30 占 폚, and the developing time is 20 to 90 seconds.

Examples of the alkaline aqueous solution include an inorganic developer and an organic developer. Examples of the inorganic developing solution include alkaline aqueous solutions obtained by dissolving sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate and sodium metasilicate so as to have a concentration of 0.001 to 10 mass%, preferably 0.01 to 1 mass% . Examples of the organic developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4 -0-ene-7-undecene in an amount of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. To the alkaline aqueous solution, a water-soluble organic solvent such as methanol and ethanol and / or a surfactant may be added in an appropriate amount. When a developer comprising such an alkaline aqueous solution is used, it is generally cleaned (rinsed) with purified water after development.

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

In the method of manufacturing a color filter having the cured film of the present invention, after the composition layer forming step, the exposure step, and the developing step described above are carried out, the cured film formed is cured by heating and / or exposure A curing process may be included.

[Color filter, light-shielding film]

The cured film formed using the composition of the present invention is preferably used as a pixel black matrix of a color filter, a light shielding film around the image sensor (frame shielding film) as described above, or a light shielding film applied to various members in an image display device or a sensor module Can be used to make.

(Color filter)

The color filter can be suitably used for a solid-state image pickup 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 exceeding one million pixels. The color filter can be disposed, for example, between a light-receiving portion of each pixel constituting a CCD or a CMOS and a microlens for condensing. The color filter may have a structure in which a cured film for forming each color pixel is embedded in a space partitioned by, for example, a lattice shape by the partition wall. In this case, the partition wall preferably has a low refractive index for each color pixel. Examples of the image pickup device having such a structure include the devices described in Japanese Unexamined Patent Application Publication No. 2002-227478 and Japanese Unexamined Patent Application Publication No. 2014-179577.

The shape of the color filter of the present invention is not particularly limited as long as it has the cured film.

In the color filter, the cured film can be suitably used as, for example, a pixel black matrix of a color filter or a light shielding film (frame shielding film) around the image sensor as described above.

(Light-shielding film)

The light shielding film can be formed and used in an image display apparatus and various members in a sensor module (for example, an infrared light cut filter, an outer peripheral portion of a solid state image pickup element, a wafer level lens outer peripheral portion, or a solid state image pickup element).

A light shielding film may be formed on at least a part of the surface of the infrared light cut filter to form an infrared light cut filter with a light shielding film.

The thickness of the light-shielding film is not particularly limited, but is preferably 0.2 to 25 占 퐉, more preferably 1.0 to 10 占 퐉. The thickness is an average thickness, and is a value obtained by measuring arbitrary five or more thicknesses 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 measured by Hitachi High-Tech Spectrometer UV4100 (trade name) when light with an incident angle of 5 to 400 to 700 nm is incident on the light-shielding film.

[Solid-state image pickup device]

The solid-state imaging element of the present invention comprises 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 it includes the cured film and functions as a solid-state imaging device.

A plurality of photodiodes constituting a light receiving area of a solid-state image sensor (a CCD image sensor, a CMOS image sensor, or the like) and a transfer electrode composed of polysilicon or the like are formed on a substrate. On the photodiode and the transfer electrode, And a device protective film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion, and has a color filter on the device protective film.

Further, it may be a configuration having a condensing means (for example, a microlens or the like) on the device protective layer, below the color filter (near the substrate), or a configuration having condensing means on the color filter. The color filter may have a structure in which a cured film for forming each color pixel is embedded in a space partitioned by, for example, a lattice shape by the partition wall. In this case, the partition wall preferably has a low refractive index for each color pixel. Examples of the image pickup device having such a structure include the devices described in Japanese Unexamined Patent Application Publication Nos. 2001-227478 and 2014-179577.

[Image display device]

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

For the definition of the display device and the details of each display device, refer to, for example, "Electronic display device (Sasaki Akio Kogyo Co., Ltd., Sakai, 1990 issued by Sakai Corporation)", "Display device (Ibukisumi Akira, ) Published in the first year of Heisei) ". The liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Uchida Tatsuo, published by Sakai High School Co., Ltd. in 1994) ". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, the present invention can be applied to 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, its form is not particularly limited.

Hereinafter, a mode in which the color filter of the present invention is applied to a liquid crystal display device will be described in detail.

The color filter of the present invention may be used in a color TFT (Thin Film Transistor) type liquid crystal display device. The color TFT type liquid crystal display device is described in, for example, "Color TFT liquid crystal display (published by Kyoritsu Shootpan Co., Ltd., 1996) ". The color filter of the present invention can be applied to a liquid crystal display device such as a transverse electric field driving system such as IPS (In Plane Switching) or a pixel division system such as MVA (Multi-domain Vertical Alignment) Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip pacer), FFS (fringe field switching) and R-OCB (Reflective Optically Compensated Bend).

In addition, the color filter in the present invention can be applied to a color-filter on array (COA) method which is bright and highly accurate. In the COA type liquid crystal display device, the required characteristics for the color filter may require the characteristics required for the interlayer insulating film, that is, the low dielectric constant and the peel liquid resistance, in addition to the above-mentioned usual required characteristics. Since the color filter of the present invention is excellent in light resistance and the like, it is possible to provide a COA-type liquid crystal display device having high resolution and excellent long-term durability. In addition, in order to satisfy the requirement of low dielectric constant, a resin film may be provided on the color filter layer.

These image display methods are described in, for example, page 43 of "EL, PDP, and LCD display technology and the latest trend in the market" (published by Toray Research Center Research Division, 2001).

The liquid crystal display device of the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, or a viewing angle assurance film in addition to the color filter in the present invention. The color filter of the present invention can be applied to a liquid crystal display device constituted by these known members. These members are described in, for example, "94 Market of Liquid Crystal Display Materials and Chemicals (published by Shimaguchi Co., Ltd., CMC 1994)," 2003 Liquid crystal display market trends and future prospects Quot; Fuji Chimera Soken, 2003 ").

Regarding the backlight, it is described in SID meeting Digest 1380 (2005) (A. Konno et al), Monthly Display December 2005, pages 18-24 (Yamazaki Shimaya), 25-30 pages (Yagi Takaaki) have.

In addition, the cured film of the present invention can be used as a portable device such as a personal computer, a tablet, a mobile phone, a smart phone, or a digital camera; An office automation (OA) device such as a printer multi-function printer or a scanner; Industrial devices such as surveillance cameras, bar code readers, ATMs, high speed cameras, or personal authentication using face image authentication; Vehicle camera equipment; A medical camera device such as an endoscope, a capsule endoscope, or a catheter; An optical filter used for space devices such as a biosensor, a biosensor, a military reconnaissance camera, a three-dimensional map camera, a weather or ocean observation camera, a land resource exploration camera, or an exploration camera for a space astronomical or deep space target It can be used for a light-shielding member or a light-shielding layer of a module. Further, the cured film of the present invention can be used for an antireflection member or an antireflection layer of the optical filter or module.

The cured film of the present invention can also be used for applications such as a micro LED (Light Emitting Diode) and a micro OLED (Organic Light Emitting Diode). It is suitably used for a member that provides a light shielding function or an antireflection function in addition to an optical filter or an optical film used in a micro LED or a micro OLED.

Examples of micro LEDs and micro OLEDs include those described in JP-A-2015-500562 and JP-A-2014-533890.

The cured film of the present invention can also be used for applications such as a quantum dot display. It is suitably used for a member that provides a light shielding function and an antireflection function in addition to an optical filter and an optical film used in a quantum dot display.

Examples of quantum dot displays are disclosed in 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 And the like.

Example

Hereinafter, the present invention will be described in more detail based on examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed to be limited by the following embodiments.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited thereto. Unless otherwise stated, "part" and "%" are based on mass.

[Composition]

Hereinafter, in preparing the compositions of Examples and Comparative Examples, the respective components contained in the composition will be described first.

&Lt; Titanium nitride-containing particles >

Titanium nitride-containing particles TiN-1 to TiN-19 prepared as described below were used as the titanium nitride-containing particles.

(Titanium nitride-containing particles TiN-1)

Titanium nitride-containing particles TiN-1 were produced by using a device similar to the apparatus for producing black composite fine particles described in FIG. 1 of International Publication No. 2010/147098.

In the black composite fine particle production 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 a mixed gas of argon gas of 50 L / min and nitrogen of 50 L / min as the plasma gas To generate an argon-nitrogen thermal plasma salt in the plasma torch. A carrier gas of 10 L / min was supplied from a spray gas supply source of the material supply device.

(Liquid) was used as the raw material 1, liquid ammonia (made by Ube Gosan) was used as the raw material 2, and Ti powder (TC-200 made by Toho Tech Co., Ltd.) Together, they were fed into the thermal plasma salt in the plasma torch and evaporated in the thermal plasma salt to be highly dispersed in the gaseous state. The flow rate ratio (volume ratio) of each of the raw materials 1 to 3 is as shown in Table 1.

Nitrogen was used as the 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 feeding rate of the titanium particles to the cyclone from the chamber was 10 m / s (average value).

Subsequently, the particles were subjected to a heat treatment using a Lavo Kiln L / K manufactured by Nisshin Seisakusho Co., Ltd. as a firing furnace. Specifically, the furnace was heat-treated at 240 캜 for 0.2 hours while supplying nitrogen as an atmosphere gas at a rate of 100 mL / min.

Thus, titanium nitride-containing particles TiN-1 were obtained.

The content of titanium (Ti) atoms and chlorine (Cl) atoms was measured by ICP emission spectroscopy for the obtained titanium nitride-containing particles TiN-1. An ICP emission spectrochemical analyzer "SPS3000" (trade name) manufactured by Seiko Instruments Inc. was used for the ICP emission spectroscopy.

The content of nitrogen atoms was measured using an oxygen / nitrogen analyzer "EMGA-620W / C" (trade name) manufactured by Horiba Seisakusho Co., Ltd. and calculated by an inert gas melting-thermal conductivity method. The results are shown in Table 1.

Also 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 by the same method as that of the titanium nitride-containing particles TiN-1. The residual amount in each particle is an impurity such as oxygen or metal element derived from the oxide present in the particle.

The results are shown in Tables 1 and 2.

X-ray diffraction of the titanium nitride-containing particles TiN-1 was measured by a wide-angle X-ray diffraction method (trade name "RU-200R", manufactured by Rigaku Denki Co., Ltd.) by filling a powder sample with a standard sample holder made of aluminum. The measurement conditions are as follows: the X-ray source is a CuK? 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 °; did.

Then, the diffraction angle 2? Of the peak derived from the TiN (200) plane was measured. From the half width of the peak, the crystallite size constituting the particles was determined using the Scherr equation. The results are shown in Table 1.

The diffraction angle 2? And crystallite size of the following titanium nitride-containing particles TiN-2 to TiN-19 were also measured by the same method as the titanium nitride-containing particles TiN-1. The results are shown in Tables 1 and 2.

The measurement of the average primary particle diameter of the titanium nitride-containing particles TiN-1 was carried out using a transmission electron microscope (TEM) in accordance with the above-described method. In addition, when observing the shape of the particles at the same time as the above-described measurement, it was confirmed that at least 60 of the 100 titanium nitride-containing particles to be observed were spherical. These results are shown in Table 1. In the evaluation of shape observation of particles, when more than 60% of the objects to be measured are spherical, they are shown as "spherical" in the table. When the number of spherical particles is less than 60% of the object to be measured, "spherical shape is less than 60%" is shown in the table. In the table, "cube" indicates the case where the number of particles in the cube is 60% or more of the object to be measured. The cube is not limited to a cube, but a polyhedron is used as a cube.

Also for the following titanium nitride-containing particles TiN-2 to TiN-19, the average primary particle diameter was measured by the same method as that of the titanium nitride-containing particle TiN-1, and further observation of the shape was carried out. The results are shown in Tables 1 and 2.

The specific surface area of the titanium nitride-containing particles TiN-1 was measured at a liquid nitrogen temperature (77K) of N ₂ gas after vacuum degassing at 100 ° C using a high precision automatic gas adsorption apparatus ("BELSORP" The isotherm was analyzed by the BET method to determine the specific surface area. The results are shown in Table 1.

The specific surface area was also determined for the following titanium nitride-containing particles TiN-2 to TiN-19 by the same method as for the titanium nitride-containing particles TiN-1.

The results are shown in Tables 1 and 2.

(Titanium nitride-containing particles TiN-2)

Titanium nitride-containing particles The titanium nitride-containing particles TiN-1 were produced in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials 1 to 3 and the flow rate ratios and the heat treatment conditions used in the preparation of the TiN- Containing particles TiN-2.

(Titanium nitride-containing particles TiN-3)

Titanium nitride-containing particles The titanium nitride-containing particles TiN-1 were produced in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials 1 to 3 and the flow rate ratios and the heat treatment conditions used in the preparation of the TiN- Containing particles TiN-3.

(Titanium nitride-containing particles TiN-4)

Titanium nitride-containing particles The titanium nitride-containing particles TiN-1 were produced in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials 1 to 3 and the flow rate ratios and the heat treatment conditions used in the preparation of the TiN- Containing particles TiN-4.

(Titanium nitride-containing particles TiN-5)

Titanium nitride-containing particles The titanium nitride-containing particles TiN-1 were produced in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials 1 to 3 and the flow rate ratios and the heat treatment conditions used in the preparation of the TiN- Containing particles TiN-5.

(Titanium nitride-containing particles TiN-6)

Titanium nitride-containing particles The titanium nitride-containing particles TiN-1 were prepared in the same manner as the 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 and the flow rate ratios thereof, the heat treatment conditions, To prepare titanium nitride-containing particles TiN-6.

(Titanium nitride-containing particles TiN-7)

Titanium nitride-containing particles TiN-7 were produced in the same manner as the titanium nitride-containing particles TiN-6 except that the flow rates in the chamber were changed as shown in Table 1.

(Titanium nitride-containing particles TiN-8)

Titanium nitride-containing particles The titanium nitride-containing particles TiN-1 were prepared in the same manner as the 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 and the flow rate ratios thereof, the heat treatment conditions, To prepare a titanium nitride-containing particle TiN-8.

(Titanium nitride-containing particles TiN-9)

Titanium nitride-containing particles TiN-9 were prepared in the same manner as the titanium nitride-containing particles TiN-8 except that the flow rates in the chamber were changed as shown in Table 1.

(Titanium nitride-containing particles TiN-10)

Titanium nitride-containing particles The titanium nitride-containing particles TiN-1 were produced in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials 1 to 3 and the flow rate ratios and the heat treatment conditions used in the preparation of the TiN- Containing particles TiN-10.

(Titanium nitride-containing particles TiN-11)

Titanium nitride-containing particles The titanium nitride-containing particles TiN-1 were produced in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials 1 to 3 and the flow rate ratios and the heat treatment conditions used in the preparation of the TiN- Containing particles TiN-11. Further, the raw material 3 of the particles was not used in TiN-11.

(Titanium nitride-containing particles TiN-12)

Titanium nitride-containing particles The titanium nitride-containing particles TiN-1 were produced in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials 1 to 3 and the flow rate ratios and the heat treatment conditions used in the preparation of the TiN- Containing particles TiN-12. Further, the raw materials 1 and 2 were not used in TiN-12.

(Titanium nitride-containing particles TiN-13)

Titanium nitride-containing particles The titanium nitride-containing particles TiN-1 were produced in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials 1 to 3 and the flow rate ratios and the heat treatment conditions used in the preparation of the TiN- Containing particles TiN-13. The heat treatment temperature of the titanium nitride-containing particles TiN-13 was set at 250 캜.

(Titanium nitride-containing particles TiN-14)

Titanium nitride-containing particles The titanium nitride-containing particles TiN-1 were produced in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials 1 to 3 and the flow rate ratios and the heat treatment conditions used in the preparation of the TiN- Containing particles TiN-14.

(Titanium nitride-containing particles TiN-15)

Titanium nitride-containing particles The titanium nitride-containing particles TiN-1 were produced in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials 1 to 3 and the flow rate ratios and the heat treatment conditions used in the preparation of the TiN- Containing particles TiN-15.

(Titanium nitride-containing particles TiN-16)

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

(Titanium nitride-containing particles TiN-17)

Titanium nitride-containing particles The titanium nitride-containing particles TiN-1 were prepared in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials 1 to 3 and the flow rates of the titanium nitride-containing particles TiN- -17.

(Titanium nitride-containing particles TiN-18)

Titanium nitride-containing particles The titanium nitride-containing particles TiN-1 were prepared in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials 1 to 3 and the flow rates of the titanium nitride-containing particles TiN- -18.

(Titanium nitride-containing particles TiN-19)

Titanium nitride-containing particles The titanium nitride-containing particles TiN-1 were produced in the same manner as the titanium nitride-containing particles TiN-1 except that the raw materials 1 to 3 and the flow rate ratios and the heat treatment conditions used in the preparation of the TiN- Containing particles TiN-19.

Production conditions and physical properties of the titanium nitride-containing particles TiN-1 to the titanium nitride-containing particles TiN-19 are shown in the following Tables 1 and 2.

In the table, all of the titanium nitride-containing particles TiN-11, TiN-12, TiN-13 and TiN-14 are all at a heat treatment temperature of 240 占 폚.

(Table 1)

[Table 1]

(Table 2)

[Table 2]

<Dispersant>

Dispersants A to E having the following structures were used as dispersants. In the dispersants A, B and D, the numerical values described in each structural unit are intended to indicate the mass% of each structural unit with respect to the total structural unit. In the dispersant C, the numerical values (a to e) described in each structural unit are intended to mean the molar ratio of each structural unit to the entire structural unit, and x and y are intended to be the number of linkages. Further, in the case of dispersant E, the numerical value described in the connector connected to Z is intended to be the number connected to Z.

[Chemical Formula 20]

[Chemical Formula 21]

<Binder Resin>

The following binder resins A and B were used as the binder resin.

· Binder Resin A (ARC Liqueur RD-F8, Nippon Shokubai Corporation, see structure below)

Binder resin B (cyclamer P (ACA) 230AA die)

[Chemical Formula 22]

<Polymerizable compound>

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

(23)

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: Product name, manufactured by ADEKA

IRGACURE-907: product name, manufactured by BASF Japan

<Solvent>

PGMEA: propylene glycol monomethyl ether acetate

· Cyclopentanone

· Acetic acid butyl

Ethyl 3-ethoxypropionate

· Distilled acetic acid butyl

· Distilled cyclopentanone

As the above-mentioned distilled acetic acid butyl and distilled cyclopentanone, commercially available butyl acetate and cyclopentanone were distilled and purified.

<Polymerization inhibitor>

· P-methoxyphenol

<Surfactant>

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

&Lt; EMI ID =

&Lt; Preparation of Pigment Dispersion >

First, the titanium nitride-containing particles, the dispersant and the solvent were mixed by a stirrer (EUROSTAR manufactured by IKA Corporation) for 15 minutes to obtain a dispersion. Next, the resulting dispersion was subjected to dispersion treatment under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprise Co., Ltd. to obtain a pigment dispersion.

(Dispersion condition)

· Bead diameter: φ0.05 mm, (YTZ manufactured by Nikkato)

· Beads filling rate: 65 vol%

· Mill speed: 10m / sec

Separator speed: 13 m / s

· Mixed liquid amount to be dispersed: 15 kg

· Circulating flow (pump supply): 90kg / hour

· Treatment temperature: 19 ~ 21 ℃

· Cooling water: water

· Processing time: 22 hours

&Lt; Preparation of composition >

Next, the pigment dispersion, the binder resin, the polymerizable compound, the polymerization initiator and the solvent were mixed and stirred to obtain the respective compositions shown in the following Tables 3 to 5 and Comparative Examples. The content (mass%) of each component contained in each composition in Examples and Comparative Examples is shown in Tables 3 to 5.

Further, the ratio ((mass ratio) D / P) of the dispersant to the titanium nitride-containing particles, the solid content concentration (mass%) in the composition, the water content (mass% %) Was the ratio shown in each of Examples and Comparative Examples in Tables 3 to 5.

(Measurement of water content in the composition)

The moisture content of each composition in the examples and comparative examples was measured by MKV-710 (trade name, manufactured by Kyoto Denshi Kogyo Co., Ltd.) having the Karl Fischer method as a measurement principle. The results are shown in Tables 3 to 5.

[Evaluation test]

The following evaluation tests were carried out for each of the compositions of Examples and Comparative Examples.

<Outgas>

Using the compositions of Examples and Comparative Examples, a frame for a color filter was produced.

Specifically, the compositions of Examples and Comparative Examples were spin-coated on a semiconductor substrate constituted by assuming an image sensor with an 8-inch substrate to have a thickness of 1.5 mu m after pre-baking to form a coating film. Subsequently, a binary mask capable of forming a light-shielding film having a width of 250 mu m and a width of 200 mu m was arranged on the outer periphery of 720 mu m in length and 520 mu m in length, and exposed using an i-line exposure apparatus (FPA-3000 + i5, manufactured by Canon Inc.) An exposure dose of 500 mJ / cm &lt; ² &gt;), and further developed.

The obtained semiconductor substrate having a plurality of picture frames for a color filter was cut into a size of 10 mm x 10 mm and the amount of Cl in the out gas was detected by a temperature rise degassing gas analysis method (TDS), and evaluation was performed according to the following criteria . The count intensity ratio of the peak position derived from Cl in the total amount of outgass (detected total ion current value) of mass number 1 to 199 when the count derived from the atmospheric component contained in the background was canceled was measured, And evaluated. The degree of vacuum at the time of measurement was set to 1 x 10 &lt; ^-7 &gt; Torr or less.

"A ": Cl in 1 L of outgas is 10 ppm or less

"B ": Cl in 1 L of outgas exceeding 10 ppm and not more than 50 ppm

"C ": Out of 1 L of Cl, the amount of Cl is more than 50 ppm and not more than 100 ppm

"D ": Cl out of 1 L of outgas exceeding 100 ppm

<Number of particles>

The sample solution diluted 500 times with the above composition by PGMEA was prepared and the number of particles having a size of 10 m or more contained in 10 ml of the sample solution was measured by a flow type particle image analyzer (trade name "FPIA-3000" did.

<OD value>

On the glass plate (EagleXG, manufactured by Corning) having a thickness of 0.7 mm and a squareness of 10 cm, the compositions of Examples and Comparative Examples were spin-coated at a rotation speed of 1.0 占 퐉 in film thickness to form a film. A dried film was obtained. The obtained substrate was subjected to OD measurement by means of a spectrophotometer U-4100 (Hitachi High Technologies), and the lowest OD value in the wavelength range from 400 nm to 1200 nm was measured and evaluated according to the following criteria.

"A": lowest OD of 4.2 or higher

"B": lowest OD is 3.8 or more and less than 4.2

"C": lowest OD is 3.5 or more and less than 3.8

"D": lowest OD less than 3.5

<Filterability>

For the compositions of Examples and Comparative Examples, the filterability was evaluated using a capsule filter DFA (Nippon Poult Co., Ltd., nylon pore diameter: 0.45 μm, 2 inches). Further, 16 kg of the composition was filtered at a flow rate of 400 ml / min and evaluated according to the following criteria.

"A": All 16 kg were filtered.

"B ": After filtration to less than 12 kg and less than 16 kg, the flow rate was less than 400 mL / min.

"C ": The filtrate was filtered from 8 kg to less than 12 kg, and 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.

&Lt; Stability of viscosity of the composition over time (stability of CM over time)

The compositions of the examples and comparative examples were stored at 23 캜 for 30 days and then at 7 캜 for 9 months. Thereafter, the viscosity of each composition before and after storage was measured using an E-type viscometer (product name: "R85 type viscometer" manufactured by Toki Sangyo Co., Ltd.) under the conditions of the number of revolutions of 10 rpm and 23 ° C, . The evaluation criteria are as follows.

(Viscosity increase rate) = (viscosity after aging) - (viscosity immediately after liquid preparation) / (viscosity immediately after liquid preparation)

"A": Less than 3% increase rate

"B": Increase rate 3% to less than 5%

"C": Increase rate 5% or more and less than 10%

"D": Increase rate 10% or more

<Patterning property (resolution)>

Using the compositions of Examples and Comparative Examples, a coating film was formed on the image sensor device substrate by a spin coater. Next, the obtained coating film was prebaked on a hot plate at 100 DEG C for 2 minutes. Subsequently, the coating film subjected to the pre-baking treatment is exposed using an i-line exposure apparatus (FPA, manufactured by Canon Inc.) and further developed so that a dicing line and a light shielding film covering the electrode portion are formed on the outer peripheral portion of the light- And 20 alignment marks having a line width of 20 mu m were formed on the substrate.

The resolution was evaluated by observing the number of the formed alignment marks using an optical microscope.

"A": 20 marks were formed.

"B ": 19 marks were formed.

"C ": 18 marks were formed.

"D": No more than 17 marks.

<Corrosion resistance of electrode>

Using the compositions of Examples and Comparative Examples, a coating film was formed on the image sensor device substrate by a spin coater. Subsequently, the obtained device substrate after the coating film formation was prebaked on a hot plate at 100 DEG C for 2 minutes. Subsequently, the coating film subjected to the pre-baking treatment was exposed to light using an i-line exposure apparatus (FPA-3000 + i5, manufactured by Canon) and further developed so that a dicing line and electrode portions Thereby forming a light-shielding film for covering. The resulting light-shielding film was subjected to heat treatment at 220 DEG C for 5 minutes using a hot plate (post-baking step).

The resulting wafer having the light-shielding film was stored for 3 days under an environment of a temperature of 110 DEG C and a humidity of 90% RH (HAST tester EHS-411M manufactured by Espec Co.), and the rust state of the electrode pattern was measured on 300 electrode pads Was observed with an optical microscope (manufactured by Olympus, trade name "LEXT OLS4500"), and the corrosion resistance of the electrode was evaluated according to the following criteria.

"A": no change observed

"B": Rust of the electrode is 2 or less

"C": Greater than 2 and less than 10 rust

"D": Greater than 10 rust of electrode

The evaluation results of the above evaluation tests are shown in Tables 3 to 5.

Further, in Example 33, the mixing ratio of M1 and PET-30 is 5: 5 by mass ratio.

[Table 3]

[Table 4]

[Table 5]

As shown in Tables 3 to 5, if the content of chlorine atoms in the titanium nitride-containing particles is in the range of 0.001 to 0.3 mass% (in other words, 10 mass ppm to 3000 mass ppm) , And a cured film excellent in patterning property (resolution) can be produced (Example).

When the content of the chlorine atoms in the titanium nitride-containing particles exceeds 0.3 mass% (in other words, 3000 mass ppm), the patterning property (resolution) and the corrosion resistance of the electrode are inferior (Comparative Example 1, Comparative Example 2).

Also, when the content of chlorine atoms in the titanium nitride-containing particles was less than 0.001 mass% (in other words, less than 10 mass ppm), the patterning properties (comparative example 3 and comparative example 4) were poor.

In contrast to Examples 17 to 21, when the content of water is 0.1 to 1% by mass (preferably 0.1 to 0.8% by mass, and more preferably 0.1 to 0.4% by mass) based on the total mass of the composition, It was confirmed that the patterning property (resolution) of the cured film and the corrosion resistance of the electrode material were more excellent. Further, it was confirmed that the content of water in the composition was 0.1 to 1% by mass with respect to the total mass of the composition to further reduce the amount of particles in the composition, and the stability of the composition over time was also superior.

Also, it was confirmed that the patterning property (resolution) of the cured film was more excellent when the D / P was 0.3 or less, by the contrast between Example 26 and Example 27. [

(Good OD value), patterning property (resolution) when the content of the titanium nitride-containing particles was 30 to 70% by mass with respect to the total solid content of the composition by the contrast of Examples 26, 31 and 32, And the corrosion resistance of the electrode was more excellent.

It is to be noted that the spectral properties (good OD value) and patterning property (resolution) of the titanium nitride-containing particles were 40 to 60 m ² / g, as determined by the BET method, . In addition, it was confirmed that the filter was also excellent in filtration.

When the diffraction angles 2? Of the peaks derived from the (200) plane of the titanium nitride-containing particles are in the range of 42.8 DEG to 43.5 DEG in the case where the CuK? Ray is an X-ray source, , A spectroscopic property (good OD value), and a patterning property (resolution).

It was also confirmed by the contrast of Examples 12 to 15 that the spectroscopic properties (good OD value) were better when the average primary particle size of the titanium nitride-containing particles was 10 to 30 nm. In addition, it was confirmed that the viscosity stability of the composition over time was also excellent. It was also confirmed that when titanium nitride-containing particles had an average primary particle diameter of 10 nm or more, the composition had excellent viscosity stability over time.

In contrast to 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 the transmission electron microscope of the titanium nitride-containing particles, the spectral properties (good OD value) And patterning property (resolution). Further, it was confirmed that the composition had excellent filterability and viscosity stability with time.

Evaluation was carried out 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 results as in Example 1 were obtained.

&Lt; Preparation of carbon black dispersion (CB dispersion) >

In the preparation of the above pigment dispersion, carbon black (trade name: "Color Black S170" manufactured by Degussa Co., Ltd., average primary particle diameter 17 nm, BET specific surface area 200 m ² / g, manufactured by the gas black method Carbon black) was used in place of the carbon black dispersion obtained in Example 1, a dispersion was prepared to obtain a carbon black dispersion.

In the preparation of the composition of Example 1, a pigment dispersion containing titanium nitride-containing particles TiN-1 and a pigment dispersion containing the titanium nitride-containing particles TiN-1 in an amount of 19 mass% [Titanium nitride-containing particles TiN-1 in composition: Carbon black in composition = 15: 4 (by mass ratio). And the total content of the titanium nitride-containing particles TiN-1 and carbon black in the composition was 19 mass%) was used in place of the titanium nitride-containing particles TiN-1 and carbon black. As a result of the evaluation, it was found that the same light shielding property as in Example 1 was obtained.

&Lt; Preparation of chromatic pigment dispersion (PY dispersion) >

The pigment dispersion was prepared in the same manner as in the preparation of the pigment dispersion except that Pigment Yellow 150 (manufactured by Hangzhou Star-up Pigment Co., Ltd., trade name: 6150 pigment sulfur 5GN) was used instead of the titanium nitride- To obtain a chromatic pigment dispersion (PY dispersion).

In the preparation of the composition of Example 1, a pigment dispersion containing titanium nitride-containing particles TiN-1 and a pigment dispersion containing the titanium nitride-containing particles TiN-1 in an amount of 19 mass% [Titanium nitride-containing particles TiN-1 in the composition: Pigment Yellow 150 = 17: 2 (mass ratio) in the composition. And the total content of the titanium nitride-containing particles TiN-1 and Pigment Yellow 150 in the composition was 19 mass%) was used in place of the titanium nitride-containing particles TiN-1 and Pigment Yellow 150 in the composition. As a result of the evaluation, it was found that the same light shielding property as in Example 1 was obtained and a dark black film was obtained.

Claims (19)

Containing titanium nitride-containing particles containing a chlorine atom,
Wherein the content of the chlorine atoms in the titanium nitride-containing particles is 0.001 to 0.3 mass%. The method according to claim 1,
Wherein the diffraction angle 2? Of the peak originating from the (200) plane of the titanium nitride-containing particles is 42.8 占 to 43.5 占 when the CuK? Ray is an X-ray source. The method according to claim 1 or 2,
Wherein the titanium nitride-containing particles have a specific surface area of 40 to 60 m ² / g as measured by the BET method. The method 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. The method according to any one of claims 1 to 4,
Wherein at least 60 of 100 objects to be observed are spherical in the photographic observation of the primary particles of the titanium nitride-containing particles using a transmission electron microscope. The method according to any one of claims 1 to 5,
Wherein the composition further comprises at least two solvents. The method according to any one of claims 1 to 6,
Further comprising a dispersing agent. The method of claim 7,
Wherein the content ratio of the dispersant to the titanium nitride-containing particles is 0.3 or less by mass ratio. The method according to any one of claims 1 to 8,
Further comprising a polymerizable compound. The method according to any one of claims 1 to 9,
Further comprising a polymerization initiator. The method according to any one of claims 1 to 10,
Wherein the solid content in the composition is 10 to 40% by mass. The method according to any one of claims 1 to 11,
Wherein the content of the titanium nitride-containing particles is 30 to 70 mass% with respect to the total solid content of the composition. The method according to any one of claims 1 to 12,
It contains more water,
Wherein the water content is 0.1 to 1% by mass with respect to the total mass of the composition. The method according to any one of claims 1 to 13,
Further comprising a dispersing agent,
Wherein the dispersant has at least one structure selected from the group consisting of polycaprolactone, polyvalerolactone, methyl polyacrylate and methyl polymethacrylate. A cured film obtained by 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 apparatus having the cured film according to claim 15.