TWI790993B - Black composition, cured film, color filter, light-shielding film, solid-state imaging element, and image display device - Google Patents

Abstract

The present invention provides a method capable of producing electrodes with excellent corrosion resistance and pattern formation. Composition of excellent hardening film. Furthermore, a cured film, a color filter, a light-shielding film, a solid-state imaging element, and an image display device are provided. The composition contains titanium nitride-containing particles containing chlorine atoms, and the content of the chlorine atoms in the titanium nitride-containing particles is 0.001 to 0.3% by mass.

Description

Black composition, hardened film, color filter, light-shielding film, solid-state imaging element components and image display devices

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

A solid-state imaging device includes an imaging lens, a solid-state imaging element such as a CCD (Charge Coupled Device) and a CMOS (Complementary Metal Oxide Semiconductor) arranged behind the imaging lens (hereinafter, the solid-state imaging element is also referred to as an "image sensor"). ".) and a circuit board on which the solid-state imaging device is mounted. The solid-state imaging device is installed in a digital camera, a mobile phone with a camera, a smartphone, and the like.

In solid-state imaging devices, noise caused by reflection of visible light sometimes occurs. Accordingly, in order to suppress the generation of noise, a predetermined light-shielding film is provided in the solid-state imaging device. As a composition for forming a light-shielding film, a black composition containing a black pigment such as titanium black is used.

On the other hand, in color filters arranged in solid-state imaging devices and liquid crystal image devices, etc., R (red), G (green), B A black matrix is formed between each pixel (blue). In addition, in order to prevent the light leakage of the light receiving part of the solid-state imaging element in the color filter, a light-shielding film around the image sensor (frame light-shielding film) is formed in the frame region.

A black composition containing black pigments such as titanium black is also used in the composition for forming the above-mentioned black matrix. For example, Patent Document 1 discloses "a black resin composition for a resin black matrix, which includes at least a light-shielding material, a resin, and a solvent, and contains at least titanium nitride particles as a light-shielding material, wherein when CuKα rays are used as the X-ray source The diffraction angle 2θ of the peak originating from the (200) plane of the above-mentioned titanium nitride particles is not less than 42.5° and not more than 42.8°." (claim 1). [Prior Art Document] [Patent Document]

[Patent Document 1]: Japanese Patent No. 5136139

A cured film of a black composition containing titanium nitride particles (titanium nitride particle-containing particles) as described above is used, for example, as a light-shielding film or a black matrix of a color filter as a component of a solid-state imaging device, or around an image sensor In the case of a light-shielding film, it may be used by laminating on a substrate on which electrodes such as electrode patterns are arranged. The inventors of the present invention produced the black composition containing titanium nitride particles (containing titanium nitride particles) described in Patent Document 1, and used it to form a cured film on the substrate on which the electrodes were arranged so as to cover the electrodes, and implemented its evaluation. As a result, it was found that depending on the type of titanium nitride particles (titanium nitride-containing particles), rust or the like was generated in the region in contact with the light-shielding film of the electrode, that is, the electrode was sometimes corroded. In addition, similarly, it has been found that when a pattern-shaped cured film is formed using the above-mentioned black composition, the resolution of the pattern (pattern formability) does not satisfy the desired requirements.

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

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

(1) A composition containing titanium nitride-containing particles containing chlorine atoms, wherein the content of the chlorine atoms in the titanium nitride-containing particles is 0.001 to 0.3% by mass. (2) The composition according to (1), wherein when CuKα rays are used as an X-ray source, the diffraction angle 2θ of the peak originating from the (200) plane of the titanium nitride-containing particles is more than 42.8° and 43.5°. ° below. (3) The composition according to (1) or (2), wherein the titanium nitride-containing particles have a specific surface area determined by the BET method of 40 to 60 m ² /g. (4) The composition according to any one of (1) to (3), wherein the titanium nitride-containing particles have an average primary particle diameter of 10 to 30 nm. (5) The composition according to any one of (1) to (4), wherein, in photographic observation of primary particle images of the titanium nitride-containing particles using a transmission electron microscope, among 100 observation objects More than 60 are spherical. (6) The composition according to any one of (1) to (5), which further contains two or more solvents. (7) The composition according to any one of (1) to (6), which further contains a dispersant. (8) The composition according to (7), wherein the content ratio of the dispersant to the titanium nitride-containing particles is 0.3 or less in mass ratio. (9) The composition according to any one of (1) to (8), which further contains a polymerizable compound. (10) The composition according to any one of (1) to (9), which further contains a polymerization initiator. (11) The composition according to any one of (1) to (10), wherein the solid content in the composition is 10 to 40% by mass. (12) The composition according to any one of (1) to (11), wherein the content of the titanium nitride-containing particles is 30 to 70% by mass relative to the total solid content of the composition. (13) The composition according to any one of (1) to (12), which further contains water, and the content of the water is 0.1 to 1% by mass relative to the total mass of the composition. (14) The composition as described in any one of (1) to (13), which further contains a dispersant, and the above-mentioned dispersant has a compound selected from the group consisting of polycaprolactone, polyvalerolactone, polymethyl acrylate and polymethyl acrylate. At least one structure of the group consisting of methyl acrylate. (15) A cured film obtained using the composition described in 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 described in (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). [Invention effect]

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

Hereinafter, the present invention will be described. In this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In the expression of the group (atomic group) in this specification, the expression which does not describe substitution and unsubstituted means the thing which has a substituent together with the thing which does not have a substituent. For example, "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In this specification, "active light" or "radiation" means, for example, the bright-line spectrum of a mercury lamp, extreme ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams. In addition, in the present invention, light means actinic light or radiation. Regarding the "exposure" in this specification, unless otherwise specified, it is not limited to the exposure based on the bright line spectrum of the mercury lamp, the extreme ultraviolet rays represented by the excimer laser, X-rays, EUV light, etc., based on the electron beam and ion beam, etc. The rendering of the particle beam is also included in the exposure. In this manual, "(meth)acrylate" means acrylate and methacrylate, "(meth)acrylic acid" means acrylic acid and methacrylic acid, "(meth)acryl" means acryl and methacrylate Acrylamide, "(meth)acrylamide" means acrylamide and methacrylamide. In addition, in this specification, "monomer" and "monomer" have the same meaning. The monomer in the present invention is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In this specification, a polymerizable compound refers to a compound having a polymerizable group, which may be a monomer or a polymer. A polymerizable group refers to a group that participates in a polymerization reaction. [Composition] The composition of the present invention contains titanium nitride-containing particles containing chlorine atoms, and the content of the chlorine atoms in the titanium nitride-containing particles is 0.001 to 0.3% by mass. According to the composition of this invention, the cured film which is excellent in corrosion resistance of an electrode and excellent in pattern formability can be produced. The inventors of the present invention conducted intensive studies, and as a result, it was confirmed that, using a black composition containing titanium nitride-containing particles containing chlorine atoms in an amount exceeding 0.3% by mass as a pigment component, the electrode is disposed When the light-shielding film is formed on the substrate, hydrochloric acid is generated by the reaction of the above-mentioned chlorine atoms with moisture in the air, depending on the environmental conditions of use, which may cause deterioration of the electrode member. On the other hand, it was found that when titanium nitride-containing particles containing less than 0.001% by mass of chlorine atoms are used as a composition of pigment components, the optical density (OD) of the obtained coating film becomes high, and the patterning property tends to decrease. . From the viewpoints described above, by setting the content of chlorine atoms in the titanium nitride-containing particles contained in the composition to 0.001 to 0.3% by mass, it is possible to form a cured film that is excellent in corrosion resistance of electrodes and excellent in pattern formability.

<Titanium Nitride-Containing Particles Containing Chlorine Atoms> When producing 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 production methods, the thermal plasma method is preferable from the viewpoints of less contamination of impurities, easier uniformity of particle diameters, and higher productivity. Examples of methods for generating thermal plasma include direct current arc discharge, multiphase arc discharge, high frequency (RF) plasma, and hybrid plasma. High frequency plasma with less impurities from the electrodes is better. good. As a specific production method of titanium nitride-containing particles based on the thermal plasma method, for example, titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced into the device as a carrier gas, and titanium Powder nitriding to synthesize titanium nitride-containing particles, etc. In addition, the thermal plasma method is not limited to the above-mentioned ones. In addition, by using the thermal plasma method to obtain titanium nitride-containing particles, it is easy to adjust the diffraction angle 2θ (details will be described later) of the peak originating from the (200) plane when CuKα rays are used as the X-ray source to More than 42.8° and less than 43.5°.

However, there is no particular limitation on the method of adding chlorine atoms to the titanium nitride-containing particles. As an example, in the thermal plasma method described above, titanium tetrachloride is used together with titanium powder, and ammonia gas is flowed as a carrier gas to synthesize titanium nitride-containing particles containing chlorine atoms. In addition, when the content of chlorine atoms in the titanium nitride-containing particles is more than a predetermined amount, the particles are heat-treated for 5 minutes at, for example, 100 to 300° C. (preferably 120 to 280° C., more preferably 120 to 250° C.). ~72 hours (preferably 3~48 hours, more preferably 3~36 hours) is more preferred. By heat treatment, the content of chlorine atoms included in the titanium nitride-containing particles can be reduced and adjusted to a predetermined amount.

The titanium powder material (titanium particles) used in the production of titanium nitride-containing particles and titanium tetrachloride are preferably high-purity ones. The titanium powder material and titanium tetrachloride are not particularly limited, and those with a purity of titanium element of 99.99% or higher can be preferably used, and more preferably, those with a purity of 99.999% or higher are used.

Titanium powder materials (titanium particles) and titanium tetrachloride used in the production of titanium nitride-containing particles may contain atoms other than titanium atoms. Examples of other atoms that may be contained in the titanium powder material include Fe atoms, Si atoms, and the like. When the titanium powder material and titanium tetrachloride contain Fe atoms, the content of Fe atoms is preferably more than 0.001% by mass based on the total mass of the titanium powder material and titanium tetrachloride. Thereby, the pattern formability of a cured film becomes more excellent. Furthermore, when the titanium powder material and titanium tetrachloride contain Fe atoms, the content of Fe atoms is preferably less than 0.4% by mass relative to the total amount of the titanium powder material and titanium tetrachloride. Thereby, the anti-corrosion property of the electrode based on the cured film is more excellent (corrosion of the electrode by the cured film can be further suppressed). That is, the titanium powder material used in the manufacture of titanium nitride-containing particles and Fe atoms contained in titanium tetrachloride are within the above-mentioned range (more than 0.001% by mass and less than 0.4% by mass), the present invention can be obtained more remarkably. The effect of the invention. When the titanium powder material and titanium tetrachloride contain Si atoms, the content of Si atoms relative to the total mass of the titanium powder material is preferably more than 0.002% by mass and less than 0.3% by mass, more preferably 0.01 to 0.15% by mass, and 0.02 to 0.1% by mass. Mass % is further more preferable. When content of Si atom exceeds 0.002 mass %, the pattern formability of a cured film improves more. And it is considered that the polarity of the outermost layer of the obtained titanium nitride-containing particles is stabilized when the content of Si atoms is less than 0.3% by mass, and the adsorption of the dispersant to the titanium nitride-containing particles when the titanium nitride-containing particles are dispersed is improved. Improvement, the reduction of undispersed matter containing titanium nitride particles, thereby having the effect of suppressing the generation of particles. That is, the effects of the present invention can be more remarkably obtained when the titanium powder material used in the production of titanium nitride-containing particles and the Si atoms contained in titanium tetrachloride are within the above-mentioned range. In addition, the moisture in the titanium powder material (titanium particles) and titanium tetrachloride used in the manufacture of titanium nitride-containing particles is preferably less than 1% by mass, more preferably less than 0.1% by mass, relative to the total mass of the titanium powder material. Better, substantially not included is further better. When the moisture in the titanium powder material and 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 more remarkably obtained.

The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 50-85% by mass, more preferably 50-80% by mass, and 50-75% by mass relative to the total mass of the titanium nitride-containing particles. for further improvement. The content of Ti atoms in the titanium nitride-containing particles can be analyzed by ICP (inductively coupled plasma) emission spectrometry. The content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 20-50% by mass, more preferably 20-45% by mass, and 20-40% by mass relative to the total mass of the titanium nitride-containing particles. for further improvement. 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 at most 12% by mass, more preferably at most 8% by mass, based on the total mass of the titanium nitride-containing particles. The content of oxygen atoms can be analyzed by inert gas fusion infrared absorption method.

The content of chlorine atoms in the titanium nitride-containing particles is 0.001 to 0.3% by mass relative to the total mass of the titanium nitride-containing particles. Among these, 0.005-0.3 mass % is preferable, 0.01-0.3 mass % is more preferable, 0.1-0.3 mass % is still more preferable, and 0.1-0.15 mass % is especially preferable. When content of a chlorine atom is 0.001 mass % or more, the pattern formability of a cured film is excellent. When content of a chlorine atom is 0.3 mass % or less, the pattern formability of a cured film is excellent, and the corrosion resistance of the electrode by a cured film is excellent. Here, the content of chlorine atoms in the titanium nitride-containing particles was measured by ICP emission spectrometry.

The diffraction angle 2θ of the peak originating from the (200) plane of the titanium nitride-containing particles when the X-ray diffraction spectrum is measured using CuKα rays as the X-ray source is preferably more than 42.8° and 43.5° or less. The OD value of the cured film (for example, a black matrix etc.) obtained using the composition containing the titanium nitride particle containing such characteristics becomes an appropriate value, and the pattern formability (resolution) is more excellent.

As mentioned above, the diffraction angle 2θ of the peak originating from the (200) plane of the titanium nitride-containing particles is preferably more than 42.8° and 43.5° or less, more preferably 42.85 to 43.3°, and still more preferably 42.9 to 43.2°. Titanium nitride-containing particles contain titanium nitride (TiN) as the main component. Usually, when it is synthesized, oxygen is mixed or the particle size is small, etc., but a part of oxygen can be contained by oxidation of the particle surface, etc. atom. Among them, titanium nitride-containing particles are preferable because a higher OD value (optical density) can be obtained when the amount of oxygen contained in the titanium nitride-containing particles is small. Furthermore, it is preferable that the titanium nitride-containing particles do not contain TiO ₂ as an auxiliary component. When titanium nitride-containing particles contain titanium oxide TiO ₂ as an auxiliary component, the peak derived from anatase-type TiO ₂ (101) appears near 2θ=25.3° as the peak with the strongest intensity, which is derived from rutile-type TiO ₂ ( 110) peak appears around 2θ=27.4°. However, TiO ₂ is white and is a factor that lowers the light-shielding properties of the black matrix, so it is preferable to reduce it to such an extent that it is not observed as a peak.

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

As a crystallite size, 20 nm or more is preferable, and 20-50 nm is more preferable. When using titanium nitride particles with a crystallite size of 20nm or more to form a black matrix, the transmitted light of the cured film is blue to blue-purple with a peak wavelength below 475nm, which can obtain both high light-shielding properties and ultraviolet sensitivity The black matrix.

The specific surface area of the titanium nitride-containing particles can be obtained by the BET method, and is preferably 40 to 60 m ² /g, more preferably 40 to 58 m ² /g, and still 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 OD (optical density) value of the obtained cured film is in a more appropriate range, and the pattern formability (resolution) is more excellent, and the composition The filterability of the material is also excellent.

The average primary particle size of the titanium nitride-containing particles is preferably from 10 to 30 nm, more preferably from 10 to 28 nm, still more preferably from 10 to 25 nm, and still more preferably from 10 to 20 nm. By setting the average primary particle size of the titanium nitride-containing particles to 10 to 30 nm, the OD (optical density) value of the obtained cured film will be in an appropriate range. Furthermore, from the viewpoint of the temporal stability of the viscosity of the composition, the titanium nitride-containing particles preferably have an average primary particle diameter of 10 nm or more. In addition, in the present invention, the average primary particle size of the titanium nitride-containing particles means that the particles can be observed by a transmission electron microscope (for example, a JEM-2100F field emission transmission electron microscope device manufactured by JEOL Ltd.), And the number-average particle diameter of primary particles was calculated from the obtained photographs. Specifically, a dispersion containing titanium nitride-containing particles was prepared by the method described in the examples, and diluted with the same solvent as the dispersion in such a manner that the solid content thereof was about 1% by mass, and placed on a carbon foil The dispersion liquid was added dropwise, and the transmission electron microscope image of the titanium nitride-containing particles existing on the carbon foil after drying was observed. The projected area of the primary particle containing the titanium nitride particle was obtained by the above-mentioned apparatus, and the circle-equivalent diameter was obtained by this. The arithmetic mean of the calculated circle-equivalent diameters was used as the primary particle diameter. More specifically, after measuring the primary particle diameter of 100 particles randomly selected to obtain the average primary particle diameter, the arithmetic average of the primary particle diameters of 80 particles excluding the 10 largest and 10 smallest particles is obtained. Out circle equivalent diameter. In addition, it is preferable that 60 or more (in other words, 60% or more) of 100 observation objects are spherical in the photographic observation of the titanium nitride-containing particles using the primary particle image of the above-mentioned transmission electron microscope. When 60% or more of the titanium nitride-containing particles used are spherical, the OD (optical density) value of the obtained cured film is in an appropriate range, and the pattern formability (resolution) is more excellent. Furthermore, since 60% or more of the titanium nitride-containing particles used are spherical, the filterability and viscosity stability of the composition are also excellent. In addition, in the present invention, the particle is "spherical" means that it does not necessarily have to be a true sphere, for example, it may be approximately spherical (the ratio of minor axis to aspect ratio in the two-dimensional figure at the time of projection is about 0.7 to 1), spheroid body.

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

<Dispersant> The composition of the present invention preferably contains a dispersant. The dispersant contributes to improving the dispersibility of the above-mentioned pigments containing titanium nitride particles and the like. In the present invention, the dispersant is a component different from the binder resin described later. As a dispersant, for example, a known pigment dispersant can be appropriately selected and used. Among them, polymer compounds are preferred. As the dispersant, high molecular dispersant [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated ester, modified polyurethane, modified polyester, modified poly(formyl base) acrylate, (meth)acrylic acid copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine and pigment derivatives, etc. Macromolecular compounds can be further classified into linear polymers, end-modified polymers, grafted polymers, and block polymers according to their structures.

The polymer compound is adsorbed on the surface of the dispersed body such as titanium nitride-containing particles and optional pigments, and plays a role in preventing the re-agglomeration of the dispersed body. Therefore, end-modified polymers, grafted polymers, and block polymers having fixed sites on the surface of the pigment are preferred. On the other hand, by modifying the surface of the titanium nitride-containing particles, the adsorption property of the polymer compound can also be promoted.

It is preferable that the polymer compound has a structural unit having a graft chain. In addition, in this specification, a "structural unit" has the same meaning as a "repeating unit". A polymer compound having a structural unit having such a graft chain has affinity with a solvent due to the graft chain, and thus is excellent in dispersibility of pigments such as titanium nitride-containing particles and dispersion stability over time. Furthermore, due to the presence of the graft chain, the polymer compound having the structural unit having the graft chain has affinity with polymerizable compounds or other applicable resins. As a result, residues are less likely to be generated during alkali image development. When the graft chain becomes longer, the steric repulsion effect increases and the dispersibility of the pigment and the like improves. On the other hand, if the graft chain is too long, the adsorption force to pigments such as titanium nitride-containing particles decreases, and the dispersibility of pigments and the like tends to decrease. Therefore, the graft chain is preferably 40 to 10,000 atoms other than hydrogen atoms, more preferably 50 to 2,000 atoms other than hydrogen atoms, and further preferably 60 to 500 atoms other than hydrogen atoms. good. Here, the graft chain means the root of the main chain of the copolymer (the atom bonded to the main chain in the group branched from the main chain) to the terminal of the group branched from the main chain.

It is preferable that the graft chain has a polymer structure, and examples of such a polymer structure include a poly(meth)acrylate structure (for example, a poly(meth)acrylic acid structure), a polyester structure, a polyurethane structure, a poly Urea structure, polyamide structure and polyether structure, etc. In order to improve the interaction between the graft chain and the solvent, and thereby improve the dispersibility, the graft chain system has at least 1 selected from the group consisting of polyester structure, polyether structure and poly(meth)acrylate structure. A grafted chain of the above species is preferred, and a grafted chain having at least one of a polyester structure and a polyether structure is more preferred.

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

Corresponding to the structural unit having a grafted chain of a polymer compound, as a commercially available macromonomer suitable for synthesizing a polymer compound, 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.), AS-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AN-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AW-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AA-714 (trade name, manufactured by TOAGOSEI CO., LTD.), AY-707 (trade name, manufactured by TOAGOSEI CO., LTD.) name, manufactured by TOAGOSEI CO., LTD.), AY-714 (trade name, manufactured by TOAGOSEI CO., LTD.), AK-5 (trade name, manufactured by TOAGOSEI CO., LTD.), AK-30 (trade name, manufactured by TOAGOSEI CO., LTD. TOAGOSEI CO., LTD.), AK-32 (trade name, manufactured by TOAGOSEI CO., LTD.), Blemmer PP-100 (trade name, manufactured by NOF CORPORATION.), Blemmer PP-500 (trade name, NOF CORPORATION. manufactured), Blemmer PP-800 (trade name, manufactured by NOF CORPORATION.), Blemmer PP-1000 (trade name, manufactured by NOF CORPORATION.), Blemmer 55-PET-800 (trade name, manufactured by NOF CORPORATION.), Blemmer PME- 4000 (trade name, manufactured by NOF CORPORATION.), Blemmer PSE-400 (trade name, manufactured by NOF CORPORATION.), Blemmer PSE-1300 (trade name, manufactured by NOF CORPORATION.), Blemmer 43PAPE-600B (trade name, manufactured by NOF CORPORATION. manufacturing), etc. Among them, AA-6 (trade name, manufactured by Toagosei. Company, Limited.), AA-10 (trade name, manufactured by TOAGOSEI CO., LTD.), AB-6 (trade name, manufactured by TOAGOSEI CO., LTD.) were used , AS-6 (trade name, manufactured by TOAGOSEI CO., LTD.), AN-6 (trade name, manufactured by TOAGOSEI CO., LTD.) and Blemmer PME-4000 (trade name, manufactured by NOF CORPORATION.) etc. are preferable .

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

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

[chemical formula 1]

In formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ each independently represent an oxygen atom or NH. W ¹ , W ² , W ³ and W ⁴ are preferably oxygen atoms. In formulas (1) to (4), X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. X ¹ , X ² , X ³ , X ⁴ , and X ⁵ are preferably each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (number of carbon atoms) from the viewpoint of restrictions on synthesis. , each independently being a hydrogen atom or a methyl group is more preferred, and a methyl group is further preferred.

In formulas (1) to (4), Y ¹ , Y ² , Y ³ , and Y ⁴ each independently represent a divalent linking group, and the structure of the linking group is not particularly limited. As the divalent linking group represented by Y ¹ , Y ² , Y ^{3 ,} and Y ⁴ , specifically, linking groups of the following (Y-1) to (Y-21) and the like are exemplified. In the structures shown below, A and B represent the bonding sites to the left end group and the right end group in formulas (1) to (4), respectively. Among the structures shown below, (Y-2) or (Y-13) is more preferable in view of the simplicity of synthesis.

[chemical formula 2]

In formulas (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, and specific examples thereof include alkyl, hydroxyl, alkoxy, aryloxy, heteroaryloxy, alkylsulfide, arylsulfide, and heteroarylsulfide and amine groups, etc. Among them, as the organic groups represented by Z ¹ , Z ² , Z ³ and Z ⁴ , those having a steric repulsion effect are preferable especially from the standpoint of improving dispersibility, and each independently has 5 to 5 carbon atoms. 24 alkyl or alkoxy group is preferred, wherein each independently is a branched alkyl group with 5 to 24 carbon atoms, a cyclic alkyl group with 5 to 24 carbon atoms or an alkoxy group with 5 to 24 carbon atoms The base is especially good. In addition, the alkyl group included in the alkoxy group may be any of linear, branched and cyclic.

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

In formula (3), R ³ represents a branched or linear alkylene group, preferably an alkylene group with 1 to 10 carbon atoms, and more preferably an alkylene group with 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R ³ may be the same or different from each other. In 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 preferably includes a hydrogen atom, an alkyl group, an aryl group and a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When ^R4 is an alkyl group, as the alkyl group, a linear alkyl group with 1 to 20 carbon atoms, a branched alkyl group with 3 to 20 carbon atoms, or a cyclic alkyl group with 5 to 20 carbon atoms is preferred. A straight-chain alkyl group having 1 to 20 carbon atoms is more preferable, and a straight-chain alkyl group having 1 to 6 carbon atoms is still more preferable. In formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

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

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

[chemical formula 3]

In formula (1A), X ¹ , Y ¹ , Z ¹ and n have the same meanings as X ¹ , Y ¹ , Z ¹ and n in formula (1), and their preferred ranges are also the same. In formula (2A), X ² , Y ² , Z ² and m have the same meanings as X ² , Y ² , Z ² and m in formula (2), and their preferred ranges are also the same.

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

[chemical formula 4]

In formula (3A) or (3B), X ³ , Y ³ , Z ³ and p have the same meanings as X ³ , Y ³ , Z ³ and p in formula (3), and the preferred ranges are also the same.

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

In polymer compounds, the structural units with grafted chains (for example, the structural units represented by the above formula (1) to formula (4)) are converted by mass, relative to the total mass of the polymer compound, at 2 to 90% It is preferable to include in the range, and it is more preferable to include in the range of 5 to 30%. If the structural unit having a graft chain is included within this range, the dispersibility of the titanium nitride-containing particles will be high, and the developability at the time of forming a cured film will be good.

Furthermore, it is preferable that the polymer compound has a hydrophobic structural unit different from the structural unit having the graft chain (that is, not corresponding to the structural unit having the graft chain). Among them, in the present invention, the hydrophobic structural unit is a structural unit that does not have an acid group (eg, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).

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

The ClogP value is a value calculated by the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides the value of "compute logP" calculated by Hansch, Leo's fragment approach (see below). Fragmentapproach divides the chemical structure into partial structures (fragments) according to the chemical structure of the compound, and calculates the logP value of the compound by summing up the logP contribution assigned to the fragment. The details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 was 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 log Poct from structure. Chem. Rev., 93, 1281-1306, 1993.

logP represents the common logarithm of the partition coefficient P (Partition Coefficient), which is a quantitative value that expresses the physical property value of how an organic compound is distributed in the equilibrium of the 2-phase system of oil (usually 1-octanol) and water, as follows expression. 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 water phase. If the value of logP increases positively (plus) between 0, it means that the oil solubility increases, and if the absolute value increases negatively (minus), it means that the water solubility increases, which is negatively correlated with the water solubility of organic compounds, as It is widely used to estimate the parameters of hydrophilicity and hydrophobicity of organic compounds.

The polymer compound preferably has, as the hydrophobic structural unit, one or more structural units selected from structural units derived from 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, bromine, etc.) or an alkyl group with 1 to 6 carbon atoms ( For example, methyl, ethyl, propyl, etc.). R ¹ , R ² and R ³ are preferably hydrogen atoms or alkyl groups with 1 to 3 carbon atoms, more preferably hydrogen atoms or methyl groups. R ² and R ³ are especially preferably 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. As the divalent linking group, divalent aliphatic groups (for example, alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, substituted alkynylene), divalent Aromatic group (for example, aryl group, substituted aryl group), divalent heterocyclic group, oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted Amino group (-NR ³¹ -, wherein, R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), a combination thereof, and the like.

A divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but a saturated aliphatic group is preferred. Also, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups, heterocyclic groups and the like.

The number of carbon atoms in the divalent aromatic group is preferably from 6 to 20, more preferably from 6 to 15, and still more preferably from 6 to 10. In addition, the aromatic group may have a substituent. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups, and heterocyclic groups.

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocyclic ring. Another heterocyclic ring, aliphatic ring or aromatic ring may be condensed on the heterocyclic ring. Also, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thioxo groups (=S), imino groups (=NH), substituted imino groups (=NR ³² , where R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

L is preferably a single bond, an alkylene group, or a divalent linking group including an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L may contain a polyoxyalkylene structure repeatedly including two or more 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 2-10.

As Z, aliphatic groups (for example, alkyl groups, substituted alkyl groups, unsaturated alkyl groups and substituted unsaturated alkyl groups), aromatic groups (for example, aryl groups, substituted aryl groups, aryl groups, substituted aryl groups, aryl), heterocyclyl and combinations of these. These groups may contain oxygen atom (-O-), sulfur atom (-S-), imino group (-NH-), substituted imino group (-NR ³¹ -, wherein, R ³¹ is an aliphatic group , aromatic or heterocyclic group) or carbonyl (-CO-).

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. The aliphatic group also includes a ring-assembled hydrocarbon group and a cross-linked ring-type hydrocarbon group, and examples of the ring-assembled hydrocarbon group include bicyclohexyl, perhydronaphthyl, biphenyl, and 4-cyclohexylphenyl. As cross-linked cyclic hydrocarbon rings, for example, pinane (pinane), bornane (bornane), norpinene (norpinane), norbornane (norbornane) and bicyclic octane ring (bicyclo[2.2.2 ]octane ring, bicyclo[3.2.1]octane ring, etc.) and other 2-ring hydrocarbon rings; homobledane (homobledane), adamantane, tricyclo[5.2.1.02,6]decane and tricyclo[4.3. 1.12,5]undecane ring and other 3-ring hydrocarbon rings; tetracyclo[4.4.0.12,5.17,10]dodecane, perhydro-1,4-methylene-5,8-methylenenaphthalene ring Such as 4-ring hydrocarbon ring and so on. Moreover, the crosslinked cyclic hydrocarbon ring also includes condensed ring hydrocarbon rings, for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene and perhydro There are multiple fused rings of 5-8 membered cycloalkane rings in the condensation of pai rings and the like. The aliphatic group is preferably a saturated aliphatic group than an unsaturated aliphatic group. Also, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups and heterocyclic groups. However, the aliphatic group does not have an acid group as a substituent.

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

The heterocyclic group preferably has a 5-membered or 6-membered ring as a heterocyclic ring. Another heterocyclic ring, aliphatic ring or aromatic ring may be condensed on the heterocyclic ring. Also, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thioxo groups (=S), imino groups (=NH), substituted imino groups (=NR ³² , where R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.

In the above formula (iii), R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), an alkyl group with 1 to 6 carbon atoms (for example, methyl , ethyl, propyl, etc.), Z or LZ. Wherein, L and Z have the same meanings as L and Z in the above. R ⁴ , R ⁵ and R ⁶ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

In the present invention, as the monomer represented by the above-mentioned general formula (i), R ¹ , R ² and R ³ are hydrogen atoms or methyl groups, and L is a single bond or an alkylene group or a divalent linkage including an oxyalkylene structure. group, X is an oxygen atom or an imine group, and Z is an aliphatic group, a heterocyclic group or an aromatic group are preferred. Also, as the monomer represented by the above 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. Furthermore, as the monomer represented by the above general formula (iii), compounds in which R ⁴ , R ⁵ and R ⁶ are hydrogen atoms or methyl groups, and Z is an aliphatic group, a heterocyclic group or an aromatic group are preferable.

Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylates, methacrylates, styrenes, and the like. In addition, as examples of typical compounds represented by formulas (i) to (iii), compounds described in paragraphs 0089 to 0093 of JP-A-2013-249417 can be referred to, and these contents are incorporated herein.

In the polymer compound, the hydrophobic structural unit is preferably included in a range of 10 to 90%, and more preferably included in a range of 20 to 80%, in terms of mass relative to the total mass of the polymer compound. A content within the above range can achieve sufficient pattern formation.

The polymer compound can introduce functional groups that can interact with pigments such as titanium nitride particles. Among them, it is preferable that the polymer compound further includes a structural unit having a functional group capable of forming an interaction with pigments such as titanium nitride-containing particles. Examples of functional groups that can interact with pigments such as titanium nitride-containing particles include acid groups, basic groups, coordinating groups, and reactive functional groups. When the polymer compound has an acid group, a basic group, a coordinating group or a reactive functional group, it contains respectively a structural unit with an acidic group, a structural unit with a basic group, a structural unit with a coordinating group or It is preferred to contain reactive structural units. In particular, the polymer compound further has an alkali-soluble group such as a carboxylic acid group as an acid group, whereby developability for pattern formation by alkali image development can be imparted to the polymer compound. That is, by introducing an alkali-soluble group into the polymer compound, in the composition of the present invention, the polymer compound serving as a dispersant that contributes to the dispersion of pigments such as titanium nitride particles has alkali solubility. A composition containing such a polymer compound has excellent light-shielding properties in exposed areas, and improves alkali developability in unexposed areas. In addition, since the polymer compound has a structural unit containing an acid group, the polymer compound tends to be easily integrated with a solvent and coatability is also improved. It is speculated that this is because the acid group in the structural unit having an acid group is easy to interact with pigments such as titanium nitride particles, and the polymer compound can stably disperse pigments such as titanium nitride particles and make titanium nitride particles and the like The viscosity of the pigment-dispersed polymer compound becomes lower, and the polymer compound itself is easily and stably dispersed.

Wherein, the structural unit having an alkali-soluble group as an acidic group can be the same structural unit as the above-mentioned structural unit having a grafted chain, or a different structural unit, but the structural unit having an alkali-soluble group as an acidic group It is a structural unit different from the above-mentioned hydrophobic structural unit (that is, it does not correspond to the above-mentioned hydrophobic structural unit).

Functional groups that can interact with pigments such as titanium nitride particles, that is, acid groups, include, for example, carboxylic acid groups, sulfonic acid groups, phosphoric acid groups, or phenolic hydroxyl groups. Among the carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups At least one of these is preferred, and a carboxylic acid group is particularly preferred in terms of good adsorption force of pigments such as titanium nitride-containing particles and high dispersibility of colored pigments. That is, the polymer compound preferably further includes a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

The polymer compound may have one or more structural units having acid groups. The polymer compound may or may not contain structural units with acid groups, but when it does, the content of structural units with acid groups is preferably 5 to 80% relative to the total mass of the polymer compound in terms of mass, ranging from 10 to 60% is more preferable from a viewpoint of suppressing the damage of the image strength by alkali image development.

As functional groups that can interact with pigments such as titanium nitride particles, that is, basic groups, there are, for example, primary amine groups, secondary amine groups, tertiary amine groups, heterocyclic rings containing N atoms, and acyl groups. Amino groups and the like, the third grade amine groups are preferable from the viewpoint of good adsorption force to pigments such as titanium nitride-containing particles and high pigment dispersibility. A polymer compound can have 1 type, or 2 or more types of these basic groups. A polymer compound may or may not contain a structural unit with a basic group. When it does, the content of the structural unit with a basic group is calculated by mass, and relative to the total mass of the polymer compound, it is 0.01% or more and 50% or less. Preferably, it is more preferably 0.01% or more and 30% or less from the viewpoint of suppressing development hindrance.

Examples of functional groups that can interact with pigments such as titanium nitride particles, that is, coordinating groups, and reactive functional groups include acetoacetyloxy groups, trialkoxysilyl groups, and isocyanate groups. base, acid anhydride and acid chloride, etc. Acetyl acetyloxy is preferable in terms of good adsorption force to pigments such as titanium nitride-containing particles and high pigment dispersibility. A polymer compound may have 1 type or 2 or more types of these groups. A polymer compound may contain a structural unit with a coordinating group or a reactive functional group, or may not contain it, but when it is contained, the content of these structural units is calculated by mass, relative to the total mass of the polymer compound, 10% It is preferably 80% or more, and more preferably 20% or more and 60% or less from the viewpoint of suppressing development hindrance.

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

[chemical formula 6]

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

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

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

A divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Also, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, aromatic groups and heterocyclic groups.

The number of carbon atoms in the divalent aromatic group is preferably 6-20, more preferably 6-15, and most preferably 6-10. In addition, the aromatic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, aliphatic groups, aromatic groups and heterocyclic groups.

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocyclic ring. One or more of other heterocyclic rings, aliphatic rings, or aromatic rings may be condensed in the heterocyclic ring. Also, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thioxo groups (=S), imino groups (=NH), substituted imino groups (=NR ³² , where R ³² is an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

It is preferable that L ₁ is a single bond, an alkylene group, or a divalent linking group including an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, _L1 may contain a polyoxyalkylene structure repeatedly including two or more 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 2-10.

In general formula (iv) to general formula (vi), Z ₁ represents a functional group other than the grafted chain that can interact with pigments such as titanium nitride particles. Carboxylic acid groups and tertiary amino groups are preferred. Carboxylic acid groups Acid groups are more preferred.

In the general formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ independently represent a hydrogen atom, a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group with 1 to 6 carbon atoms (such as , methyl, ethyl and propyl, etc.), -Z ₁ or L ₁ -Z ₁ . Wherein, the meanings of _L1 and _Z1 are the same as those of _L1 and _Z1 mentioned above, and the preferred examples are also the same. R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

In the present invention, as a monomer represented by the general formula (iv), R ¹¹ , R ¹² and R ¹³ are each independently a hydrogen atom or a methyl group, and L ₁ is an alkylene group or a divalent link including an alkylene oxide structure. Group, X ₁ is an oxygen atom or an imine group, and Z ₁ is a compound of a carboxylic acid group is preferred. Furthermore, 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 methine group is preferable. Furthermore, as a monomer represented by the general formula (vi), 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 compound of a carboxylic acid group. better.

Representative examples of monomers (compounds) represented by the general formulas (iv) to (vi) are shown below. Examples of monomers include reactions of methacrylic acid, crotonic acid, isocrotonic acid, compounds having addition-polymerizable double bonds and hydroxyl groups in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride Products, reactants of compounds having addition polymerizable double bonds and hydroxyl groups in the molecule and phthalic anhydride, reactants of compounds having addition polymerizable double bonds and hydroxyl groups in the molecule and tetrahydroxyphthalic anhydride, Reactants of compounds having addition polymerizable double bonds and hydroxyl groups in the molecule with trimellitic anhydride, reactants of compounds having addition polymerizable double bonds and hydroxyl groups in the molecule and pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid Oligomers, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol and 4-hydroxybenzyl acrylic acid, etc.

From the viewpoint of interaction with pigments such as titanium nitride-containing particles, dispersion stability, and penetrability to developing solutions, the content of structural units having functional groups that can interact with pigments such as titanium nitride-containing particles is relative to The total mass of the polymer compound is preferably 0.05% by mass to 90% by mass, more preferably 1.0% by mass to 80% by mass, and still more preferably 10% by mass to 70% by mass.

Moreover, in order to improve various properties such as image strength, the polymer compound may further contain a structural unit with a grafted chain, a hydrophobic structural unit, and a structure unit with a titanium nitride-containing particle, etc., without impairing the effect of the present invention. The structural unit that forms the functional group that interacts with the pigment is different from other structural units that have various functions (for example, a structural unit that has a functional group that has an affinity with the dispersion medium used for the dispersion, etc.). Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like. A polymer compound can use one or more than two types of these other structural units, and its content is calculated by mass. Relative to the total mass of the polymer compound, it is preferably more than 0% and less than 80%, and more than 10% and 60% The following are particularly preferred. When the content is within the above range, sufficient pattern formability can be maintained.

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

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

When forming a cured film, the weight average molecular weight of the polymer compound in the present invention is a polystyrene-equivalent value based on the GPC (gel permeation chromatography) method from the viewpoint of pattern peeling suppression and developability during development, It is preferably from 4,000 to 300,000, more preferably from 5,000 to 200,000, still more preferably from 6,000 to 100,000, and particularly preferably from 10,000 to 50,000. The GPC method is based on a method using HLC-8020GPC (manufactured by TOSOH CORPORATION.), using TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by TOSOH CORPORATION, 4.6mmID×15cm) as a column, and using THF as an eluent. (tetrahydrofuran).

High molecular compounds can be synthesized according to known methods. Examples of solvents used in the synthesis of high molecular compounds include dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethyl Methyl formamide, N,N-dimethylacetamide, dimethylsulfide, toluene, ethyl acetate, methyl lactate and ethyl lactate, etc. These solvents may be used alone or in combination of two or more.

Specific examples of polymer compounds that can be used in the present invention include "DA-7301" manufactured by Kusumoto Chemicals, Ltd., "Disperbyk-101" (polyamide amine phosphate) manufactured by BYK Chemie, 107 (carboxy ester), 110 (copolymer containing acid groups), 111 (phosphate-based dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer) ", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", manufactured by EFKA "EFKA4047, 4050-4010-4165 (polyurethane), EFKA4330-4340 (block copolymer), 4400-4402 (modified Polyacrylate), 5010 (polyamide ester), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)", Ajinomoto "AJISPER PB821, PB822, PB880, PB881" manufactured by Fine-Techno Co., Inc., "Floren TG-710 (urethane oligomer)" manufactured by KYOEISHA CHEMICAL Co., LTD, "Polyflow No.50E, No.300 (acrylic copolymer)", manufactured by Kusumoto Chemicals, Ltd. "Disparlon KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA- 705, DA-725”, Kao Corporation’s “DEMOL RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymeric polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "ACETAMIN 86 (stearylamine acetate)", manufactured by The Lubrinzol Corporation" SOLSPERSE 5000 (phthalocyanine derivatives), 22000 (azo pigment derivatives), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymers with functional parts at the end), 24000, 28000, 32000, 38500 (graft copolymer)", Nikko Chemicals Co., Ltd. "Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)", Kawaken Fine Chemicals Co., Ltd. manufactures Hinoakuto T-8000E, etc., Shin-Etsu Chemical Co., Ltd. manufactures polyorganosiloxane polymer KP341, Yusho Co Ltd manufactures "W001: Cationic Surfactant", poly Oxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol Nonionic surfactants such as alcohol distearate and sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", "EFKA-46, EFKA- 47. EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450", "Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100" manufactured by SAN NOPCO LIMITED Molecular dispersant, "Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123" manufactured by ADEKA CORPORATION and Sanyo Chemical Industries, Ltd. manufactures "Ionet (trade name) S-20" and the like. Furthermore, Acrylicbase FFS-6752, Acrylicbase FFS-187, Akurikyua-RD-F8, and Cyclomer P can also be used. In addition, examples of commercially available amphoteric resins include DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001 manufactured by BYK Additives & Instruments, DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, AJISPER PB821, AJISPER PB822, AJISPER PB881 manufactured by Ajinomoto Fine-Techno Co., Inc., etc. These polymer compounds may be used alone or in combination of two or more.

In addition, as examples of specific examples of the polymer compound, polymer compounds described in paragraphs 0127 to 0129 of JP-A-2013-249417 can be referred to, and these contents are incorporated in the present specification.

In addition, as a dispersant, in addition to the above polymer compounds, graft copolymers of paragraphs 0037 to 0115 of JP-A-2010-106268 (corresponding to paragraphs 0075 to 0133 of US2011/0124824) can also be used. These contents can be cited and incorporated into this specification. In addition to the above, it is also possible to use the structure including side chains having acidic groups bonded through linking groups in paragraphs 0028 to 0084 of JP-A-2011-153283 (corresponding to columns 0075 to 0133 of US2011/0279759). The composition of the polymer compound, these contents can be cited and incorporated into this specification.

When the composition contains a dispersant, the content of the dispersant is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, based on the total solid content of the composition. The dispersants may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the total amount becomes the said range.

<Binder resin> It is preferable that the composition of this invention contains a binder resin. As the binder resin, it is preferable to use a linear organic polymer. As such a linear organic polymer, known ones can be used arbitrarily. In order to realize water development or weak alkaline water development, it is better to choose a linear organic polymer that is soluble or swellable in water or weak alkaline water. Among them, an alkali-soluble resin (resin having a group that promotes alkali solubility) is particularly preferable as the binder resin. As a binder resin, it can be obtained from a linear organic polymer and has at least one group that promotes alkali solubility in the molecule (preferably a molecule with a (meth)acrylic copolymer or a styrene copolymer as the main chain) Appropriate selection among alkali soluble resins. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, (meth)acrylic resins, (meth)acrylamide resins, (meth)acrylic/(meth)acryl Amine copolymer resins are preferred, and from the viewpoint of developability control, (meth)acrylic resins, (meth)acrylamide-based resins, and (meth)acrylic acid/(meth)acrylamide copolymer resins are better. Examples of the alkali-solubility-promoting group (hereinafter also referred to as an acidic group) include, for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Among them, those that are soluble in an organic solvent and can be developed by a weak alkaline aqueous solution are preferable, and more preferable ones include alkali-soluble resins having a structural unit derived from (meth)acrylic acid. These acid groups may be only one type, or may be two or more types.

As the binder resin, for example, a radical polymer having a carboxylic acid group in a side chain, such as Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. Publicly disclosed No. 54-25957, JP-A-54-92723, JP-A-59-53836 and JP-A-59-71048, that is, monomers having carboxyl groups alone or copolymerized Resins, monomers with acid anhydrides alone or copolymerized and hydrolyzed or half-esterified or half-amidated resins and epoxy acrylics modified by unsaturated monocarboxylic acids and acid anhydrides Esters etc. Examples of monomers having carboxyl groups include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Examples of monomers having acid anhydrides include Maleic anhydride etc. are mentioned. In addition, an acidic cellulose derivative having a carboxylic acid group in a side chain can also be cited as an example. In addition, it is useful to add a cyclic acid anhydride to a polymer having a hydroxyl group. In addition, the acetal-modified polyvinyl alcohol-based adhesive resin having an acid group described in the publications of European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463 has an excellent balance between film strength and developability. , is better. Furthermore, polyvinylpyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon and polyether, which is a reaction product of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin, are also useful.

In particular, among these, [benzyl (meth)acrylate/(meth)acrylic acid/other addition-polymerizable vinyl monomer] copolymers and [(meth)acrylate/(meth)acrylic acid ) acrylic acid/according to need other addition-polymerizable vinyl monomer] copolymer is preferable because it is excellent in balance of film strength, sensitivity and developability. Examples of commercially available products include Acrylicbase FF-187, FF-426 (manufactured by FUJIKURA KASEI CO., LTD.), Akurikyua-RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.) and DAICEL-ALLNEX LTD. Cyclomer P (ACA) 230AA, etc.

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

Furthermore, it is also preferable to use a polymer including a structural unit having a graft chain and a structural unit having an acidic group (alkali-soluble group) as the binder resin. The definition of the structural unit having a graft chain is the same as that of the above-mentioned dispersant having a structural unit having a graft chain, and the preferred range is also the same. The acid group includes, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is preferred, and a carboxylic acid group is more preferred.

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

[chemical formula 7]

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

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

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

A divalent aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, and still more preferably 1-10. Regarding the aliphatic group, a saturated aliphatic group is more preferable than an unsaturated aliphatic group. Also, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, aromatic groups and heterocyclic groups.

The number of carbon atoms in the divalent aromatic group is preferably from 6 to 20, more preferably from 6 to 15, and still more preferably from 6 to 10. In addition, the aromatic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, aliphatic groups, aromatic groups and heterocyclic groups.

The divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocyclic ring. One or more of other heterocycles, aliphatic rings, or aromatic rings may be condensed on the heterocycle. Also, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thiol groups (=S), imino groups (=NH), substituted imino groups (=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.

It is preferable that L ₂ is a single bond, an alkylene group, or a divalent linking group including an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, _L2 may contain a polyoxyalkylene structure repeatedly including two or more 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 2-10.

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

In the general formula (ix), R ²⁴ , R ²⁵ and R ²⁶ independently represent a hydrogen atom, a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group with 1 to 6 carbon atoms (such as , methyl, ethyl, propyl, etc.), -Z ₂ or L ₂ -Z ₂ . Wherein, the meanings of _L2 and _Z2 are the same as those of _L2 and _Z2 mentioned above, and the preferred examples are also the same. R ²⁴ , R ²⁵ and R ²⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

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

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

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

The content of the binder resin in the composition of the present invention is preferably 0.1 to 30% by mass, more preferably 0.3 to 25% by mass, relative to the total solid content of the composition. One type of binder resin may be used alone, or two or more types may be used. When using 2 or more types, it is preferable that the total amount becomes the said range.

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

<Polymerizable Compound> It is preferable that the composition of the present invention contains a polymerizable compound. The polymerizable compound is preferably a compound containing one or more groups having an ethylenically unsaturated bond, more preferably a compound having two or more groups, still more preferably having three or more groups, and especially preferably having five or more groups. The upper limit is, for example, 15 or less. As a group which has an ethylenically unsaturated bond, a vinyl group, (meth)allyl group, (meth)acryl group etc. are mentioned, for example.

The polymerizable compound may be in any of chemical forms such as monomers, prepolymers, oligomers, mixtures of these, and multimers of these, for example, and monomers are preferred. The molecular weight of the polymerizable compound is preferably from 100 to 3,000, more preferably from 250 to 1,500. It is preferable that a polymeric compound is a 3-15 functional (meth)acrylate compound, and it is more preferable that it is a 3-6 functional (meth)acrylate compound. Examples of monomers and prepolymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides , and multimers of these, esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyamine compounds, and multimers of these are preferred. In addition, addition reactants of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amine groups, and mercapto groups, and monofunctional or polyfunctional isocyanates or epoxies, or the above-mentioned Dehydration condensation reaction products of unsaturated carboxylic acid esters or amides and monofunctional or polyfunctional carboxylic acids, etc. Also, reactants of unsaturated carboxylates or amides with electrophilic substituents such as isocyanate groups and epoxy groups, and monofunctional or polyfunctional alcohols, amines, and thiols, and those with halogen groups or toluene Reactants of unsaturated carboxylic acid esters or amides with separable substituents such as sulfonyl groups and monofunctional or polyfunctional alcohols, amines, and thiols are also preferred. In addition, instead of the unsaturated carboxylic acid described above, unsaturated phosphonic acid, styrene derivatives such as styrene, and compounds substituted with vinyl ether, allyl ether, and the like can also be used. As these specific compounds, compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be suitably used in the present invention.

In the present invention, as the polymerizable compound, a compound containing one or more groups having an ethylenically unsaturated bond and having a boiling point of 100° C. or higher under normal pressure is also preferable. As examples thereof, for example, compounds described in paragraph 0227 of JP-A-2013-29760 and paragraphs 0254-0257 of JP-A-2008-292970 can be referred to, and the content thereof is incorporated herein.

As the polymerizable compound, dipentaerythritol triacrylate (commercially available, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available, KAYARAD D-320; Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) A base structure (for example, SR454, SR499 commercially available from Sartomer company Inc.) is preferred. Oligomer types of these can also be used. Furthermore, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), and the like can also be used. The states of preferable polymerizable compounds are shown below.

A polymeric compound may have acid groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group. As a polymeric compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and an acid group is obtained by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. The polymeric compound is more preferable, and among the esters, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol is still more preferable. As a commercial item, ARONIX TO-2349, M-305, M-510, M-520 etc. manufactured by TOAGOSEI CO., LTD. are mentioned, for example.

The preferable acid value of the polymeric compound which has an acid group is 0.1-40 mgKOH/g, More preferably, it is 5-30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the image development solubility property is favorable, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.

Regarding the polymerizable compound, a compound having a caprolactone structure is also preferable. The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. It is obtained by esterifying polyhydric alcohols such as methyl propane, ditrimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin, trimethylol melamine with (meth)acrylic acid and ε-caprolactone , ε-caprolactone modified multifunctional (meth)acrylate. Among them, a compound having a caprolactone structure represented by the following general formula (Z-1) is preferable.

[chemical formula 8]

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

[chemical formula 10]

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

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

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

[chemical formula 11]

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

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

The compounds represented by general formula (Z-4) or general formula (Z-5) may be used alone or in combination of two or more. In particular, the form in which all 6 Xs in the general formula (Z-5) are acryloyl groups, the compound in which all 6 Xs in the general formula (Z-5) are acryloyl groups and at least one of the 6 Xs The form of a mixture of compounds with hydrogen atoms is preferred. Developability can be improved more by setting it as such a structure.

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

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

Among the compounds represented by general formula (Z-4) or general formula (Z-5), pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferable. Specifically, 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 polymeric compounds represented by general formulas (Z-4) and (Z-5) include SR- 494. DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., and TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, etc. .

As a polymerizable compound, in addition to urethane acrylate as described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Publication No. 51-37193, Japanese Patent Publication No. 2-32293 and Japanese Patent Publication No. 2-16765 Urethanes with oxirane-based skeletons described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 Compounds are also preferred. In addition, it is also possible to use the amine structure and thioether structure in the molecule described in JP-A-63-277653, JP-A-63-260909 and JP-1-105238. Addition-polymerizable compounds to obtain compositions with excellent photosensitivity. Commercially available urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by KYOEISHA CHEMICAL Co., LTD.), etc.

Furthermore, the SP (solubility parameter) value of the polymerizable compound used in the present invention is preferably at least 9.50, more preferably at least 10.40, and still more preferably at least 10.60. In addition, in this specification, the SP value is calculated|required by the Hoy method (HL Hoy Journal of Painting, 1970, Vol.42, 76-118) unless otherwise indicated. In addition, although the unit is omitted and shown for the SP value, the unit is cal ^1/2 cm ^-3/2 .

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

General formula (Q3) [Chemical formula 14]

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

In the above-mentioned general formula (Q3), the aryl group represented by Ar ¹¹ to Ar ¹⁴ comprising a benzene ring surrounded by a dotted line is preferably an aryl group with 6 to 14 carbon atoms, and an aryl group with 6 to 10 carbon atoms ( For example, phenyl, naphthyl) are more preferable, and phenyl (limited to the benzene ring surrounded by a dotted line) is still more preferable.

In the general formula (Q3), X ¹ to X ⁴ each independently represent a substituent having a polymerizable group, and carbon atoms in the substituent may be substituted with a heteroatom. The substituents having polymerizable groups represented by X ¹ to X ⁴ are not particularly limited, but aliphatic groups having polymerizable groups are preferred. The aliphatic group having the polymerizable groups represented by X ¹ to X ⁴ is not particularly limited, but an alkylene group having 1 to 12 carbon atoms other than the polymerizable group is preferable, and the carbon number is 2 An alkylene group of ∼10 is more preferable, and an alkylene group having 2 to 5 carbon atoms is still more preferable. In addition, among the aliphatic groups having polymerizable groups represented by X ¹ to X ⁴ , when the aliphatic groups are substituted by heteroatoms, they are replaced by -NR- (R is a substituent), an oxygen atom or a sulfur atom. Preferably, the non-adjacent -CH ₂ - in the above aliphatic group is more preferably replaced by an oxygen atom or a sulfur atom, and it is still more preferable that the non-adjacent -CH ₂ - in the above aliphatic group is replaced by an oxygen atom. Preferably, 1 to 2 positions of the aliphatic group having the polymerizable groups represented by X ¹ to X ⁴ are substituted by heteroatoms, more preferably 1 position is substituted by heteroatoms, and Ar ¹¹ to Ar ¹⁴ include It is further preferred that one position adjacent to the aryl group of the benzene ring surrounded by a dotted line is substituted with a heteroatom. As the polymerizable group included in the aliphatic group having the polymerizable groups represented by ^X1 to ^X4 , a polymerizable group capable of radical polymerization or cationic polymerization (hereinafter also referred to as radically polymerizable group and cationic polymerizable group) is preferred. As the radical polymerizable group, a generally known radical polymerizable group can be used, and as a preferred one, a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization is mentioned. Specifically, Vinyl, (meth)acryloyloxy, etc. are mentioned. Among them, (meth)acryloxy is preferred, and acryloxy is more preferred. As the cationic polymerizable group, generally known cationic polymerizable groups can be used, specifically, alicyclic ether group, cyclic acetal group, cyclic lactone group, cyclic thioether group, spiro Cyclic ortho ester group and vinyloxy group, etc. Among them, alicyclic ether group or vinyloxy group is preferred, and epoxy group, oxetanyl group or vinyloxy group is particularly preferred. It is preferable that the above-mentioned polymerizable group contained in the substituent included in Ar ¹ to Ar ⁴ is a radical polymerizable group. Two or more of Ar ¹ to Ar ⁴ contain a substituent having a polymerizable group, preferably 2 to 4 of Ar ¹ to Ar ⁴ contain a substituent having a polymerizable group, and among Ar ¹ to Ar ⁴ It is more preferable that 2 or 3 of Ar ^{1 to Ar 4 include a substituent having a polymerizable group, and it is still more preferable that 2 of Ar 1} to Ar ⁴ include a substituent having a polymerizable group. When Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a dotted line as one of the condensed rings, X ¹ to X ⁴ may be independently substituted by a benzene ring surrounded by a dotted line, or is a ring other than the benzene ring surrounded by a dotted line.

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

In the above general formula (Q3), R ¹ to R ⁴ each independently represent a substituent. The substituents represented by R ¹ to R ⁴ are not particularly limited, for example, halogen atoms, halogenated alkyl groups, alkyl groups, alkenyl groups, acyl groups, hydroxyl groups, hydroxyalkyl groups, alkoxy groups, aromatic groups, etc. group, heteroaryl group and alicyclic group, etc. The substituents represented by R ¹ to R ⁴ are preferably alkyl, alkoxy or aryl, more preferably alkyl with 1 to 5 carbon atoms, alkoxy with 1 to 5 carbon atoms or phenyl , methyl, methoxy or phenyl are further preferred. In the above general formula (Q3), when Ar ¹¹ to Ar ¹⁴ are each independently a polycyclic aromatic hydrocarbon group including a benzene ring surrounded by a dotted line as one of the condensed rings, R ¹ to R ⁴ can be independently substituted by a dotted line The surrounded benzene ring may be substituted with a ring other than the benzene ring surrounded by a dotted line.

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

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

When the composition of the present invention contains a polymerizable compound, the content of the polymerizable compound is preferably 0.1 to 40% by mass relative to the total solid content of the composition. The lower limit is, for example, more preferably 0.5 mass % or more, and still more preferably 1 mass % or more. The upper limit is, for example, more preferably 30 mass % or less, and further preferably 20 mass % or less. A polymerizable compound may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the total amount becomes the said range.

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

As photopolymerization initiators, for example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, Oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, and the like. As the above-mentioned halogenated hydrocarbon compound having a triazine skeleton, for example, compounds described in Wakabayashi et al., Bull. Compounds described in KOKAI Publication No. 53-133428, compounds described in specification of German Patent No. 3337024, compounds described in J.Org. Chem.; 29, 1527 (1964) based on F.C. Schaefer et al., JP-A-62-58241 Compounds described in the gazette, compounds described in Japanese Patent Application Laid-Open No. 5-281728, compounds described in Japanese Patent Laid-Open No. 5-34920, compounds described in US Patent No. 4212976, and the like.

In addition, from the viewpoint of exposure sensitivity, it is selected from trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, Metallocene compounds, oxime compounds, triaryl imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and Compounds of the group consisting of salts thereof, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds are preferred.

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

In particular, when producing a light-shielding film for a solid-state imaging device using the composition of the present invention, it is necessary to form a fine pattern in a sharp shape, so it is important to develop without residue in unexposed parts together with curability. From such a viewpoint, it is particularly preferable to use an oxime compound as a photopolymerization initiator. In particular, when forming a fine pattern in a solid-state imaging element, stepping exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and it is necessary to keep the amount of photopolymerization initiator added low, so, When these points are considered, it is particularly preferable to use an oxime compound as a photopolymerization initiator when forming a fine pattern such as a solid-state imaging device. Furthermore, by using an oxime compound, color transferability can be further optimized. As a specific example of a photoinitiator, paragraphs 0265-0268 of Unexamined-Japanese-Patent No. 2013-29760 can be referred, for example, The content is incorporated in this-application specification.

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

As a photoinitiator, an oxime compound is mentioned more preferably. In particular, an oxime-based initiator has high sensitivity and high polymerization efficiency, can be cured regardless of the concentration of the color material, and is easy to design the concentration of the color material to be high, so it is preferable. Specific examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068, and compounds described in JP-A-2006-342166. In the present invention, as oxime compounds that can be preferably used, for example, 3-benzoyloxyiminobutane-2-one, 3-acetyloxyiminobutane-2- Ketone, 3-propionyloxyiminobutan-2-one, 2-acetyloxyiminopentan-3-one, 2-acetyloxyimino-1-phenylpropane- 1-keto, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-tosyloxy)iminobutan-2-one and 2-ethoxy Carbonyloxyimino-1-phenylpropan-1-one, etc. In addition, J.C.S.Perkin II (1979) pp.1653-1660), J.C.S.Perkin II (1979) pp.156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232, Japan Compounds described in JP-A-2000-66385, compounds described in JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166, etc. Among commercially available products, IRGACURE-OXE01 (manufactured by BASF Corporation) and IRGACURE-OXE02 (manufactured by BASF Corporation) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Qiangli Electronic New Material Co., Ltd.), Adeka Arkls NCI-831, and Adeka Arkls NCI-930 (manufactured by Adeka Corporation) can also be used. Also, N-1919 (manufactured by ADEKA CORPORATION) can be used.

In addition, as oxime compounds other than those described above, compounds described in Japanese PCT Publication No. 2009-519904 in which an oxime is linked to the N-position of carbazole, and U.S. Patent No. 7,626,957 in which a hetero substituent is introduced into a benzophenone site can be used. Compounds described in Japanese Patent Publication No. 2, compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced into the pigment site, ketoxime compounds described in International Laid-Open Patent No. 2009-131189, Compounds described in U.S. Patent No. 7,556,910 that contain a triazine skeleton and an oxime skeleton in the same molecule, and compounds described in Japanese Patent Application Laid-Open No. 2009-221114 that have a maximum absorption at 405 nm and have good sensitivity to g-ray light sources, etc. For example, paragraphs 0274 to 0275 of JP-A-2013-29760 can be preferably referred to, and the contents thereof are incorporated into this specification. Specifically, as an oxime compound, a compound represented by the following formula (OX-1) is preferable. In addition, the N-O bond of the oxime may be the oxime compound of the (E) body, or the oxime compound of the (Z) body, or a mixture of the (E) body and (Z) body.

[chemical formula 15]

In the general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. As the monovalent substituent represented by R in the general formula (OX-1), a monovalent non-metal atomic group is preferable. Examples of the monovalent non-metal atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. In addition, these groups may have one or more substituents. And, the aforementioned substituents may be further substituted with other substituents. 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. As the one-valent substituent represented by B in the general formula (OX-1), an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group are preferable. These groups may have one or more substituents. As a substituent, the said substituent can be illustrated. As the divalent organic group represented by A in the general formula (OX-1), an alkylene group, cycloalkylene group or alkynylene group having 1 to 12 carbon atoms is preferable. These groups may have one or more substituents. As a substituent, the said substituent can be illustrated.

In this invention, the oxime compound which has a fluorine atom can also be used as a photoinitiator. Specific examples of oxime compounds having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471 Compound (C-3) etc. described in the gazette. This content is incorporated into this specification.

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

[chemical formula 16]

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

In formula (2), R ¹ , R ² , R ³ and R ⁴ have the same meanings as R ¹ , R ² , R ³ and R ⁴ in formula (1), and R ⁵ represents -R ⁶ , -OR ⁶ , -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, halogen atom or Hydroxyl, ^R6 represents an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, an aralkyl group with 7 to 30 carbon atoms or a heterocyclic group with 4 to 20 carbon atoms, and X represents a single a bond or a carbonyl group, and a represents an integer of 0-4.

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

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

[chemical formula 17]

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

Furthermore, the commercially available polymerization initiator is not particularly limited, and IRGACURE OXE 01 (1.2-octanedione, 1-[4-(phenylthio)-, 2-( O-benzoyl oxime)]), IRGACURE OXE 02 (ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1 -(O-acetyloxime)), 2-(acetyloxyiminomethyl)thioxanthen-9-one, O-acyl oxime-based compounds (for example, ADEKAOPTOMER N-1919 manufactured by ADEKA CORPORATION, Adeka Arkls NCI-831), Adeka ArklsNCI-930, IRGACURE-OXE03, IRGACURE-OXE04, etc., these contents are incorporated into this specification.

The oxime compound has a maximum absorption wavelength in the wavelength region of 350nm to 500nm is preferred, and one with a maximum absorption wavelength in the wavelength region of 360nm to 480nm is more preferred, and those with higher absorbance at 365nm and 405nm are especially preferred. Among the oxime compounds, the molar absorption coefficient at 365 nm or 405 nm is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, and still more preferably from 5,000 to 200,000, from the viewpoint of sensitivity. The molar absorptivity of the compound can be measured by a known method, for example, with an ultraviolet-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian), using ethyl acetate solvent, preferably at a concentration of 0.01 g/L. The photoinitiator used in this invention can be used combining 2 or more types as needed.

When the composition of the present invention contains a polymerization initiator, the content of the polymerization initiator is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and 1 to 10% by mass relative to the total solid content of the composition. % is further preferred. The composition of this invention may contain only 1 type of polymerization initiator, and may contain 2 or more types. When containing 2 or more types, it is preferable that the total amount becomes the said range.

<Solvent> The composition of the present invention preferably contains a solvent, and more preferably contains an organic solvent. Examples of organic solvents include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, dichloroethylene, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl ether. , propylene glycol monomethyl ether, propylene glycol monoethyl ether, 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, Methoxyethoxyethanol, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Dimethyl Ether , diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-ethoxy ethyl propionate (Ethyl 3-ethoxypropionate), 3-methoxy propyl acetate, N,N-Dimethylformamide, dimethylsulfoxide, γ-butyrolactone, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, etc., are not limited thereto.

The composition of the present invention may contain one type of organic solvent, or may contain two or more types of organic solvents, but from the perspective of suppressing the particle size variation of the titanium nitride-containing particles when adjusting the composition of the present invention, it is preferable to contain two types of organic solvents. above organic solvents. When containing more than two kinds of organic solvents, it is selected from the above-mentioned methyl 3-ethoxy propionate, ethyl 3-ethoxy propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol di Methyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol mono A mixed solution composed of two or more of methyl ether, ethyl 3-ethoxypropionate, and propylene glycol monomethyl ether acetate is particularly preferable.

When the composition of the present invention contains an organic solvent, the content of the organic solvent is preferably 10 to 90% by mass, more preferably 60 to 90% by mass, based on the total mass of the composition. When two or more types of organic solvents are included, it is preferable that the total amount is within the above-mentioned range.

<Water> The composition of the present invention may contain water. Water may be added intentionally, 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 from 0.1 to 1% by mass, more preferably from 0.1 to 0.8% by mass, and still more preferably from 0.1 to 0.4% by mass, based on the total mass of the composition. When content of water exists in the said range, the pattern formation property (resolution) at the time of producing a cured film is excellent, and the corrosion resistance of an electrode material is also excellent. Furthermore, by setting the water content to 0.1 to 1% by mass relative to the total mass of the composition, the amount of particles in the composition can be further reduced, and the viscosity stability of the composition over time is also more excellent.

<Other Components> The composition of the present invention may contain other components than the above-mentioned components. Each component will be described in detail below.

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

It is preferable that the silane coupling agent has a group represented by the following formula (Z). * Indicates bond position. Formula (Z)*-Si-(R _Z1 ) ₃ In formula (Z), R _Z1 represents a hydrolyzable group, and its definition is as above.

The silane coupling agent preferably has at least one hardening functional group selected from the group consisting of a (meth)acryloxy group, an epoxy group, and an oxetanyl group. The hardening functional group can be directly bonded to the silicon atom, or can be bonded to the silicon atom through a linking group. Moreover, a radical polymerizable group is also mentioned as a preferable aspect of the curable functional group contained in the said silane coupling agent.

The molecular weight of the silane coupling agent is not particularly limited. From the viewpoint of operability, it is often 100-1000, and from the viewpoint of better effects of the present invention, it is preferably 270 or more, and more preferably 270-1000.

As one of the preferable aspects of the silane coupling agent, the silane coupling agent X represented by the formula (W) can be mentioned. The formula (W) R _Z2 -Lz-Si-(R _Z1 ) ₃ R _z1 represents a hydrolyzable group as defined above. R _z2 represents a hardening functional group, the definition is as above, and the preferred range is also as 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 arylylene 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 them, at least one selected from the group consisting of an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms and an arylylene group which may be substituted by a halogen atom having 6 to 12 carbon atoms, or a group containing these groups group and at least one group selected from the group consisting of -NR ¹² -, -CONR ¹² -, -CO-, -CO ₂ -, SO ₂ NR ¹² -, -O-, -S- and SO ₂ - The combination of groups is preferably an alkylene group, -CO ₂ -, -O-, -CO-, -CONR ¹² - or a group consisting of a halogen atom with 2 to 10 carbon atoms which may be substituted Combined groups are more preferred. Wherein, the above-mentioned R ¹² represents a hydrogen atom or a methyl group.

Examples of the silane coupling agent X include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N -β-aminoethyl-γ-aminopropyl-trimethoxysilane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N-β-aminoethyl-γ-aminopropyl-trimethoxysilane Ethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-trimethoxysilane (trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), γ-aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co. , Ltd. (trade name KBM-503), glycidoxyoctyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. trade name KBM-4803), etc.

Another preferred aspect of the silane coupling agent is a silane coupling agent Y having at least a silicon atom, a nitrogen atom, and a hardening functional group in the molecule, and a hydrolyzable group bonded to the silicon atom. The silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. These may be the same atom or substituent, or may be different. Atoms and substituents that can be bonded include hydrogen atoms, halogen atoms, hydroxyl groups, alkyl groups with 1 to 20 carbon atoms, alkenyl groups, alkynyl groups, aryl groups, and amino groups that may be substituted with alkyl and/or aryl groups , silyl, alkoxy and aryloxy groups with 1 to 20 carbon atoms, etc. These substituents may be further substituted by silyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, thioalkoxy, amino groups that may be substituted by alkyl and/or aryl, halogen atoms, Sulfonamide group, alkoxycarbonyl group, amide group, urea group, ammonium group, alkylammonium group, carboxyl group or its salt, sulfo group or its salt, etc. In addition, at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as above. The silane coupling agent Y may contain a group represented by the above formula (Z).

The silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably 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 Group is better. In addition, as the structure of the amino group, it may exist in the molecule as a partial structure of a nitrogen-containing heterocyclic ring, or may exist as a substituted amino group such as aniline. Among these, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have substituents, and examples of substituents that can be introduced include silyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, thioalkoxy groups, amino groups, and halogen atoms. , sulfonamide group, alkoxycarbonyl group, carbonyloxy group, amido group, urea group, alkyleneoxyammonium group, alkylammonium group, carboxyl group or its salt, sulfo group and the like. Furthermore, it is preferable that the nitrogen atom is bonded to the curable functional group via an arbitrary organic linking group. As a preferable organic linking group, the substituent which can be introduced into the said nitrogen atom and the organic group bonded to it is mentioned.

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

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

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

The composition of this invention may contain 1 type of silane coupling agent independently, and may contain 2 or more types. When the composition contains two or more types of silane coupling agents, the total of them may be within the above-mentioned range.

(Ultraviolet absorber) The composition of this invention may contain an ultraviolet absorber. Thereby, the pattern shape can be set to a more excellent (fine) one. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. As specific examples thereof, compounds of paragraphs 0137 to 0142 of JP-A-2012-068418 (corresponding to paragraphs 0251 to 0254 of US2012/0068292) can be used, and these contents can be incorporated into the present specification. In addition, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by DAITO CHEMICAL CO., LTD., trade name: UV-503) and the like can also be preferably used. Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP-A-2012-32556. The composition of the present invention may or may not contain an ultraviolet absorber, but when included, the content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, based on the total solid content of the composition , 0.1 to 5% by mass is still more preferable.

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

By including the fluorine-based surfactant in the composition of the present invention, the liquid properties (especially, fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid-saving property can be further improved. That is, when a film is formed using a coating solution containing a composition containing a fluorine-based surfactant, the interfacial tension between the surface to be coated and the coating solution decreases, and the wettability to the surface to be coated is improved. The applicability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with less unevenness in thickness.

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

Examples of fluorine-based surfactants include Megaface F171, Megaface F172, Megaface F173, Megaface F176, Megaface F177, Megaface F141, Megaface F142, Megaface F143, Megaface F144, Megaface R30, Megaface F437, Megaface F475, Megaface F479 , Megaface F482, Megaface F554, Megaface F780, RS-72-K (above, manufactured by DIC CORPORATION), Fluorado FC430, Fluorado FC431, Fluorado FC171 (above, manufactured by 3M Japan Limited), Surflon S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above, manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA SOLUTIONS INC.), etc. As the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used. A block polymer can also be used as a fluorine-type surfactant, and as a specific example, the compound described in Unexamined-Japanese-Patent No. 2011-89090 is mentioned, for example. Fluorine-based surfactants can also preferably use the following fluorine-containing polymer compounds, which include repeating units derived from (meth)acrylate compounds having fluorine atoms and derived from 2 or more (5 or more are preferred) ) repeating unit of (meth)acrylate compound of alkyleneoxy group (ethyleneoxy group and propyleneoxy group are preferred), and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

[chemical formula 18]

The weight average molecular weight of the above-mentioned compound is preferably 3,000-50,000, for example, 14,000. Furthermore, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used as a fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050-0090 and 0289-0295 of JP-A-2010-164965, such as Megaface RS-101, RS-102, RS-718K and RS-72 manufactured by DIC CORPORATION. -K etc.

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

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

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

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

Surfactants may be used alone or in combination of two or more. 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-mentioned components, the following components may be further added to the composition of the present invention. For example, sensitizers, co-sensitizers, cross-linking agents, hardening accelerators, fillers, thermosetting accelerators, polymerization inhibitors, plasticizers, diluents, fat-sensitizing agents, and also based on It is necessary to add adhesion promoters and other additives to the surface of the substrate (for example, conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling accelerators, antioxidants, fragrances, surface tension regulators and chain transfer agent, etc.) and other known additives. These components can be referred to, for example, paragraphs 0183-0228 of JP-A-2012-003225 (corresponding <0237>-<0309> of US Patent Application Publication No. 2013/0034812), JP-A-2008-250074 The descriptions in paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, and paragraph numbers 0159 to 0184 of JP-A-2013-195480 are incorporated into this specification.

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

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

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

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

Various well-known black pigments can be used for a black pigment. For example, carbon black or the black metal-containing organic pigment shown below is mentioned. Examples of black metal-containing organic pigments include metal oxides containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. substances, metal nitrides. These can be used only by 1 type, and can also use it as a mixture of 2 or more types. In addition, it can be prepared to have desired light-shielding properties by further combining inorganic pigments of other hues with black pigments. Examples of specific inorganic pigments that can be used in combination include zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, lead red, oxide Iron red, chrome yellow, zinc yellow (1 type of zinc yellow, 2 types of zinc yellow), ultramarine blue, Prussian blue (potassium ferrocyanide) zircon gray, chrome yellow, chrome titanium yellow, chrome green, peacock, Victoria Green, iron blue (not related to Prussian blue), vanadium zirconium blue, chrome tin red, manganese red, orange red, etc. In particular, in order to express light-shielding properties in a wide wavelength range from ultraviolet to infrared, not only these black pigments or other color tones can be used alone, but also a plurality of pigments can be mixed and used.

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

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

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

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

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

By adjusting the content ratio (Si/Ti) of Si atoms and Ti atoms in the dispersed body containing titanium black and Si atoms to an appropriate range (for example, 0.05 or more), using a composition containing the dispersed body to form When the light-shielding film is used, the residue derived from the composition outside the formation area of the light-shielding film is reduced. In addition, the residue contains components derived from the composition such as titanium black particles and resin components. Although the reason for the reduction of residues is not yet clear, it is inferred as follows: as the above-mentioned dispersed body has a tendency to become small in particle size (for example, the particle size is 30nm or less), and the components containing Si atoms in the dispersed body increase, by This decrease in the adsorption of the film as a whole to the substrate contributes to the improvement of the development removability of the uncured composition (especially titanium black) when the light-shielding film is formed. And, titanium black has excellent light-shielding properties with respect to light covering a wide range of wavelength regions from ultraviolet light to infrared light, so the above-mentioned dispersed body comprising titanium black and Si atoms (Si/Ti is calculated by mass, 0.05 or more) is used. is better) to form a light-shielding film that exhibits excellent light-shielding properties. In addition, the content ratio (Si/Ti) of Si atoms and Ti atoms in the dispersed body can be, for example, the method (1-1) or method (1-2) described in paragraph 0033 of JP-A-2013-249417. Determination. In addition, when determining whether the content ratio (Si/Ti) of Si atoms to Ti atoms in the dispersed body contained in the light-shielding film obtained by curing the composition is 0.05 or more, JP-A-2013 - Method (2) described in paragraph 0035 of Publication No. 249417.

Among the dispersed materials containing titanium black and Si atoms, those mentioned above can be used for titanium black. In addition, in this to-be-dispersed body, in order to adjust dispersibility, colorability, etc., together with titanium black, one or more kinds of composite oxides containing Cu, Fe, Mn, V, Ni, etc., cobalt oxide, Black pigments such as iron oxide, carbon black, and aniline black can be used as dispersions. At this time, it is preferable that the dispersed body containing titanium black accounts for 50% by mass or more of the total dispersed body. In addition, other colorants (organic pigments, dyes, etc.) may be used together with titanium black as needed in the dispersion to adjust the light-shielding property and the like within the range that does not impair the effect of the present invention. Hereinafter, materials used for introducing Si atoms into the dispersed body will be described. When Si atoms are introduced into the dispersed body, Si-containing substances such as silicon dioxide may be used. Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, and synthetic silica, which can be appropriately selected for use. Furthermore, if the particle size of the silica particles is smaller than the film thickness when forming the light-shielding film, the light-shielding property will be more excellent, so it is preferable to use fine-particle type silicon dioxide as the silicon dioxide particles. Moreover, as an example of the microparticle type silica, the silica described in paragraph 0039 of Unexamined-Japanese-Patent No. 2013-249417 is mentioned, for example, The content is incorporated in this specification.

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

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

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

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

When x/y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, generation of impurity phases in the tungsten compound can be reliably avoided. When z/y is 2.2 or more, the chemical stability as a material can be improved more, and when it is 3.0 or less, infrared rays can be fully shielded.

Specific examples of the tungsten oxide compound represented by the above general formula (I) include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 ,} etc., Cs _0.33 WO ₃ or Rb _0.33 WO 3 ₃ is preferred, and Cs _0.33 WO ₃ is more preferred.

The tungsten compound is preferably fine particles. The average primary particle size of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and still more preferably 200 nm or less. When the average primary particle diameter is within this range, the tungsten particles are less likely to shield visible light due to light scattering, and thus can reliably realize light transmission in the visible light region. From the viewpoint of avoiding light scattering, the smaller the average primary particle diameter, the better. However, for reasons such as ease of handling during production, the average primary particle diameter of tungsten fine particles is usually 1 nm or more.

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

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

Furthermore, examples of metal borides include lanthanum boride (LaB ₆ ), manganese boride (PrB ₆ ), neodymium boride (NdB ₆ ), cerium boride (CeB ₆ ), yttrium boride (YB ₆ ), Titanium boride (TiB ₂ ), zirconium boride (ZrB ₂ ), hafnium boride (HfB ₂ ), vanadium boride (VB ₂ ), tantalum boride (TaB ₂ ), chromium boride (CrB, CrB ₂ ), One or more kinds of molybdenum boride (MoB ₂ , Mo ₂ B ₅ , MoB), tungsten boride (W ₂ B ₅ ), and the like, and lanthanum boride (LaB ₆ ) is preferable.

The metal boride is preferably fine particles. The average primary particle diameter of the metal boride fine particles is preferably at most 800 nm, more preferably at most 300 nm, and still more preferably at most 100 nm. When the average primary particle size is in this range, the metal boride fine particles are less likely to block visible light due to light scattering, and thus can more reliably achieve light transmission in the visible light region. From the viewpoint of avoiding light scattering, the smaller the average primary particle diameter, the better. However, for reasons such as ease of handling during production, the average primary particle diameter of metal boride fine particles is usually 1 nm or more.

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

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

((Dye)) As the dye, for example, JP-A-64-90403, JP-A-64-91102, JP-1-94301, JP-6-11614, JP-A Board No. 2592207, U.S. Patent No. 4808501 Specification, U.S. Patent No. 5667920 Specification, U.S. Patent No. 505950 Specification, U.S. Patent No. 5667920 Specification, Japanese Patent Application Publication No. 5-333207, Japanese Patent Application Publication No. 6-35183, Japanese Patent Application Publication No. 6 - Pigments disclosed in JP-A-51115, JP-A-6-194828, etc. If classified as chemical structures, pyrazole azo compounds, pyrromethene compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazole compounds, Azolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenthiazine compounds, pyrrolopyrazole carboximine compounds, and the like. Furthermore, as a dye, a pigment multimer can be used. Examples of the dye multimer include compounds described in JP-A-2011-213925 and JP-A-2013-041097.

The composition of the present invention may contain an extender pigment as needed in addition to the colorant. Examples of such extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, luster white, titanium white, and hydrotalcite. These extender pigments can be used individually or in mixture of 2 or more types. The usage-amount of an extender pigment is 0-100 mass parts normally with respect to 100 mass parts of colorants, Preferably it is 5-50 mass parts, More preferably, it is 10-40 mass parts. In the present invention, the colorant and the extender pigment can be used by modifying the surface of the polymer as the case may be.

The coloring agent may be used alone or in combination of two or more. As a coloring agent, coloring organic pigments, such as red, blue, yellow, green, and purple, can be contained. When a light-shielding pigment (specifically, titanium nitride-containing particles) and a colored organic pigment are used, it is preferable to use 1 to 40% by mass of the colored organic pigment relative to the light-shielding pigment. From the viewpoint of adjusting the color tone, red pigments and light-shielding pigments are preferred, and although not particularly limited, Pigment Red 254 is preferred as the red pigment. In addition, from the viewpoint of improving the light-shielding property, a yellow pigment and a light-shielding pigment are preferable, and although not particularly limited, Pigment Yellow 150 is preferable as the yellow pigment.

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

(Pigment Derivative) The composition of the present invention may contain a pigment derivative. Examples of pigment derivatives include compounds having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group, or a phthalimide methyl group. Examples of organic pigments used to constitute pigment derivatives include dioxopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, and dioxazine pigments. , peroxide pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, shihlin pigments, metal complex pigments, etc. In addition, as the acidic groups of the pigment derivatives, sulfonic acid groups, carboxylic acid groups and quaternary ammonium salt groups are preferred, carboxylic acid groups and sulfonic acid groups are further preferred, and sulfonic acid groups are particularly preferred. As the basic group of the pigment derivative, an amine group is preferable, and a tertiary amine group is particularly preferable. Specific examples of pigment derivatives include, for example, the following compounds. In addition, the description in paragraphs 0162 to 0183 of JP-A-2011-252065 can be referred to, and the contents thereof are incorporated into the present specification.

[chemical formula 19]

When the composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, based on the total mass of the colorant. The composition of the present invention may contain only one type of pigment derivative, or may contain two or more types. When containing 2 or more types, it is preferable that the total amount becomes the said range.

<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, mixer, homogenizer, high-pressure emulsification device, wet pulverizer, wet disperser). In order to remove foreign substances, reduce defects, etc., it is preferable to filter the composition of the present invention with a filter. As a filter, if it is conventionally used for a filtration use etc., it can use without limitation in particular. Examples include filters based on fluorine resins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, polyolefin resins such as polyethylene and polypropylene (PP) (including high density and ultrahigh molecular weight), etc. . Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred. The pore diameter of the filter is preferably about 0.1 to 7.0 μm, more preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and still more preferably about 0.3 to 0.7 μm. By setting it as this range, the filter clogging of a pigment can be suppressed, and the impurity contained in a pigment and fine foreign matter, such as an aggregate, can be reliably removed. When using filters, different filters can be combined. At this time, the filtration with the first filter may be performed only once, or may be performed two or more times. When performing two or more filtrations in combination with different filters, it is preferable that the pore diameter after the second filtration be the same or larger than the pore diameter of the first filtration. In addition, first filters having different pore diameters within the above-mentioned range may be combined. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it is possible to select from various filters offered by NIHON PALL LTD., Toyo Roshi Kaisha, Ltd., Nihon Entegris K.K. (formerly Mykrolis Corporation), or KITZ MICROFILTER CORPORATION or the like. The second filter can use the same material as that of the above-mentioned first filter. The pore diameter of the second filter is preferably about 0.2 to 10.0 μm, more preferably about 0.2 to 7.0 μm, and more preferably about 0.3 to 6.0 μm.

The solid content of the composition of the present invention is preferably 10 to 40% by mass, more preferably 12 to 35% by mass. When the solid content of a composition is 10 mass % or more, the light-shielding property of a cured film improves more. Furthermore, when the solid content of the composition is 40% by mass or less, the viscosity stability of the composition over time becomes more favorable.

[Cured Film (Light-shielding Film)] The cured film of the present invention is obtained using the above-mentioned composition. It is preferable that the said cured film has a surface uneven structure. By doing so, it is possible to reduce the reflectance of the light-shielding film or the light-shielding layer having the light-shielding film. The aforementioned concave-convex structure may be one having a concave-convex structure on the surface of the light-shielding film itself, or another layer may be provided on the light-shielding film to impart the concave-convex structure. The shape of the surface uneven structure is not particularly limited, and the surface roughness is preferably in the range of 0.55 μm to 1.5 μm. The reflectance of the shading film is preferably 5% or less, more preferably 3% or less, and most preferably 2% or less. The method of making the surface concave-convex structure is not particularly limited, and it can be a method of including organic fillers or inorganic fillers in the light-shielding film or other layers, or by lithography using exposure and development, or etching or sputtering, nanometer A method of roughening the surface of a light-shielding film or other layers such as the embossing method. And, as the method of reducing the reflectance of the above-mentioned cured film, in addition to the above, the method of providing a low refractive index layer on the light shielding film, or further providing a plurality of layers with different refractive indices (for example, a high refractive index layer) ), or the method of forming a low optical density layer and a high optical density layer such as described in Japanese Patent Application Laid-Open No. 2015-1654. The cured film of the present invention mainly contains the above-mentioned titanium nitride-containing particles. The cured film of the present invention is preferably used as a light-shielding film, specifically, as a light-shielding film around an image sensor such as a CCD image sensor or a CMOS image sensor (frame light-shielding film). Hereinafter, a case where a cured film is used as a light-shielding film around an image sensor will be described as an example. When the hardened film is used as a light-shielding film around the image sensor, it is possible to form a light-shielding film around the image sensor on the color filter, which is suitable for a CCD image sensor or a CMOS image sensor. appearance. That is, the above-mentioned cured film can be formed in a region where the color filter is in contact with a frame region such as a CCD image sensor or a CMOS image sensor. The color filter having the light-shielding film around the image sensor of the present invention is formed using the above-mentioned composition (especially, the above-mentioned photosensitive composition). The image sensor peripheral light-shielding film obtained using the composition of this invention is excellent in the pattern formation property and the corrosion resistance of an electrode.

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

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

The method for producing a patterned cured film of the present invention is characterized in that it includes: coating the composition of the present invention on a substrate to form a composition layer (coating film) (hereinafter, appropriately referred to as "composition layer formation") process”); the process of exposing the above-mentioned composition layer through a mask (hereinafter, referred to as “exposure process” as appropriate;); and the process of developing the exposed composition layer to form a patterned cured film ( Hereinafter, it is appropriately abbreviated as "development process".).

Specifically, directly or through other layers, the composition of the present invention is coated on a substrate to form a composition layer (composition layer formation process), and exposure is performed through a predetermined mask pattern, so that only the composition irradiated with light The layer is partially cured (exposure process) and developed with a developer (development process) to form a patterned cured film including pixels. Hereinafter, each process will be described.

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

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

Various coating methods such as slit coating method, inkjet method, spin coating method, cast coating method, roll coating method, and screen printing method are applicable as coating methods for coating the composition of the present invention on a substrate. method.

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

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

(Exposure process) In the exposure process, the composition layer (coating film) formed in the composition layer formation process is exposed through a mask, and only the part of the coating film irradiated with light is cured. Exposure by irradiation with actinic light or radiation is preferred, and in particular, ultraviolet rays such as g-rays, h-rays, and i-rays can be preferably used, and a high-pressure mercury lamp is more preferred. The irradiation intensity is preferably 5 to 1500 mJ/cm ² , more preferably 10 to 1000 mJ/cm ² .

(Development process) Next to the exposure process, alkali development treatment (development process) is performed, and the part not irradiated with light in the exposure process is dissolved in an aqueous alkali solution. Thereby, only the photohardened part (the part of the coating film irradiated with light) remains. As the developer, an organic alkali developer that does not damage the circuit of the base is preferable when producing a color filter having a light-shielding film around the image sensor. As image development temperature, it is 20-30 degreeC normally, and image development time is 20-90 second.

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

As an image development method, the spin-on-dip image development method, the shower image development method, etc. can be utilized, for example.

In addition, in the method of manufacturing a color filter having a cured film of the present invention, after performing the above-mentioned composition layer formation process, exposure process, and development process, it may include heating and/or exposure to the formed color filter as necessary. The hardening process of hardening the hardened film.

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

(Color filter) The color filter can be preferably used in solid-state imaging elements such as CCD (charge-coupled device) or CMOS (complementary metal oxide semiconductor), especially suitable for high-resolution CCD or more than 1 million pixels. CMOS etc. The color filter can be used, for example, arranged between the light receiving portion of each pixel constituting a CCD or CMOS and a microlens for condensing light. In addition, the color filter may have a structure in which a cured film forming pixels of each color is embedded in a space divided into, for example, a lattice by partition walls. In this case, it is preferable that the partition wall has a low refractive index with respect to each color pixel. Examples of imaging elements having such a structure include devices described in JP-A-2012-227478 and JP-A-2014-179577. The form of the color filter of the present invention is not particularly limited as long as it has the above-mentioned cured film. In the color filter, the hardened film can be preferably used as, for example, a pixel black matrix of the color filter or as the above-mentioned light-shielding film around the image sensor (frame light-shielding film).

(Light-shielding film) A light-shielding film can be formed on various components in an image display device or a sensor module (for example, an infrared light cut filter, the outer periphery of a solid-state imaging element, the outer periphery of a wafer-level lens, the back surface of a solid-state imaging element, etc.) etc.) etc. to use. In addition, a light-shielding film may be formed on at least a part of the surface of the infrared cut filter to form an infrared cut filter with a light-shielding film. The thickness of the light-shielding film is not particularly limited, preferably 0.2-25 μm, more preferably 1.0-10 μm. The above-mentioned thickness is an average thickness, and is a value obtained by measuring the thickness of arbitrary 5 or more points of the light-shielding film and taking an arithmetic mean of these. The reflectance of the light-shielding film is preferably at most 10%, more preferably at most 8%, even more preferably at most 6%, and most preferably at most 4%. In addition, the reflectance of the light-shielding film is to make the light of 400-700nm incident on the light-shielding film at an incident angle of 5°, and measure the value of the reflectance with a spectrometer UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation.

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

It has the following structure: on the substrate, there are a plurality of transfer electrodes including photodiodes and polysilicon that constitute the light-receiving area of solid-state imaging elements (CCD image sensors, CMOS image sensors, etc.), and the photodiodes On the body and the transfer electrode, there is a light-shielding film that only opens to the light-receiving part of the photodiode, and on the light-shielding film is a device protection made of silicon nitride formed to cover the front of the light-shielding film and the light-receiving part of the photodiode. film, with a color filter on the device protective film. Moreover, it is also possible to have a light-condensing mechanism (for example, a microlens, etc., the same below) on the device protective layer and under the color filter (the side close to the substrate), and have a light-condensing mechanism on the color filter. structure etc. In addition, the color filter may have a structure in which a cured film forming pixels of each color is embedded in a space divided into, for example, a lattice by partition walls. In this case, it is preferable that the partition wall has a low refractive index with respect to each color pixel. Examples of imaging devices having such a configuration include devices described in JP-A-2012-227478 and JP-A-2014-179577.

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

For the definition of the display device or the details of each display device, for example, it is described in "Electronic Display Device (written by Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd. in 1990)", "Display Device (written by Shunaki Ibuki, Industrial Books (Co., Ltd. issued in the first year of Heisei)" and so on. Further, liquid crystal display devices are described, for example, in "Second Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd., 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "second-generation liquid crystal display technology".

When applying the color filter in this invention to a liquid crystal display device, the form is not specifically limited. Hereinafter, the case where the color filter of this invention is applied to a liquid crystal display device is demonstrated in full detail. The color filter of the present invention can be used in a color TFT (Thin Film Transistor) type liquid crystal display device. A color TFT liquid crystal display device is described, for example, in "Color TFT Liquid Crystal Display (Published by KYORITSU SHUPPAN CO., LTD. in 1996)". Moreover, the color filter of the present invention can also be applied to liquid crystal display devices or STN (Super-Twist Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching) and R-OCB (Reflective Optically Compensated Bend), etc. Furthermore, the color filter in the present invention can also be used in a bright and high-definition COA (Color-filter On Array) system. Regarding the liquid crystal display device of the COA method, the required characteristics of the color filter are sometimes required of the required characteristics of the interlayer insulating film, that is, low dielectric constant and stripping liquid resistance, in addition to the above-mentioned general 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 required characteristics of low dielectric constant, a resin film may be provided on the color filter layer. These image display methods are described, for example, on page 43 of "EL, PDP, LCD Displays - Latest Trends in Technology and Market - (published by TORAY Research Center, Inc. in 2001)".

The liquid crystal display device of the present invention may be composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, or a viewing angle protection film, in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device composed of these known members. These components are described, for example, in "'94 Liquid Crystal Display Peripheral Materials and Chemical Products Market (Kentaro Shima CMC-Group. Published in 1994)", "2003 Liquid Crystal Related Market Status and Future Prospects (Volume 2)" (Omoyoshi Fuji Chimera Research Institute, Inc., published in 2003)". Regarding the backlight, in addition to SID meeting Digest 1380 (2005) (A.Konno et.al), it is described in Monthly Display December 2005, pages 18 to 24 (Shima Yasuhiro), and it is described in SID meeting Digest 1380 (2005) 25 ~30 pages (Takaaki Yagi), etc.

In addition, the cured film of the present invention can be used in portable devices such as personal computers, tablet computers, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as multi-function printers and scanners; surveillance cameras, barcode readers, and Industrial equipment such as automatic deposit and withdrawal machines (ATMs), high-speed cameras, or personal authentication using face image authentication; vehicle-mounted camera equipment; medical camera equipment such as endoscopes, capsule endoscopes, and catheters; biosensors Detectors, biological sensors (Biosensor), cameras for military reconnaissance, cameras for three-dimensional maps, cameras for meteorological or oceanographic observation, cameras for reconnaissance of land resources, or astronomical or deep-space target exploration cameras for space equipment, etc. Light-shielding member or light-shielding layer of an optical filter or module. Furthermore, the cured film of the present invention can be used for an optical film or an antireflection member or an antireflection layer of a module.

Moreover, the cured film of this invention can also be used for uses, such as a micro LED (Light Emitting Diode) and a micro OLED (Organic Light Emitting Diode). Although not particularly limited, it can be preferably used for a member imparting a light-shielding function or an antireflection function other than 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.

Moreover, the cured film of this invention can also be used for uses, such as a quantum dot display. Although not particularly limited, in addition to optical filters and optical films used in quantum dot displays, it can also be preferably used for members imparting light-shielding functions and anti-reflection functions. Examples of quantum dot displays include U.S. Patent Application Publication No. 2013/0335677, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, and U.S. Patent Application Publication No. 2014/0035960. Recorder. [Example]

Hereinafter, the present invention will be described in more detail based on examples. Materials, usage amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed unless departing from the gist of the present invention. Accordingly, the scope of the present invention should not be limitedly interpreted by the Examples shown below.

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

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

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

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

The content of titanium (Ti) atoms and chlorine (Cl) atoms in the obtained titanium nitride-containing particles TiN-1 was measured by ICP emission spectrometry. In addition, in the ICP emission spectrometry, an ICP emission spectrometry apparatus "SPS3000" (trade name) manufactured by Seiko Instruments Inc. was used. In addition, the content of nitrogen atoms was measured using an oxygen and nitrogen analyzer "EMGA-620W/C" (trade name) manufactured by HORIBA, Ltd., and calculated by the inert gas fusion thermal conductivity method. The results are shown in Table 1. In addition, 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. In addition, the balance in each particle is impurities such as oxygen derived from oxides and metal elements present in the particles. The results are shown in Table 1 and Table 2.

Regarding the X-ray diffraction of TiN-1 containing titanium nitride particles, the powder sample was placed in an aluminum standard sample holder, and it was carried out by a wide-angle X-ray diffraction method (manufactured by Rigaku Corporation, trade name "RU-200R") Determination. As the measurement conditions, the X-ray source is set to CuKα ray, the output is set to 50kV/200mA, the slit system is set to 1°-1°-0.15mm-0.45mm, the measurement step (2θ) is set to 0.02°, and the scanning speed is set to 2°/min. Furthermore, the diffraction angle (2θ) of the peak originating from the TiN (200) plane was measured. Then, from the half-value width of this peak, the crystallite size constituting the particles was obtained using Scherrer's formula. The results are shown in Table 1. In addition, for the following titanium nitride-containing particles TiN-2 to TiN-19, the diffraction angle 2θ and the crystallite size were measured by the same method as that of the titanium nitride-containing particle TiN-1. The results are shown in Table 1 and Table 2.

The measurement of the average primary particle size of the titanium nitride-containing particles TiN-1 was carried out by a transmission electron microscope (Transmission Electron Microscope; TEM) according to the method described above. Further, particle shape observation was carried out simultaneously with the above measurement, and as a result, it was confirmed that 60 or more of the 100 titanium nitride-containing particles to be observed were spherical. These results are shown in Table 1. In addition, regarding the shape observation evaluation of particles, when 60% or more of the measurement objects are spherical, they are shown as "spherical" in the table. When the number of spherical particles is less than 60% of the measurement object, it is indicated as "spherical less than 60%" in the table. In addition, when "cubic" is described in the table, it means that the number of cubic particles is 60% or more of the measurement object. In addition, the cube is not limited to what is observed as a cube, and a polyhedron whose corners can be observed is also measured as a cube. In addition, the following titanium nitride-containing particles TiN-2 to TiN-19 were also measured by the same method as the titanium nitride-containing particle TiN-1, and the shape observation was further performed. The results are shown in Table 1 and Table 2.

Regarding the specific surface area of titanium nitride-containing particles TiN-1, _N2 was measured after vacuum degassing at 100°C using a high-precision fully automatic gas adsorption device (“BELSORP” 36) manufactured by nippon-bel Co., Ltd. The adsorption isotherm at the liquid nitrogen temperature (77K) of the gas was analyzed by the BET method to obtain the specific surface area. The results are shown in Table 1. In addition, for the following titanium nitride-containing particles TiN-2 to TiN-19, the specific surface area was obtained by the same method as that of the titanium nitride-containing particle TiN-1. The results are shown in Table 1 and Table 2.

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

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

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

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

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

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

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

(Titanium nitride-containing particles TiN-9) Except that the flow rate in the chamber was set as shown in Table 1, titanium nitride-containing particles TiN was produced by the same method as that of titanium nitride-containing particles TiN-8. -9.

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

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

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

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

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

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

(TiN-16 containing titanium nitride particles) Except that the heat treatment conditions were set as shown in Table 2, TiN-16 containing titanium nitride particles was produced by the same method as TiN-15 containing titanium nitride particles. .

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

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

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

The production conditions and physical properties of the above-mentioned titanium nitride-containing particles TiN-1 to titanium nitride-containing particles TiN-19 are shown in Table 1 and Table 2 below. In addition, in the table, the heat treatment temperature is 240° C. except for the titanium nitride-containing particles TiN-11, TiN-12, TiN-13, and TiN-14.

(Table 1) [Table 1]

(Table 2) [Table 2]

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

[chemical formula 20]

[chemical formula 21]

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

[chemical formula 22]

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

[chemical formula 23]

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

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

<Solvent> ・PGMEA: Propylene Glycol Monomethyl Ether Acetate・Cyclopentanone・Butyl Acetate・Ethyl 3-Ethoxypropionate・Distilled Butyl Acetate・Distilled Cyclopentanone For distillation of cyclopentanone, commercially available butyl acetate and cyclopentanone were purified by distillation.

＜Polymerization inhibitor＞ ・p-Methoxyphenol

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

[chemical formula 24]

<Preparation of Pigment Dispersion> First, titanium nitride-containing particles, a dispersant, and a solvent were mixed for 15 minutes with a stirrer (Eurostar manufactured by IKA COMPANY) to obtain a dispersion. Next, the obtained dispersion was subjected to dispersion treatment under the following conditions using NPM-Pilot manufactured by Shinmaru Enterprises Corporation, thereby obtaining a pigment dispersion. (Dispersion conditions) ・Bead diameter: φ0.05mm, (NIKKATO CORPORATION YTZ) ・Microbead filling rate: 65% by volume ・Grinding peripheral speed: 10m/sec ・Separator peripheral speed: 13m/s ・Mixed solution for dispersion treatment Volume: 15kg ・Circulation flow (pump supply): 90kg/hour ・Temperature of treatment liquid: 19～21℃ ・Cooling water: water ・Treatment time: 22 hours

<Preparation of composition> Next, the above-mentioned pigment dispersion, binder resin, polymerizable compound, polymerization initiator, and solvent were mixed and stirred to obtain the following examples and comparisons shown in Tables 3 to 5 Each composition of the example. The content (mass %) of each component contained in each composition of the example and the comparative example is shown in the 3rd table - the 5th table. In addition, the ratio of the dispersant to the titanium nitride-containing particles ((mass ratio) D/P), the solid content concentration (mass %) in the composition, and the water content (mass %) in the composition are shown below. method.), and the pigment concentration (mass %) in the solid content was prepared in such a manner that the ratios shown in the respective examples and comparative examples in Tables 3 to 5 were obtained.

(Measurement of Moisture Amount in Composition) The moisture content of each composition of Examples and Comparative Examples was measured by MKV-710 (trade name, manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD. ) were measured. The results are shown in Tables 3 to 5.

[Evaluation Tests] The following evaluation tests were performed on the compositions of Examples and Comparative Examples.

<Degassing> Using each composition of an Example and a comparative example, the frame for color filters was produced. Specifically, on a semiconductor substrate configured as an image sensor on an 8-inch substrate, the compositions of Examples and Comparative Examples were spin-coated to form coatings so that the film thickness after prebaking became 1.5 μm. membrane. Next, a binary mask capable of forming a light-shielding film with a width of 250 μm and a total width of 200 μm is placed on the outer periphery of 720 μm in width and 520 μm in length, and exposure is performed with an i-ray exposure device (FPA-3000+i5, manufactured by Canon Inc.) (exposure amount 500 mJ /cm ² ), further development was carried out. The obtained semiconductor substrate having a plurality of frames for color filters was cut into a size of 10mm×10mm, and the amount of Cl in the outgassing was detected by thermal desorption spectroscopy (TDS), and evaluated according to the following criteria. The count intensity ratio of the peak position originating from Cl in the total outgassing amount (detection total ion current value) from mass numbers 1 to 199 when the counting originating from atmospheric components included in the background was cancelled, was carried out based on the following criteria evaluate. The degree of vacuum at the time of measurement was set to be 1×10 ^-7 Torr or less. "A": In 1 L of degassing, the amount of Cl is 10 ppm or less "B": In 1 L of degassing, the amount of Cl is more than 10 ppm and less than 50 ppm "C": In 1 L of degassing, the amount of Cl is more than 50 ppm and less than 100 ppm "D": In 1L of degassing, the amount of Cl exceeds 100ppm

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

<OD value> On a glass plate (manufactured by EagleXG, Corning Inc.) with a thickness of 0.7 mm and an angle of 10 cm, the compositions of Examples and Comparative Examples were spin-coated at a speed of 1.0 μm in film thickness to form a film, and the film was formed on a hot plate A dry film was obtained by heat treatment at 100° C. for 2 min. For the obtained substrate, OD was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation.) to measure the lowest OD value in the wavelength range from 400 nm to 1200 nm, and evaluated based on the following criteria. "A": The minimum OD is above 4.2 "B": The minimum OD is above 3.8 and below 4.2 "C": The minimum OD is above 3.5 and below 3.8 "D": The minimum OD is below 3.5

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

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

<Pattern Formability (Resolution)> Using the compositions of Examples and Comparative Examples, a coating film was formed on an image sensing device substrate with a spin coater. Next, the obtained coating film was pre-baked at 100° C. for 2 minutes on a hot plate. Next, the coating film subjected to the above-mentioned prebaking treatment is exposed using an i-ray exposure device (FPA, manufactured by Canon Inc.), and further developed to form a coated cut line and an electrode portion on the outer peripheral portion of the light-receiving portion on the substrate. 20 alignment marks with a line width of 20 μm were formed on the substrate simultaneously with a light-shielding film. The resolution was evaluated by observing the number of objects of the alignment mark formed with the optical microscope. "A": 20 marks were formed. "B": 19 marks were formed. "C": 18 marks were formed. "D": marked as 17 or less.

<Corrosion resistance of electrodes> Using the compositions of Examples and Comparative Examples, a coating film was formed on an image sensing device substrate with a spin coater. Next, the obtained device substrate after the coating film was formed was prebaked at 100° C. for 2 minutes on a hot plate. Next, the coating film subjected to the above-mentioned prebaking treatment is exposed using an i-ray exposure device (FPA-3000+i5, manufactured by Canon Inc.), and further developed to form a coated cut line and Light-shielding film other than the electrode part. Furthermore, the obtained light-shielding film was subjected to heat treatment at 220° C. for 5 minutes using a hot plate (post-baking process). The wafer with the obtained light-shielding film was stored in an environment with a temperature of 110°C and a humidity of 90%RH (ESPEC CORP. HAST tester EHS-411M) for 3 days, and the 300 electrodes formed on the wafer were tested. The state of occurrence of rust on the electrode pattern was observed with an optical microscope (manufactured by Olympus Corporation, trade name "LEXT OLS4500"), and the corrosion resistance of the electrode was evaluated according to the following criteria. "A": No change was observed "B": Rust of electrode was 2 or less "C": Rust of electrode was more than 2 and less than 10 "D": Rust of electrode was more than 10

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

[table 3]

[Table 4]

[table 5]

As shown in Tables 3 to 5, it is shown that the content of chlorine atoms in titanium nitride-containing particles is within the range of 0.001 to 0.3 mass % (in other words, 10 mass ppm to 3000 mass ppm), and it is possible to produce A cured film with excellent anti-corrosion properties of electrodes and excellent pattern formation (resolution) (Example). And, it shows that if the content of chlorine atoms in the titanium nitride-containing particles exceeds 0.3% by mass (in other words, 3000 mass ppm), the pattern formation (resolution) and corrosion resistance of the electrode are poor (Comparative Example 1, Comparative Example 2). Furthermore, it was shown that when the content of chlorine atoms in the titanium nitride-containing particles is less than 0.001% by mass (in other words, less than 10 mass ppm), the pattern formation properties (resolution) are poor (Comparative Example 3, Comparative Example 4).

And, by comparison between Examples 17-21, it is confirmed that the content of water is 0.1-1% by mass (preferably 0.1-0.8% by mass, more preferably 0.1-0.4% by mass) relative to the total mass of the composition , the pattern formation (resolution) of the cured film and the corrosion resistance of the electrode material are more excellent. Furthermore, it was confirmed that by setting the water content to 0.1 to 1% by mass relative to the total mass of the composition, the amount of particles in the composition can be further reduced, and the viscosity stability of the composition over time is also more excellent. And it confirmed that the pattern formability (resolution) of a cured film is more excellent when D/P is 0.3 or less from the comparison of Example 26 and Example 27. By comparing Examples 26, 31, and 32, it was confirmed that when the content of titanium nitride-containing particles is 30 to 70% by mass relative to the total solid content of the composition, the spectroscopic properties (good OD value), pattern formation properties ( resolution) and the corrosion resistance of the electrode is more excellent. In addition, by comparing Examples 6 to 9, it was confirmed that when the specific surface area of the titanium nitride-containing particles determined by the BET method is 40 to 60 m ² /g, the spectroscopic properties (good OD value) and pattern formation properties (resolution) is even better. Furthermore, it was confirmed that filterability is also excellent. Furthermore, by comparing Examples 10 to 14, it was confirmed that when CuKα rays are used as the X-ray source, when the diffraction angle 2θ of the peak originating from the (200) plane of titanium nitride particles exceeds 42.8° and is not more than 43.5° , Spectroscopy (good OD value) and pattern formation (resolution) are more excellent. In addition, from the comparison of Examples 12 to 15, it was confirmed that when the average primary particle diameter of the titanium nitride-containing particles is 10 to 30 nm, the spectroscopic properties (favorable OD value) are more excellent. Furthermore, it was confirmed that the viscosity stability of the composition was also excellent over time. Furthermore, it was confirmed that when the average primary particle size of the titanium nitride-containing particles is 10 nm or more, the viscosity stability of the composition over time is excellent. In addition, by comparing Example 12 with Example 16, it was confirmed that in the shape of the primary particle of the titanium nitride-containing particle using a transmission electron microscope, when the ratio of spherical shape is 60% by mass or more, the spectroscopic property (good OD value) and pattern formation (resolution) are more excellent. In addition, it was confirmed that the filterability and viscosity stability of the composition were also excellent.

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

<Preparation of carbon black dispersion (CB dispersion liquid)> In the preparation of the above-mentioned pigment dispersion, carbon black (trade name "Color Black S170", manufactured by Degussa-Hüls AG, average primary particle A diameter of 17 nm, a BET specific surface area of 200 m ² /g, and a carbon black produced by a gas black method), a dispersion was produced by the same method, and a carbon black dispersion was obtained.

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

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

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

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Claims (22)

A black composition comprising a polymerizable compound, titanium nitride-containing particles containing chlorine atoms, and water, and the content of the chlorine atoms in the titanium nitride-containing particles is 0.001 to 0.3% by mass, and the content of the water is relative to The total mass of the aforementioned black composition is 0.1-1% by mass. A black composition comprising a polymerizable compound, titanium nitride-containing particles containing chlorine atoms, a dispersant, and water, and the content of the chlorine atoms in the titanium nitride-containing particles is 0.001 to 0.3% by mass, and the dispersant The content ratio of the aforementioned titanium nitride-containing particles is 0.3 or less in terms of mass ratio, the aforementioned polymerizable compound is a polymerizable compound having an acid group with an acid value of 0.1 to 40 mgKOH/g, and the aforementioned water content is relative to the aforementioned black composition The total mass is 0.1 to 1% by mass. A black composition, which contains a polymerizable compound, titanium nitride-containing particles containing chlorine atoms, and water, and the content of the chlorine atoms in the titanium nitride-containing particles is 0.001 to 0.3% by mass, as measured by a transmission electron microscope In the photographic observation of the primary particle image of the titanium nitride-containing particles, 60 or more of the 100 observed objects are spherical, and the content of the water is 0.1 to 1% by mass relative to the total mass of the black composition. The black composition as described in any one of items 1 to 3 of the scope of the patent application, wherein When CuKα rays are used as the X-ray source, the diffraction angle 2θ of the peak originating from the (200) plane of the titanium nitride-containing particles exceeds 42.8° and is 43.5° or less. The black composition as described in any one of claims 1 to 3, wherein the titanium nitride-containing particles have a specific surface area of 40 to 60 m ² /g as determined by the BET method. The black composition as described in any one of the claims 1 to 3, wherein the average primary particle diameter of the titanium nitride-containing particles is 10-30 nm. The black composition as described in claim 1 or claim 2, wherein in the photographic observation of the primary particle image of the aforementioned titanium nitride-containing particles using a transmission electron microscope, 60 or more of the 100 observed objects are spherical. The black composition described in any one of claims 1 to 3 further contains two or more solvents. The black composition as described in item 1 of the patent claims further contains a dispersant. The black composition according to claim 9, wherein the content ratio of the dispersant to the titanium nitride-containing particles is 0.3 or less in mass ratio. The black composition described in any one of claims 1 to 3 further contains a polymerization initiator. The black composition as described in any one of claims 1 to 3, wherein the solid content in the black composition is 10 to 40% by mass. The black composition according to any one of claims 1 to 3, wherein the content of the titanium nitride-containing particles is 30 to 70% by mass relative to the total solid content of the black composition. The black composition as described in item 1 or item 3 of the scope of the patent application, which also contains a dispersant, and the aforementioned dispersant has a compound selected from polycaprolactone, polyvalerolactone, polymethyl acrylate and polymethacrylic acid At least one structure of the group consisting of methyl esters. The black composition as described in item 2 of the scope of application, wherein the aforementioned dispersant has at least 1 selected from the group consisting of polycaprolactone, polyvalerolactone, polymethyl acrylate and polymethyl methacrylate. kind of structure. The black composition as described in claim 1 or claim 3, wherein the aforementioned polymerizable compound is a polymerizable compound having an acid group with an acid value of 0.1-40 mgKOH/g. The black composition as described in any one of the claims 1 to 3, wherein the content of the chlorine atoms is 0.001% by mass to 0.15% by mass relative to the total mass of the titanium nitride-containing particles. A cured film obtained by using the black composition described in any one of items 1 to 17 of the patent application. A color filter having the cured film described in claim 18 of the patent application. A light-shielding film having the hardened film described in item 18 of the scope of the patent application. A solid-state imaging element having the cured film described in claim 18 of the patent application. An image display device having the cured film described in claim 18 of the patent application.