JPWO2019069609A1 - Manufacturing method of cured film, manufacturing method of solid-state image sensor, manufacturing method of image display device - Google Patents

Abstract

A method for producing a cured film capable of producing a cured film having excellent rectangularness in cross-sectional shape and maintaining excellent rectangularness even when a reserved curable composition layer is used, a method for producing a solid-state image sensor, and an image. Provided is a method for manufacturing a display device. As a method for producing a cured film, a curable composition containing a black pigment and a polymerizable compound is used, the optical density A at a wavelength of 365 nm per 1.5 μm film thickness is 2.60 to 10.00, and the cured film is produced. The step of forming a curable composition layer having an optical density B of 2.00 to 10.00 at a wavelength of 550 nm per 1.5 μm film thickness and the curable composition layer having an oxygen concentration of 30 to 50% by volume. It includes a step of exposing under the above conditions and a step of developing the curable composition layer after the exposure to form a cured film.

Description

The present invention relates to a method for manufacturing a cured film, a method for manufacturing a solid-state image sensor, and a method for manufacturing an image display device.

A method for producing a cured film used in a solid-state imaging device and an image display device (for example, a liquid crystal display device, an organic EL (electroluminescence) device, etc.) is a method of producing a cured film after forming a curable composition layer on a substrate. A method of curing this is common. There, it is typical that the curable composition layer is irradiated with light through a predetermined mask pattern, and then a development process is performed.
Further, in order to improve the performance of the cured film to be formed, the optical density (OD: Optical absorbance) of the curable composition layer for a specific wavelength may be adjusted within a predetermined range.

For example, in Patent Document 1, when a film having a thickness of 2.0 μm after drying is formed using a colored photosensitive composition, the optical density of the film at a wavelength of 365 nm is 1.5 or more. The photosensitive composition is disclosed (claim 1).

International Publication 2016/158114

As a result of examining the colored photosensitive composition described in Patent Document 1, the present inventors have room for improvement in the rectangularness of the cross-sectional shape of the cured film formed by using the colored photosensitive composition. Was found.
In addition, it is required to be able to produce a cured film of stable quality under various production conditions, and there is a period (for example, one week) from the formation of the curable composition layer to the exposure. However, it is also required that the obtained cured film has a good rectangular cross-sectional shape.
Hereinafter, the fact that the object to be processed that has undergone a specific process is made to wait until the next process is also referred to as "reservation".

Therefore, the present invention provides a method for producing a cured film capable of producing a cured film having excellent rectangularity in cross-sectional shape and maintaining excellent rectangularness even when a reserved curable composition layer is used. Make it an issue. Another object of the present invention is to provide a method for manufacturing a solid-state image sensor and a method for manufacturing an image display device.

[1] Using a curable composition containing a black pigment and a polymerizable compound, the optical density A at a wavelength of 365 nm per 1.5 μm film thickness is 2.60 to 10.00, and the film thickness is 1.5 μm. The step of forming a curable composition layer having an optical density B of 2.00 to 10.00 at a wavelength of about 550 nm and the exposure of the curable composition layer under conditions of an oxygen concentration of 30 to 50% by volume. A method for producing a cured film, which comprises a step of developing the curable composition layer after the exposure to form a cured film.
[2] The curing according to [1], wherein the black pigment is a nitride or oxynitride of a Group 4 metal element, a nitride or oxynitride of a Group 5 metal element, or carbon black. Method of manufacturing a membrane.
[3] The black pigment is titanium nitride or oxynitride, zirconium nitride or oxynitride, vanadium nitride or oxynitride, niobium nitride or oxynitride, or carbon black. , [1] or [2], the method for producing a cured film.
[4] The black pigment is titanium nitride or oxynitride, zirconium nitride or oxynitride, vanadium nitride or oxynitride, or niobium nitride or oxynitride. [1] ] To [3]. The method for producing a cured film according to any one of [3].
[5] The method for producing a cured film according to any one of [1] to [4], wherein the black pigment is titanium nitride or oxynitride, or zirconium nitride or oxynitride.
[6] The method for producing a cured film according to any one of [1] to [5], wherein the irradiance in the above exposure is 20000 to 50000 W / m ² .
[7] The method for producing a cured film according to any one of [1] to [6], wherein the irradiance in the above exposure is 2500 to 40,000 W / m ² .
[8] The cured film according to any one of [1] to [7], wherein the optical density A is 2.80 to 4.00 and the optical density B is 2.50 to 7.00. Production method.
[9] The method for producing a cured film according to any one of [1] to [8], wherein the ratio of the optical density B to the optical density A is 0.5 to 2.0.
[10] The curable composition further contains a resin, the resin contains a resin containing an ethylenically unsaturated group, and the content of the ethylenically unsaturated group with respect to the total mass of the resin. The method for producing a cured film according to any one of [1] to [9], wherein the amount is 0.10 to 3.00 mmol / g.
[11] The method for producing a cured film according to any one of [1] to [10], wherein the curable composition further contains a polymerization initiator.
[12] The method for producing a cured film according to any one of [1] to [11], wherein the curable composition further contains a polymerization inhibitor.
[13] When the optical density A is X, the oxygen concentration at the time of exposure is Y, and the irradiance is Z, the values calculated by the formula (1) described later are 2.80 × ^{10-5 to} 5. The method for producing a cured film according to any one of [1] to [12], which comprises 20 × ^10-5 .
[14] The method for producing a cured film according to any one of [1] to [13], wherein the cured film is a light-shielding film.
[15] A method for manufacturing a solid-state image sensor, which manufactures a solid-state image sensor having a cured film through the manufacturing method according to any one of [1] to [14].
[16] A method for manufacturing an image display device, which manufactures an image display device having a cured film through the manufacturing method according to any one of [1] to [14].

According to the present invention, it is possible to provide a cured film having an excellent rectangularity in cross-sectional shape, and to provide a method for producing a cured film capable of maintaining an excellent rectangularity even when a reserved curable composition layer is used.
Further, according to the present invention, a method for manufacturing a solid-state image sensor and a method for manufacturing an image display device can also be provided.

It is the schematic sectional drawing which shows the structural example of the solid-state image sensor. It is the schematic sectional drawing which shows the image pickup part of FIG. 1 enlarged. It is schematic cross-sectional view which shows the structural example of an infrared sensor.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.

Further, in the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substituent includes a group containing a substituent as well as a group containing no substituent. For example, the "alkyl group" includes not only an alkyl group containing no substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).

Further, the term "active ray" or "radiation" in the present specification means, for example, far ultraviolet rays, extreme ultraviolet rays (EUV: Extreme ultraviolet lithium), X-rays, electron beams, and the like. Further, in the present specification, light means active light rays and radiation. Unless otherwise specified, the term "exposure" as used herein includes not only exposure with far ultraviolet rays, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams.

Further, in the present specification, "(meth) acrylate" represents acrylate and methacrylate. Further, in the present specification, "(meth) acrylic" represents acrylic and methacrylic. Further, in the present specification, "(meth) acryloyl" represents acryloyl and methacryloyl. Moreover, in this specification, "(meth) acrylamide" represents acrylamide and metaacrylamide. Further, in the present specification, "monomer" and "monomer" are synonymous.

In the present specification, the weight average molecular weight (Mw) is a polystyrene-equivalent value obtained by a GPC (Gel Permeation Chromatography) method.
In the present specification, the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns, and THF (tetrahydrofuran, manufactured by Tosoh Corporation) as an eluent. ) Is used.

In the production method of the present invention, a curable composition containing a black pigment and a polymerizable compound is used, the optical density A at a wavelength of 365 nm per 1.5 μm film thickness is 2.60 to 10.00, and the film is formed. The step of forming a curable composition layer having an optical density B of 2.00 to 10.00 at a wavelength of 550 nm per 1.5 μm thickness and the curable composition layer having an oxygen concentration of 30 to 50% by volume. It includes a step of exposing under conditions and a step of developing the curable composition layer after the exposure to form a cured film.

When the curable composition layer formed by using a curable composition containing a colorant (particularly a black pigment) is exposed to obtain a patterned cured film, the surface layer portion of the curable composition layer is used. There is a problem that the shape of the obtained patterned cured film is deteriorated because the way of shining light is different from that of the lower layer portion. More specifically, there is a problem that light does not easily penetrate into the lower layer portion with respect to the surface layer portion, and curing does not easily proceed in the lower layer portion, and as a result, the rectangularity of the cross-sectional shape of the patterned cured film deteriorates. ..
On the other hand, the reason why a cured film (patterned cured film) having an excellent rectangular cross-sectional shape can be obtained by using the production method of the present invention is not always clear, but the present inventors have described as follows. I'm thinking about it. That is, by exposing the curable composition layer exhibiting a predetermined optical density to a specific wavelength under a high oxygen concentration, oxygen appropriately inhibits the curing reaction in the surface layer portion, and the curable composition It is considered that this is because the curing can proceed in a well-balanced manner between the surface layer portion and the lower layer portion of the material layer. Further, since the curing can proceed in a well-balanced manner as described above, even when a curable composition layer having a period (for example, one week) after its formation is used, the obtained cured film has a good rectangular property. I think I can maintain it.
Further, it is considered that the curable composition layer used in the production method of the present invention has an optical density A and an optical density B in a predetermined range, which contributes to the improvement of the rectangularity of the cross-sectional shape of the cured film. ing.

In the production method of the present invention, as described above, a cured film is produced by exposing a curable composition layer containing a specific component and exhibiting a predetermined optical density under a constant oxygen concentration.
In the present specification, first, the curable composition used in the production method of the present invention will be described. Next, a method of forming a curable composition layer using this curable composition and exposing the curable composition layer to produce a cured film will be described.
Then, the use of the cured film obtained by using the production method of this invention will be described.

[Curable composition]
Next, the curable composition used in the production method of the present invention will be described.
The components contained in the curable composition used in the production method of the present invention will be described.

<Black pigment>
The curable composition contains a black pigment. As the black pigment, various known black pigments can be used. The black pigment may be an inorganic pigment or an organic pigment.
Examples of the black inorganic pigment include Group 4 metal elements such as titanium (Ti) and zirconium (Zr), Group 5 metal elements such as vanadium (V) and niobium (Nb), cobalt (Co) and chromium ( One or 2 selected from the group consisting of Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and silver (Ag). Examples thereof include metal oxides, metal nitrides, and metal oxynitrides containing more than one kind of metal element. The inorganic pigment may be subjected to a surface modification treatment. Examples thereof include inorganic particles that have been surface-modified with a surface treatment agent having both a silicone group and an alkyl group, and examples thereof include the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., Ltd.). Further, the metal oxide, the metal nitride, and the metal oxynitride may be used as particles in which other atoms are further mixed. For example, it may be used as a metal nitride-containing particle further containing an atom (preferably an oxygen atom and / or a sulfur atom) selected from the elements of Groups 13 to 17 of the periodic table.
Examples of the black pigment include carbon black. Specific examples of carbon black include commercially available C.I. I. Pigment Black 1 and other organic pigments, and C.I. I. Examples thereof include inorganic pigments such as Pigment Black 7.

Among them, as the black pigment, the nitride or oxide of the metal element of Group 4, the nitride or oxynitride of the metal element of Group 5, or carbon black is preferable, and the nitride or oxynitride of titanium is preferable. , Nitride or oxynitride of zirconium, nitride or oxynitride of vanadium, nitride or oxynitride of niobium, or carbon black, more preferably nitride or oxynitride of titanium, nitride of zirconium or Oxynitrides, vanadium nitrides or oxynitrides, or niobium nitrides or oxynitrides are more preferred, and titanium nitrides or oxynitrides, or zirconium nitrides or oxynitrides are particularly preferred.
The nitride of titanium is titanium nitride, the nitride of zirconium is zirconium nitride, the nitride of vanadium is vanadium nitride, and the nitride of niobium is niobium nitride. Further, the oxynitride of titanium is titanium oxynitride, the oxynitride of zirconium is zirconium oxynitride, the oxynitride of vanadium is vanadium oxynitride, and the oxynitride of niobium is oxynitride. Niobium.
Further, as a black pigment, a commercially available product "NITRBLACK (Night Black) UB-1" (manufactured by Mitsubishi Materials Corporation, zirconium nitride powder described in JP-A-2017-222559, and patent No. 4931011). Black pigments such as a fine particle low-order zirconium oxide / zirconium nitride composite can also be mentioned.

Further, in the production method of the present invention, as the black pigment, titanium nitride or oxynitride, zirconium nitride or oxynitride, vanadium nitride or oxynitride, or niobium nitride or oxynitride. Surprisingly, when using, the cured film obtained after forming the curable composition layer with the curable composition, even if there is a period (eg, one week) before exposure. Deterioration of the rectangularness of the cross-sectional shape can be further suppressed.

The black pigment is preferably as fine as possible. Considering the handleability, the average primary particle size of the black pigment is preferably 0.01 to 0.1 μm, more preferably 0.01 to 0.05 μm.

The average primary particle size of the black pigment can be measured using a transmission electron microscope (TEM). As the transmission electron microscope, for example, a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
Maximum length (Dmax: maximum length at two points on the contour of the particle image) and maximum length vertical length (DV-max: two straight lines parallel to the maximum length) of the particle image obtained using a transmission electron microscope. When the image is sandwiched between, the length is measured (the shortest length that connects the two straight lines vertically), and the synergistic average value (Dmax × DV-max) ^1/2 is taken as the particle size. The particle size of 100 particles is measured by this method, and the arithmetic mean value thereof is used as the average particle size to obtain the average primary particle size of the black pigment.

In the present specification, the titanium nitride is intended to be TiN and may contain oxygen atoms unavoidable in production (for example, the surface of TiN particles is unintentionally oxidized, etc.).
In the present specification, the titanium nitride is intended to be a compound in which the diffraction angle 2θ of the peak derived from the (200) plane when CuKα ray is used as an X-ray source is 42.5 ° to 42.8 °.
Further, in the present specification, the titanium oxynitride is intended to be a compound having a peak diffraction angle of 2θ of more than 42.8 ° derived from the (200) plane when CuKα ray is used as an X-ray source. The upper limit of the diffraction angle 2θ of titanium oxynitride is not particularly limited, but is preferably 43.5 ° or less.
The titanium nitride, for example, include titanium black or the like, more specifically, for _example, low-order titanium oxide represented by _{TiO 2, Ti n O 2n-} 1 (1 ≦ n ≦ 20), and / or, forms containing TiN _x O _y titanium oxynitride represented by (0 <x <2.0,0.1 <y <2.0) can be mentioned. In the following description, titanium nitride (the diffraction angle 2θ is 42.5 ° to 42.8 °) and titanium oxynitride (the diffraction angle 2θ is more than 42.8 °) are collectively referred to as titanium nitride. The form will be described.
Further, the titanium nitride may be used as particles in which other atoms are further mixed. For example, the titanium nitride may be used as titanium nitride-containing particles further containing an atom (preferably a sulfur atom) selected from the elements of Groups 13 to 17 of the periodic table. The same applies to other metal nitrides, and the metal nitride, which is a combination of the metal nitride and the oxynitride metal, may be used as particles in which other atoms are further mixed. For example, the metal nitride may be used as metal nitride-containing particles further containing an atom (preferably a sulfur atom) selected from the elements of Groups 13 to 17 of the Periodic Table.

When the X-ray diffraction spectrum of titanium nitride is measured using CuKα ray as an X-ray source, TiN has a peak derived from the (200) plane as the strongest peak near 2θ = 42.5 °, and TiO is ( 200) A peak derived from the plane is observed near 2θ = 43.4 °. On the other hand, most peaks not strength strong peak is anatase TiO ₂ is derived from the (200) plane in the vicinity 2 [Theta] = 48.1 °, rutile TiO ₂ and a peak derived from (200) plane is 2 [Theta] = 39 It is observed near 2 °. Therefore, as the titanium oxynitride contains more oxygen atoms, the peak position shifts to a higher angle side with respect to 42.5 °.

When the titanium nitride contains titanium oxide TiO ₂ , the peak derived from anatase-type TiO ₂ (101) is derived from rutile-type TiO ₂ (110) in the vicinity of 2θ = 25.3 ° as the strongest peak. The peak is seen near 2θ = 27.4 °. However, TiO ₂ is white and causes a factor of lowering the light-shielding property of the light-shielding film obtained by curing the curable composition, so that it is preferably reduced to the extent that it is not observed as a peak.

From the half-value width of the peak obtained by the above-mentioned measurement of the X-ray diffraction spectrum, the crystallite size constituting the titanium nitride can be obtained. The crystallite size can be calculated using Scheller's equation.

The crystallite size constituting the titanium nitride is preferably 50 nm or less, preferably 20 nm or more. When the crystallite size is 20 to 50 nm, the cured film formed by using the curable composition tends to have higher ultraviolet (particularly i-ray (wavelength 365 nm)) transmittance and more photosensitive curability. The composition is obtained.

The specific surface area of the titanium nitride is not particularly limited, but can be determined by the BET (Brunauer, Emmett, Teller) method. The specific surface area of the titanium nitride is preferably ^{5~100m 2 / g, 10~60m 2 /} g is more preferable.

The method for producing the black pigment is not particularly limited, and a known production method can be used, and examples thereof include a gas phase reaction method. Examples of the gas phase reaction method include an electric furnace method and a thermal plasma method, but the thermal plasma method is preferable in that impurities are less mixed, the particle diameters are easily uniform, and the productivity is high.
In the thermal plasma method, the method for generating thermal plasma is not particularly limited, and examples thereof include DC arc discharge, multi-layer arc discharge, high frequency (RF) plasma, hybrid plasma, etc., and there is little contamination of impurities from the electrodes. High frequency plasma is more preferred.
The specific method for producing the black pigment by the thermal plasma method is not particularly limited, but for example, as a method for producing the titanium nitride, a method of reacting titanium tetrachloride with ammonia gas in a plasma flame (Japanese Patent Laid-Open No. 2-22110). No.), a method of evaporating titanium powder with high-frequency thermal plasma, introducing nitrogen as a carrier gas, and nitriding and synthesizing in the cooling process (Japanese Patent Laid-Open No. 61-11140), and ammonia gas at the periphery of the plasma. Examples thereof include a method of blowing (Japanese Patent Laid-Open No. 63-85007).
However, the method for producing a black pigment is not limited to the above, and the production method is not limited as long as a black pigment having desired physical properties can be obtained.

The black pigment may contain a layer of a silicon-containing compound (hereinafter referred to as "silicon-containing compound") on its surface. That is, the (acid) nitride of the metal atom may be coated with a silicon-containing compound to obtain a black pigment.
The method for coating the (acid) nitride of the metal atom is not particularly limited, and a known method can be used. For example, it is described in JP-A-53-33228, page 2, lower right to page 4, upper right. Method (using (acid) nitride of metal atom instead of titanium oxide), method described in paragraphs 0015 to 0043 of JP-A-2008-69193 (instead of fine titanium dioxide, (acid) of metal atom. ) Using a nitride), the methods described in paragraphs 0020 and 0124 to 0138 of JP-A-2016-74870 (using (acid) nitride of a metal atom instead of metal oxide fine particles). The above contents are incorporated herein by reference.

The content of the black pigment in the curable composition is preferably 40 to 70% by mass, more preferably 45 to 70% by mass, still more preferably 50 to 65% by mass, based on the total solid content of the curable composition. ..
By setting the content in such a range, it is easy to set the optical density of the curable composition layer formed from the curable composition in a desired range.
One type of black pigment may be used alone, or two or more types may be used in combination. When two or more kinds of black pigments are used in combination, the total content is preferably within the above range.

<Colorant>
The curable composition may contain a colorant other than the black pigment. The colorant is not particularly limited, and a known colorant can be used. As the colorant, various known pigments (coloring pigments), dyes (coloring dyes) and the like can be used.
The content of the colorant in the curable composition is not particularly limited, but is preferably 20 to 99% by mass, more preferably 20 to 80% by mass, based on the total solid content of the curable composition.
One type of colorant may be used alone, or two or more types may be used in combination. When two or more kinds of colorants are used in combination, the total content is preferably within the above range.

Examples of the coloring dye include chromatic dyes (chromatic dyes) such as R (red), G (green), and B (blue), as described in paragraphs 0027 to 0200 of JP-A-2014-42375. Colorants can also be used. Also, black dye can be used.
As the coloring pigment, for example, chromatic pigments (chromatic pigments) such as R (red), G (green), and B (blue) can also be used.

(Pigment)
The pigment used as the colorant may be an inorganic pigment or an organic pigment.

-Inorganic pigment The inorganic pigment is not particularly limited, and a known inorganic pigment can be used.
Examples of inorganic pigments include zinc chromate, lead white, lithopon, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, lead tan, iron oxide red, chrome yellow, and zinc yellow (zinc yellow 1 type, Zinc Oxide (2 types), Ultramarine Blue, Prussian Blue (Ferrosian Iron Potassium) Zinc Congray, Placeozim Yellow, Chromium Titanium Yellow, Chromium Green, Peacock, Victoria Green, Prussian Blue (unrelated to Prussian Blue), Vanadium Zinc Chrysanthemum Blue, Examples include chrome tin pink, ceramic red, and salmon pink.
The inorganic pigment may be surface-modified. For example, an inorganic pigment which has been surface-modified with a surface treatment agent having both a silicone group and an alkyl group can be mentioned, and the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned.

Pigments with infrared absorption can also be used.
As the pigment having infrared absorption, a tungsten compound, a metal boride and the like are preferable, and among them, a tungsten compound is preferable from the viewpoint of excellent light-shielding property at wavelengths in the infrared region. In particular, a tungsten compound is preferable from the viewpoint of excellent light absorption wavelength region of the oxime polymerization initiator and the visible light region, which are related to the curing efficiency by exposure.

Two or more of these pigments may be used in combination, or may be used in combination with a dye described later. To adjust the tint and to enhance the light-shielding property in the desired wavelength region, for example, a pigment having black or infrared light-shielding property is chromatic colors such as red, green, yellow, orange, purple, and blue. Examples thereof include a form in which a pigment or a dye described later is mixed. It is preferable to mix a red pigment or dye, or a purple pigment or dye with a pigment having an infrared light-shielding property, and more preferably to mix a red pigment with a pigment having an infrared light-shielding property.
Further, an infrared absorber described later may be added.

-Organic pigments Examples of organic pigments include Color Index (CI) Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18, 20, 24, 31, 32, 34, 35, 35: 1,36,36: 1,37,37: 1,40,42,43,53,55,60,61,62,63,65,73, 74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc.,
C. I. Pigment Orange 2,5,13,16,17: 1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73, etc. ,
C. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48: 1,48: 2,48: 3,48: 4, 49,49: 1,49: 2,52: 1,52: 2,53: 1,57: 1,60: 1,63: 1,66,67,81: 1,81: 2,81: 3, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279, etc.;
C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc .;
C. I. 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 .;
Can be mentioned. The pigment may be used alone or in combination of two or more.

(dye)
Examples of the dye include JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-A-2592207, and US Pat. No. 4,808.501. , U.S. Pat. No. 5,667,920, U.S. Patent No. 505950, JP-A-5-333207, JP-A-6-35183, JP-A-6-511115, JP-A-6-194828, etc. The disclosed dyes can be used. When classified as a chemical structure, pyrazole azo compound, pyromethene compound, anilino azo compound, triphenylmethane compound, anthraquinone compound, benzylidene compound, oxonor compound, pyrazorotriazole azo compound, pyridone azo compound, cyanine compound, phenothiazine compound, or pyropyrazole azomethine. Compounds and the like can be used. Moreover, you may use a dye multimer as a dye. Examples of the dye multimer include compounds described in JP-A-2011-213925 and JP-A-2013-041097. Further, a polymerizable dye having an intramolecular polymerizable dye may be used, and examples of commercially available products include the RDW series manufactured by Wako Pure Chemical Industries, Ltd.

(Infrared absorber)
The colorant may further contain an infrared absorber.
The infrared absorber means a compound having absorption in a wavelength region in the infrared region (preferably, a wavelength of 650 to 1300 nm). As the infrared absorber, a compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferable.
Examples of the colorant having such spectral characteristics include pyrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, and quaterylene. Examples thereof include compounds, dithiol metal complex compounds, and croconium compounds.
As the phthalocyanine compound, the naphthalocyanine compound, the iminium compound, the cyanine compound, the squarylium compound, and the croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP2010-111750A may be used, and the contents thereof are described herein. Incorporated into the book. For the cyanine compound, for example, "Functional dye, Shin Ogawara / Ken Matsuoka / Eijiro Kitao / Tsuneaki Hirashima, Kodansha Scientific" can be referred to, and this content is incorporated in the present specification.

Examples of the colorant having the above spectral characteristics include the compounds disclosed in paragraphs 0004 to 0016 of JP-A-07-164729 and / or the compounds disclosed in paragraphs 0027 to 0062 of JP-A-2002-146254, JP 2011-164583. Near-infrared absorbing particles composed of crystallites of oxides containing Cu and / or P disclosed in paragraphs 0034 to 0067 of the publication and having a number average aggregated particle diameter of 5 to 200 nm can also be used.

As the compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm, at least one selected from the group consisting of a cyanine compound, a pyrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound is preferable.
The infrared absorber is preferably a compound that dissolves in water at 25 ° C. in an amount of 1% by mass or more, and more preferably a compound that dissolves in water at 25 ° C. in an amount of 10% by mass or more. By using such a compound, the solvent resistance is improved.
For the pyrrolopyrrole compound, paragraphs 0049 to 0062 of JP2010-222557A can be referred to, and the contents thereof are incorporated in the present specification. The cyanine compound and the squarylium compound are described in paragraphs 0022 to 0063 of International Publication No. 2014/088063, paragraphs 0053 to 0118 of International Publication No. 2014/03628, paragraphs 0028 to 0074 of JP2014-59550A, and International Publication 2012 /. Paragraphs 0013 to 0091 of JP-A-169447, paragraphs 0019 to 0033 of JP-A-2015-176046, paragraphs 0053 to 00099 of JP-A-2014-63144, paragraphs 0085-0150 of JP-A-2014-52431, JP-A. Paragraphs 0076 to 0124 of JP2014-444301, paragraphs 0045 to 0078 of JP2012-8532, paragraphs 0027 to 0067 of JP2015-172102, paragraphs 0029 to 0067 of JP2015-172004, Paragraphs 0029 to 0085 of JP-A-2015-40895, paragraphs 0022 to 0036 of JP-A-2014-126642, paragraphs 0011-0017 of JP-A-2014-148567, and paragraphs 0010-0025 of JP-A-2015-157893. Paragraphs, paragraphs 0013 to 0026 of JP2014-095007, paragraphs 0013 to 0047 of JP2014-80487, and paragraphs 0007 to 0028 of JP2013-227403 can be referred to. Incorporated herein.

<Polymerizable compound>
The curable composition contains a polymerizable compound. In the present specification, the polymerizable compound is intended to be a compound that polymerizes under the action of a polymerization initiator described later, and is intended to be a component different from the dispersant and the alkali-soluble resin described later.

The content of the polymerizable compound in the curable composition is not particularly limited, but is preferably 5 to 30% by mass with respect to the total solid content of the curable composition. As the polymerizable compound, one type may be used alone, or two or more types may be used in combination. When two or more kinds of polymerizable compounds are used in combination, the total content is preferably within the above range.
The molecular weight of the polymerizable compound is preferably 2000 or less.

The polymerizable compound is preferably a compound containing one or more groups containing an ethylenically unsaturated bond (hereinafter, also simply referred to as "ethylene unsaturated group"), more preferably two or more, and three or more. The compound contained is more preferable, and the compound containing 5 or more is particularly preferable. The upper limit is, for example, 15 or less. Examples of the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.

As the polymerizable compound, for example, the compounds described in paragraph 0050 of JP2008-260927 and paragraph 0040 of JP2015-68893 can be used, and the above contents are incorporated in the present specification. Is done.

The polymerizable compound may be in any chemical form such as, for example, a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof.
The polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities.

As the polymerizable compound, a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100 ° C. or higher under normal pressure is also preferable. For example, the compounds described in paragraphs 0227 of JP2013-29760A and paragraphs 0254 to 0257 of JP2008-292970 can be referred to, and the contents thereof are incorporated in the present specification.

The polymerizable compounds are dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayakusha), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; manufactured by Nippon Kayakusha), and di. Pentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayakusha), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayakusha, A-DPH-) 12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and structures in which these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues (for example, SR454, SR499 commercially available from Sartmer) are preferable. .. These oligomer types can also be used. Further, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can also be used.
The preferred embodiments of the polymerizable compound are shown below.

The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. As the polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and an acid is obtained by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. A polymerizable compound having a group is more preferable, and in this ester, those in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol are further preferable. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Corporation.

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

As the polymerizable compound, a compound containing a caprolactone structure is also a preferable embodiment.
The compound containing a caprolactone structure is not particularly limited as long as the caprolactone structure is contained in the molecule, and for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, dimethylolpropane, pentaerythritol, and dipenta are used. Ε-caprolactone-modified polyfunctional (meth) obtained by esterifying polyhydric alcohols such as erythritol, tripentaerythritol, glycerin, diglycerol, or trimethylolmelamine with (meth) acrylic acid and ε-caprolactone. ) Acrylate can be mentioned. Of these, a compound containing a caprolactone structure represented by the following formula (Z-1) is preferable.

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

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

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

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

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

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

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

The compound represented by the formula (Z-4) or the formula (Z-5) may be used alone or in combination of two or more. In particular, among the forms in which all 6 Xs are acryloyl groups in the formula (Z-5), the compounds in which all 6 Xs are acryloyl groups in the formula (Z-5), and the 6 Xs. An embodiment in which at least one is a mixture with a compound having a hydrogen atom is preferable. With such a configuration, the developability can be further improved.

The total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, more preferably 50% by mass or more.
Among the compounds represented by the formula (Z-4) or the formula (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative is more preferable.

Moreover, the polymerizable compound may contain a cardo skeleton.
As the polymerizable compound containing a cardo skeleton, a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable.
Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, Oncoat EX series (manufactured by Nagase & Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).
As the polymerizable compound, a compound containing an isocyanuric acid skeleton as a central core is also preferable. Examples of such a polymerizable compound include NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
The content of ethylenically unsaturated groups in the polymerizable compound (intended to be the value obtained by dividing the number of ethylenically unsaturated groups in the polymerizable compound by the molecular weight (g / mol) of the polymerizable compound) is 5.0 mmol / It is preferably g or more. The upper limit is not particularly limited, but is generally 20.0 mmol / g or less.
When the curable composition contains a plurality of types of polymerizable compounds and their double bond equivalents are not the same, the mass ratio of each polymerizable compound in the total polymerizable compound and each polymerizable compound. It is preferable that the total value of the products of the compounds with the double bond equivalents is within the above range.

<Resin>
The curable composition preferably contains a resin. Examples of the resin include a dispersant and an alkali-soluble resin.
The content of the resin in the curable composition is not particularly limited, but is preferably 3 to 60% by mass, more preferably 5 to 40% by mass, based on the total solid content of the curable composition. As the resin, one type may be used alone, or two or more types may be used in combination. When two or more kinds of resins are used in combination, the total content is preferably within the above range.
The molecular weight of the resin is over 2000. When the molecular weight of the resin is polydisperse, the weight average molecular weight is more than 2000.

(Dispersant)
The curable composition preferably contains a dispersant. In this specification, the dispersant is intended to be a compound different from the alkali-soluble resin described later.
The content of the dispersant in the curable composition is not particularly limited, but is preferably 2 to 40% by mass, more preferably 5 to 30% by mass, based on the total solid content of the curable composition.
The dispersant may be used alone or in combination of two or more. When two or more kinds of dispersants are used in combination, the total content is preferably within the above range.

As the dispersant, for example, a known dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
Dispersants include polymer dispersants [for example, polyamide amines and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylics. Copolymers, naphthalene sulfonic acid formarin condensates], polyoxyethylene alkyl phosphates, polyoxyethylene alkyl amines, pigment derivatives and the like.
Polymer compounds can be further classified into linear polymers, terminally modified polymers, graft-type polymers, and block-type polymers based on their structures.

-Polymer compound The polymer compound is adsorbed on the surface of a dispersant such as a black pigment and other pigments to be used in combination if desired (hereinafter, the black pigment and other pigments are collectively referred to as "pigment"). , Acts to prevent reaggregation of the disperse. Therefore, a terminal-modified polymer, a graft-type (containing a polymer chain) polymer, or a block-type polymer containing an anchor site on the pigment surface is preferable.

The polymer compound may contain a curable group.
Examples of the curable group include an ethylenically unsaturated group (for example, (meth) acryloyl group, vinyl group, styryl group, etc.), a cyclic ether group (for example, epoxy group, oxetanyl group, etc.) and the like. However, it is not limited to these.
Of these, an ethylenically unsaturated group is preferable as the curable group in that polymerization can be controlled by a radical reaction. The ethylenically unsaturated group is more preferably a (meth) acryloyl group.

The resin containing a curable group preferably contains at least one selected from the group consisting of a polyester structure and a polyether structure. In this case, the main chain may contain a polyester structure and / or a polyether structure, and as described later, when the resin contains a structural unit containing a graft chain, the polymer The chain may contain a polyester structure and / or a polyether structure.
As the resin, it is more preferable that the polymer chain contains a polyester structure.

The polymer compound preferably contains a structural unit containing a graft chain. In addition, in this specification, "structural unit" is synonymous with "repeating unit".
Since the polymer compound containing a structural unit containing such a graft chain has an affinity with a solvent due to the graft chain, the dispersibility of pigments and the like and the dispersion stability after aging (stability with time) It is excellent in. Further, due to the presence of the graft chain, the polymer compound containing the structural unit containing the graft chain has an affinity with the polymerizable compound or other resin that can be used in combination. As a result, alkaline development is less likely to generate residues.
The longer the graft chain, the higher the steric repulsion effect and the better the dispersibility of pigments and the like. On the other hand, if the graft chain is too long, the adsorption force to the pigment or the like is lowered, and the dispersibility of the pigment or the like tends to be lowered. Therefore, the graft chain preferably has an atomic number of 40 to 10,000 excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and an atomic number excluding hydrogen atoms. It is more preferably 60 to 500.
Here, the graft chain indicates from the root of the main chain of the copolymer (atom bonded to the main chain in the group branched from the main chain) to the end of the group branched from the main chain.

The graft chain preferably contains a polymer structure, and examples of such a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide. Examples include a structure and a polyether structure.
The graft chain is selected from the group consisting of a polyester structure, a polyether structure, and a poly (meth) acrylate structure in order to improve the interoperability between the graft chain and the solvent and thereby enhance the dispersibility of pigments and the like. A graft chain containing at least one of the above is preferable, and a graft chain containing at least one of a polyester structure and a polyether structure is more preferable.

The macromonomer containing such a graft chain (a monomer having a polymer structure and binding to the main chain of a copolymer to form a graft chain) is not particularly limited, but has a reactive double-binding group. The contained macromonomer can be preferably used.

Commercially available macromonomers that correspond to structural units containing graft chains contained in polymer compounds and are suitably used for the synthesis of polymer compounds include AA-6 (trade name, manufactured by Toa Synthetic Co., Ltd.) and AA-10. (Product name, manufactured by Toa Synthetic Co., Ltd.), AB-6 (Product name, manufactured by Toa Synthetic Co., Ltd.), AS-6 (Product name, manufactured by Toa Synthetic Co., Ltd.), AN-6 (Product name, manufactured by Toa Synthetic Co., Ltd.), AW -6 (trade name, manufactured by Toa Synthetic), AA-714 (trade name, manufactured by Toa Synthetic), AY-707 (trade name, manufactured by Toa Synthetic), AY-714 (trade name, manufactured by Toa Synthetic). , AK-5 (trade name, manufactured by Toa Synthetic), AK-30 (trade name, manufactured by Toa Synthetic), AK-32 (trade name, manufactured by Toa Synthetic), Blemmer PP-100 (trade name, NOF) Blemmer PP-500 (trade name, manufactured by NOF Corporation), 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), Blemmer PME-4000 (trade name, manufactured by NOF), Blemmer PSE-400 (trade name, manufactured by NOF), Blemmer PSE-1300 (trade name, manufactured by NOF) (Manufactured by NOF CORPORATION) or Blemmer 43PAPE-600B (trade name, manufactured by NOF CORPORATION) or the like is used. Among these, AA-6 (trade name, manufactured by Toagosei), AA-10 (trade name, manufactured by Toagosei), AB-6 (trade name, manufactured by Toagosei), AS-6 (trade name, manufactured by Toagosei). (Toagosei Co., Ltd.), AN-6 (trade name, manufactured by Toagosei Co., Ltd.), or Blemmer PME-4000 (trade name, manufactured by Nichiyu Co., Ltd.) is preferable.

The dispersant preferably contains at least one structure selected from the group consisting of methyl polyacrylate, polymethyl methacrylate, and cyclic or chain polyester, and methyl polyacrylate, polymethacrylic acid. It is more preferable to contain at least one structure selected from the group consisting of methyl and chain polyester, and it is preferable to contain a methyl polyacrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. It is more preferable to contain at least one structure selected from the group consisting of. The dispersant may be a dispersant containing the above structures alone in one dispersant, or may be a dispersant containing a plurality of these structures in one dispersant.
Here, the polycaprolactone structure refers to a structure containing a ring-opened structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure refers to a structure containing a ring-opened structure of δ-valerolactone as a repeating unit.
Specific examples of the dispersant containing a polycaprolactone structure include dispersants having j and k of 5 in the following formula (1) and the following formula (2). Specific examples of the dispersant containing the polyvalerolactone structure include dispersants in which j and k in the following formula (1) and the following formula (2) are 4.
Examples of dispersants containing polymethyl acrylate structure, X ⁵ in formula (4) is a hydrogen atom, R ⁴ can be cited dispersants are methyl groups. Specific examples of dispersants containing polymethyl methacrylate structure, X ⁵ in formula (4) is a methyl group, R ⁴ can be cited dispersants are methyl groups.

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

In formulas (1) to (4), W ¹ , W ² , W ³ and W ⁴ independently represent an oxygen atom or NH, respectively. It is preferable that W ¹ , W ² , W ³ and W ⁴ are 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 each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (carbon atoms) from the viewpoint of synthetic constraints. It is preferable that they are each independently a hydrogen atom or a methyl group, and a methyl group is further preferable.

In the formulas (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly structurally restricted. Specific examples of the divalent linking groups represented by Y ¹ , Y ² , Y ³ , and Y ⁴ include the following linking groups (Y-1) to (Y-21). Be done. In the structure shown below, A and B mean the binding sites with the left terminal group and the right terminal group in the formulas (1) to (4), respectively. Of the structures shown below, (Y-2) or (Y-13) is more preferable because of the ease of synthesis.

In formulas (1) to (4), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, but specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. And so on. Among these, as the organic group represented by Z ¹ , Z ² , Z ³ and Z ⁴ , a group containing a steric repulsion effect is preferable from the viewpoint of improving dispersibility, and each group has an independent carbon number. Alkyl groups or alkoxy groups of 5 to 24 are more preferable, and among them, branched alkyl groups having 5 to 24 carbon atoms, cyclic alkyl groups having 5 to 24 carbon atoms, or alkoxy groups having 5 to 24 carbon atoms are particularly preferable. Groups are even more preferred. The alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

In the formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500.
Further, in the equations (1) and (2), j and k each independently represent an integer of 2 to 8. J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and more preferably 5 from the viewpoint of stability over time and developability of the composition.
Further, in the formulas (1) and (2), n and m are preferably an integer of 10 or more, and more preferably an integer of 20 or more. When the dispersant contains a polycaprolactone structure and a polyvalerolactone structure, the sum of the number of repetitions of the polycaprolactone structure and the number of repetitions of the polyvalerolactone is preferably an integer of 10 or more, preferably 20 or more. Integers are more preferred.

In the formula (3), R ³ represents a branched chain or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. when p is 2 to 500, R ³ existing in plural numbers may be different from one another the same.
In the formula (4), R ⁴ represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly structurally limited. The R ^4, a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, the alkyl group includes a linear alkyl group having 1 to 20 carbon atoms, a branched chain alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. Preferably, a linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is further preferable. In the formula (4), when q is 2 to 500, a plurality of X ⁵ and R ⁴ present in the graft copolymer may be the same or different from each other.

In addition, the polymer compound can contain two or more structural units containing graft chains having different structures. That is, the molecules of the polymer compound may contain structural units represented by the formulas (1) to (4) having different structures from each other, and n, m, p in the formulas (1) to (4). When, and q represent integers of 2 or more, respectively, in equations (1) and (2), j and k may contain structures different from each other in the side chain, and equations (3) and (4) may be included. in), R ^3, R 4 a plurality present in the ^molecule, and, X ⁵ may be different be the same as each other.

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

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

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

Wherein (3A) or ^(3B), X ^3, Y 3, ^{Z 3} and, p is, ^{X 3,} Y 3, ^{Z 3} in Formula (3), and has the same meaning as p, preferred ranges are also the same Is.

The polymer compound more preferably contains the structural unit represented by the formula (1A) as the structural unit containing the graft chain.

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

-Hydrophobic structural unit Further, the polymer compound preferably contains a hydrophobic structural unit different from the structural unit containing the graft chain (that is, not corresponding to the structural unit containing the graft chain). However, in the present specification, the hydrophobic structural unit is a structural unit having no acid group (for example, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).

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

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

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

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

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

L is a single bond or divalent linking group. The divalent linking group includes a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group) and a divalent aromatic group (for example, an arylene group). , substituted arylene group), a divalent heterocyclic group an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group ^{(-NR 31} -, wherein ^{R 31} Is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), and a combination thereof.

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

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

The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocycle. Another heterocycle, an aliphatic ring, or an aromatic ring may be condensed with the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of substituents are halogen atom, hydroxyl group, oxo group (= O), thioxo group (= S), imino group (= NH), substituted imino group (= N-R ³² , where R ³² is an aliphatic group. Groups, aromatic groups or heterocyclic groups), aliphatic groups, aromatic groups and heterocyclic groups can be mentioned.

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

As Z, an aliphatic group (for example, an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group) and an aromatic group (for example, an aryl group, a substituted aryl group, an arylene group, a substituted arylene group) , A heterocyclic group, or a combination thereof. These groups an oxygen atom (-O-), sulfur atom (-S-), an imino group (-NH-), a substituted imino group ^{(-NR 31} -, wherein ^{R 31} is an aliphatic group, an aromatic A group or a heterocyclic group) or a carbonyl group (−CO−) may be contained.

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group further includes a ring-assembled hydrocarbon group and a cross-linked ring-type hydrocarbon group. Examples of the ring-assembled hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -Includes cyclohexylphenyl groups and the like. Examples of the crosslinked cyclic hydrocarbon ring include 2 such as pinan, bornan, norpinan, norbornane, and bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.). Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredane, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, and tricyclo [4.3.1.1 ^2,5 ] undecane rings. , And tetracyclo [4.4.0.1 ^2,5 . 17 and ¹⁰ ] Dodecane and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene rings can be mentioned. In addition, the crosslinked cyclic hydrocarbon ring includes fused cyclic hydrocarbon rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and the like. A fused ring in which a plurality of 5- to 8-membered cycloalkane rings such as a perhydrophenanthrene ring are condensed is also included.
As the aliphatic group, a saturated aliphatic group is preferable to an unsaturated aliphatic group. In addition, 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 of the aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. Moreover, the aromatic group may have a substituent. Examples of substituents include halogen atoms, aliphatic groups, aromatic groups and heterocyclic groups. However, the aromatic group does not have an acid group as a substituent.

The heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocycle. Another heterocycle, an aliphatic ring or an aromatic ring may be condensed with the heterocycle. Moreover, the heterocyclic group may have a substituent. Examples of substituents are halogen atom, hydroxyl group, oxo group (= O), thioxo group (= S), imino group (= NH), substituted imino group (= N-R ³² , where R ³² is an aliphatic group. Groups, aromatic or heterocyclic groups), aliphatic groups, aromatic groups, and heterocyclic groups. However, the heterocyclic group does not have an acid group as a substituent.

In the above formula (iii), R ⁴ , R ⁵ , and R ⁶ are independently hydrogen atoms, halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.), and alkyl groups having 1 to 6 carbon atoms. Represents (eg, methyl group, ethyl group, propyl group, etc.), Z, or LZ. Here, L and Z are synonymous with those in the above. R ^{4, R 5} and, as the ^{R 6,} a hydrogen atom, or, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

As the monomer represented by the above formula (i), R ¹ , R ² and R ³ are hydrogen atoms or methyl groups, and L contains a single bond or an alkylene group or an oxyalkylene structure. A compound having a divalent linking group in which X is an oxygen atom or an imino group and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable.
Further, as the monomer represented by the above formula (ii), R ¹ is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. The base compound is preferred. Further, as the monomer represented by the above formula ^{(iii), R 4, R} 5, and, ^{R 6} is a hydrogen atom or a methyl group, Z is an aliphatic group, a heterocyclic group, or an aromatic The base compound is preferred.

Examples of typical compounds represented by the formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes and the like.
As examples of the representative compounds represented by the formulas (i) to (iii), the compounds described in paragraphs 089 to 093 of JP2013-249417A can be referred to, and the contents thereof are described herein. Is incorporated into.

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

-Functional groups capable of forming an interaction with pigments and the like High molecular compounds can introduce functional groups capable of forming interactions with pigments and the like. Here, it is preferable that the polymer compound further contains a structural unit containing a functional group capable of forming an interaction with a pigment or the like.
Examples of the functional group capable of forming an interaction with the pigment or the like include an acid group, a basic group, a coordinating group, and a reactive functional group.
When the polymer compound contains an acid group, a basic group, a coordinating group, or a functional group having reactivity, a structural unit containing an acid group, a structural unit containing a basic group, and a arrangement, respectively. It is preferable to contain a structural unit containing a positional group or a reactive structural unit.
In particular, when the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as an acid group, the polymer compound can be imparted with developability for pattern formation by alkali development.
That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as a dispersant that contributes to the dispersion of pigments and the like contains alkali-soluble in the above composition. The composition containing such a polymer compound has excellent light-shielding properties in the exposed portion and improves the alkali developability in the unexposed portion.
Further, when the polymer compound contains a structural unit containing an acid group, the polymer compound tends to be easily compatible with the solvent and the coatability tends to be improved.
This is because the acid group in the structural unit containing the acid group easily interacts with the pigment or the like, the polymer compound stably disperses the pigment or the like, and the viscosity of the polymer compound in which the pigment or the like is dispersed becomes low. It is presumed that this is because the polymer compound itself is easily dispersed stably.

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

Examples of the acid group which is a functional group capable of forming an interaction with a pigment or the like include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxyl group and the like, and a carboxylic acid group, a sulfonic acid group, and an acid group. , At least one of the phosphate groups is preferable, and a carboxylic acid group is more preferable. The carboxylic acid group has good adsorption power to pigments and the like, and has high dispersibility.
That is, the polymer compound preferably further contains a structural unit containing 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 containing an acid group.
The polymer compound may or may not contain a structural unit containing an acid group, but when it is contained, the content of the structural unit containing an acid group is the total mass of the polymer compound in terms of mass. On the other hand, it is preferably 5 to 80% by mass, and more preferably 10 to 60% by mass from the viewpoint of suppressing damage to the image intensity due to alkaline development.

Examples of the basic group which is a functional group capable of forming an interaction with a pigment or the like include a primary amino group, a secondary amino group, a tertiary amino group, a heterocycle containing an N atom, and an amide. A preferred basic group having a group or the like is a tertiary amino group in that it has a good adsorptivity to a pigment or the like and has high dispersibility. The polymer compound can contain one or more of these basic groups.
The polymer compound may or may not contain a structural unit containing a basic group, but when it is contained, the content of the structural unit containing a basic group is the total mass of the polymer compound. 0.01 to 50% by mass is preferable with respect to the mass, and 0.01 to 30% by mass is more preferable from the viewpoint of suppressing developmental inhibition.

Coordinating groups, which are functional groups capable of forming an interaction with pigments, and reactive functional groups include, for example, acetylacetoxy groups, trialkoxysilyl groups, isocyanate groups, acid anhydrides, and acidified groups. Things etc. can be mentioned. A preferable functional group is an acetylacetoxy group in that it has a good adsorptivity to a pigment or the like and has a high dispersibility of the pigment or the like. The polymer compound may have one or more of these groups.
The polymer compound may or may not contain a structural unit containing a coordinating group or a structural unit containing a reactive functional group, but if it is contained, the content of these structural units. Is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, based on the total mass of the polymer compound, from the viewpoint of suppressing developmental inhibition.

When the polymer compound contains a functional group capable of forming an interaction with a pigment or the like in addition to the graft chain, it suffices to contain a functional group capable of forming an interaction with the various pigments or the like described above. How these functional groups are introduced is not particularly limited, but the polymer compound is selected from structural units derived from the monomers represented by the following formulas (iv) to (vi). It preferably contains more than a species of structural unit.

In formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ each independently have a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 to 1. Represents an alkyl group of 6 (eg, methyl group, ethyl group, propyl group, etc.).
In formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ are preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, respectively, and each of them is independently a hydrogen atom or methyl. More preferably it is a group. In the general formula (iv), it is more preferable that R ¹² and R ¹³ are hydrogen atoms, respectively.

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

Further, L ₁ in the formulas (iv) to (v) represents a single bond or a divalent linking group. The definition of the divalent linking group is the same as the definition of the divalent linking group represented by L in the above formula (i).

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

In the formulas (iv) to (vi), Z ₁ represents a functional group capable of forming an interaction with a pigment or the like other than the graft chain, and is preferably a carboxylic acid group and a tertiary amino group, preferably a carboxylic group. It is more preferably an acid group.

In formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ are independently hydrogen atoms, halogen atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.), and alkyl groups having 1 to 6 carbon atoms (for example, fluorine atoms, chlorine atoms, bromine atoms, etc.). for example, a methyl group, an ethyl group, a propyl group, etc.), - _{Z 1,} or an _L 1 -Z _1. Wherein _{L 1} and _{Z 1} are the same meaning as _{L 1} and _{Z 1} in the above, it is the preferable examples. R ^{1
4, R 15} and, ^as the ^{R 16,} each independently represent a hydrogen atom, or preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

As the monomer represented by the formula (iv), R ¹¹ , R ¹² and R ¹³ are independently hydrogen atoms or methyl groups, and L ₁ is a divalent group containing an alkylene group or an oxyalkylene structure. A compound having a linking group in which X ₁ is an oxygen atom or an imino group and Z ₁ is a carboxylic acid group is preferable.
Further, as the monomer represented by the formula (v), R ¹¹ is a hydrogen atom or a methyl group, L ₁ is an alkylene group, Z ₁ is a carboxylic acid group, and Y is a methine group. Is preferred.
Further, as the monomers represented by the formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ are independently hydrogen atoms or methyl groups, L ₁ is a single bond or an alkylene group, and Z. A compound in which ₁ is a carboxylic acid group is preferable.

Representative examples of the monomers (compounds) represented by the formulas (iv) to (vi) are shown below.
Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction of a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) with succinic anhydride. A compound, a reaction product of a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule and phthalic acid anhydride, a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule, and a tetrahydroxyphthalic acid anhydride. Reaction product of, a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule and crotonic acid anhydride Examples thereof include a reaction product with, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, 4-hydroxyphenylmethacrylate and the like.

The content of the structural unit containing a functional group capable of forming an interaction with a pigment or the like is the total mass of the polymer compound from the viewpoint of interaction with the pigment or the like, stability over time, and permeability to a developing solution. On the other hand, 0.05 to 90% by mass is preferable, 1.0 to 80% by mass is more preferable, and 10 to 70% by mass is further preferable.

-Other structural units Further, the polymer compound is a structural unit containing a graft chain, a hydrophobic structural unit, and a pigment for the purpose of improving various performances such as image intensity, as long as the effects of the present invention are not impaired. Other structural units having various functions (for example, structural units containing functional groups having an affinity with a solvent, which will be described later), which are different from the structural units containing functional groups capable of forming an interaction with the above. You may also have more.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
The polymer compound can use one or more of these other structural units, and the content thereof is preferably 0 to 80% by mass, preferably 10 to 80% by mass, based on the total mass of the polymer compound. More preferably, it is 60% by mass or less. Sufficient pattern formation is maintained when the content is in the above range.

-Physical properties of the polymer compound The acid value of the polymer compound is preferably in the range of 0 mg to 250 mgKOH / g, more preferably in the range of 10 to 200 mgKOH / g, and even more preferably in the range of 20 to 120 mgKOH / g.
When the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development when forming a cured film can be suppressed more effectively. Further, when the acid value of the polymer compound is 10 mgKOH / g or more, the alkali developability becomes better. Further, when the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of pigments and the like 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 specification, the acid value can be calculated from, for example, the average content of acid groups in the compound. Further, a resin having a desired acid value can be obtained by changing the content of the structural unit containing an acid group which is a constituent component of the resin.

The weight average molecular weight of the polymer compound is preferably 4,000 to 300,000, more preferably 5,000 to 200,000, still more preferably 6,000 to 100,000. It is particularly preferably 10,000 to 50,000.
The polymer compound can be synthesized based on a known method.

Specific examples of the polymer compound include "DA-7301" manufactured by Kusumoto Kasei Co., Ltd., "Disperbyk-101 (polyamidoamine phosphate)" manufactured by BYK Chemie, 107 (carboxylic acid ester), and 110 (polymer containing an acid group). ), 111 (phosphate dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer) "," BYK-P104, P105 (high molecular weight non-polymer) "Saturated polycarboxylic acid", EFKA 4047, 4050-4010-4165 (polyurethane type), EFKA4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyesteramide), 5765 ( High molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”, Ajinomoto Fine Techno Co., Ltd.“ Ajispar PB821, PB822, PB880, PB881 ” TG-710 (urethane oligomer) ”,“ Polyflow No. 50E, No. 300 (acrylic copolymer) ”, Kusumoto Kasei Co., Ltd.“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polyvalent carboxylic acid) ), # 7004 (polyether ester), DA-703-50, DA-705, DA-725 ", Kao" Demor RN, N (naphthalene sulfonate formalin polycondensate), MS, C, SN-B (Aromatic formalin sulfonate polycondensate) ”,“ Homogenol L-18 (polymer polycarboxylic acid) ”,“ Emargen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ Acetamine 86 (stearyl) Aminacetate) ”, Nippon Lubrizol“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymers containing functional parts at the ends) ), 24000, 28000, 32000, 38500 (graft copolymer) ", Nikko Chemicals" Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ", Kawaken Fine Chemicals Hinoact T-8000E, etc., Shin-Etsu Chemical Industry, Organosiloxane Polymer KP-341, Yusho "W001: Cationic Surfactant", Polyoxyethylene Lauryl Ether, Polyoxyethylene Stearyl Ether, Polyoxyethylene Oleyl Ether, Polyoxyethylene Octylphenyl Ether, Polyoxyethylene Nonylphenyl Ether, Polyethylene Glycol Dilaurate, Polyethylene Nonionic surfactants such as glycol distearate and sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", Morishita Sangyo "EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100" , EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 ", San Nopco's" Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 "and other polymer dispersants, ADEKA's" Adecapluronic L31 " , F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ", and Sanyo Kasei" Ionet (trade name) S -20 ”and the like. Further, Acrybase FFS-6752 and Acrybase FFS-187 can also be used.

It is also preferable to use an amphoteric resin containing an acid group and a basic group. The amphoteric resin is preferably a resin having an acid value of 5 mgKOH / g or more and an amine value of 5 mgKOH / g or more.
Examples of commercially available amphoteric resins include DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2001, DISPERBY, manufactured by Big Chemie. Examples thereof include DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajinomoto Fine-Techno's Ajispar PB821, Ajispar PB822, and Ajispar PB881.
These polymer compounds may be used alone or in combination of two or more.

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

Further, as the dispersant, in addition to the above-mentioned polymer compounds, graft copolymers of paragraphs 0037 to 0115 of JP-A-2010-106268 (paragraphs 0075 to 0133 of the corresponding US2011 / 0124824) can be used. The contents of are hereby incorporated into this specification.
In addition to the above, it also contains a side chain structure in which acidic groups of paragraphs 0028 to 0084 (corresponding paragraphs 0075 to 0133 of US2011 / 0279759) of JP2011-153283A are bonded via a linking group. Polymer compounds containing the constituents are available, the contents of which can be incorporated and incorporated herein by reference.

Further, as the dispersant, the resins described in paragraphs 0033 to 0049 of JP-A-2016-109763 can also be used, and the contents thereof are incorporated in the present specification.

(Alkali-soluble resin)
The curable composition preferably contains an alkali-soluble resin. In the present specification, the alkali-soluble resin is intended to be a resin containing a group (alkali-soluble group) that promotes alkali solubility, and is intended to be a resin different from the dispersant described above.
The content of the alkali-soluble resin in the curable composition is not particularly limited, but is preferably 1 to 30% by mass, more preferably 1 to 15% by mass, based on the total solid content of the curable composition.
One type of alkali-soluble resin may be used alone, or two or more types may be used in combination. When two or more kinds of alkali-soluble resins are used in combination, the total content is preferably within the above range.

Examples of the alkali-soluble resin include resins containing at least one alkali-soluble group in the molecule, and examples thereof include polyhydroxystyrene resin, polysiloxane resin, (meth) acrylic resin, (meth) acrylamide resin, and (meth). Acrylic / (meth) acrylamide copolymer resin, epoxy resin, polyimide resin and the like can be mentioned.

Specific examples of the alkali-soluble resin include a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound.
The unsaturated carboxylic acid is not particularly limited, but is a monocarboxylic acid such as (meth) acrylic acid, crotonic acid, and vinylacetic acid; a dicarboxylic acid such as itaconic acid, maleic acid, and fumaric acid, or an acid anhydride thereof. Products; and polyvalent carboxylic acid monoesters such as mono (2- (meth) acryloyloxyethyl); and the like.

Examples of the copolymerizable ethylenically unsaturated compound include methyl (meth) acrylate. Further, the compounds described in paragraphs 0027 of JP-A-2010-97210 and paragraphs 0036 to 0037 of JP-A-2015-68893 can also be used, and the above contents are incorporated in the present specification.

Further, a copolymerizable ethylenically unsaturated compound which contains an ethylenically unsaturated group in the side chain may be used in combination. As the ethylenically unsaturated group, a (meth) acrylic acid group is preferable. The acrylic resin containing an ethylenically unsaturated group in the side chain is, for example, an addition reaction of an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to the carboxylic acid group of the acrylic resin containing a carboxylic acid group. Can be obtained.

As the alkali-soluble resin, an alkali-soluble resin containing a curable group is also preferable.
Examples of the curable group include curable groups that may be contained in the above-mentioned polymer compound, and the preferred range is also the same.
As the alkali-soluble resin containing a curable group, an alkali-soluble resin having a curable group in the side chain or the like is preferable. Examples of the alkali-soluble resin containing a curable group include Dianal NR series (manufactured by Mitsubishi Rayon), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamlock Co., Ltd.), Viscort R-264, and KS resist 106 (manufactured by Ltd.). All are manufactured by Osaka Organic Chemical Industry Co., Ltd., Cyclomer P series (for example, ACA230AA), Praxel CF200 series (all manufactured by Daicel Co., Ltd.), Ebeclyl3800 (manufactured by Daicel Ornex), and Acrylic RD-F8 (Nippon Catalyst Co., Ltd.). Made) and the like.

Examples of the alkali-soluble resin include Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Application Laid-Open No. 54-34327, Japanese Patent Application Laid-Open No. 58-125777, Japanese Patent Application Laid-Open No. 54-25957, Japanese Patent Application Laid-Open No. 54-92723, and Japanese Patent Application Laid-Open No. 59- A radical polymer containing a carboxylic acid group in the side chain described in Japanese Patent Application Laid-Open No. 53863 and JP-A-59-71048; European Patent No. 9993966, European Patent No. 1204000, and JP-A-2001-318436. Acetal-modified polyvinyl alcohol-based binder resin containing an alkali-soluble group, polyvinylpyrrolidone; polyethylene oxide; alcohol-soluble nylon, and 2,2-bis- (4-hydroxyphenyl) -propane Polyethers and the like which are reactants with epichlorohydrin; and the polyimide resin described in International Publication No. 2008/123097; and the like can be used.

As the alkali-soluble resin, for example, the compounds described in paragraphs 0225 to 0245 of JP2016-75845A can also be used, and the above contents are incorporated in the present specification.

A polyimide precursor can also be used as the alkali-soluble resin. The polyimide precursor is intended as a resin obtained by an addition polymerization reaction of a compound containing an acid anhydride group and a diamine compound at 40 to 100 ° C.
Examples of the polyimide precursor include a resin containing a repeating unit represented by the formula (1). The structure of the polyimide precursor includes, for example, the amic acid structure represented by the following formula (2), the following formula (3) in which the amic acid structure is partially imide-closed, and the following formula (4) in which all imide rings are formed. ), Examples of the polyimide precursor containing the imide structure.
In the present specification, a polyimide precursor having an amic acid structure may be referred to as a polyamic acid.

In the above formulas (1) to (4), R ₁ represents a tetravalent organic group having 2 to 22 carbon atoms, R ₂ represents a divalent organic group having 1 to 22 carbon atoms, and n represents 1 or 2 Represents.

Specific examples of the polyimide precursor include the compounds described in paragraphs 0011 to 0031 of JP-A-2008-106250, the compounds described in paragraphs 0022-0039 of JP-A-2016-122101, and Japanese Patent Application Laid-Open No. 2016-122101. Examples thereof include the compounds described in paragraphs 0061 to 0092 of JP-A-2016-68401, and the above contents are incorporated in the present specification.

The alkali-soluble resin contains at least one selected from the group consisting of the polyimide resin and the polyimide precursor in that the pattern shape of the patterned cured film obtained by using the curable composition is more excellent. Is also preferable.
The polyimide resin containing an alkali-soluble group is not particularly limited, and a known polyimide resin containing an alkali-soluble group can be used. Examples of the polyimide resin include the resin described in paragraph 0050 of JP-A-2014-137523, the resin described in paragraph 0058 of JP-A-2015-187676, and JP-A-2014-106326. Examples thereof include the resins described in paragraphs 0012 to 0013, and the above contents are incorporated in the present specification.

(Resin containing ethylenically unsaturated group)
The curable composition used in the production method of the present invention preferably contains a resin containing an ethylenically unsaturated group, from the viewpoint that the cross-sectional shape of the obtained cured film is more rectangular. The resin containing an ethylenically unsaturated group may be a dispersant or an alkali-soluble resin. Further, it may be a resin other than the dispersant or the alkali-soluble resin.
The lower limit of the content of the resin containing an ethylenically unsaturated group in the curable composition is preferably 40% by mass or more, more preferably 45% by mass or more, based on the total mass of the resin contained in the curable composition. It is preferable, and more preferably 50% by mass or more.
The upper limit of the content of the resin containing an ethylenically unsaturated group in the curable composition is preferably 100% by mass or less with respect to the total mass of the resin contained in the curable composition.
The resin containing an ethylenically unsaturated group means a resin containing one or more ethylenically unsaturated groups in one molecule.

The content of the resin containing an ethylenically unsaturated group may be calculated from the amount of the raw material charged.

The content of the ethylenically unsaturated group with respect to the total mass of the resin is not particularly limited, but is preferably 0.001 to 5.00 mmol / g, more preferably 0.10 to 3.00 mmol / g, and 0. More preferably, it is 26 to 2.50 mmol / g. When the ethylenically unsaturated group content is in the range of 0.10 to 3.00 mmol / g, the rectangularity of the cross-sectional shape of the cured film obtained by using the curable composition is more excellent.
The total mass of the resin is intended to be the total mass of the resins contained in the curable composition. For example, the curable composition of a resin containing an ethylenically unsaturated group and a resin not containing an ethylenically unsaturated group. When a substance is contained, the total mass of both corresponds to the total mass of the resin.
Therefore, the content of the ethylenically unsaturated group represents the content of the ethylenically unsaturated group in the resin containing the ethylenically unsaturated group with respect to the total mass of the resin.
Further, the resin is a component dissolved in the curable composition and is intended to be a component having a weight average molecular weight of more than 2000.

In the present specification, the ethylenically unsaturated group content may be referred to as "C = C value".
In the present specification, the ethylenically unsaturated group content (C = C valence) is intended to be a value measured by the following method. When synthesizing a resin containing an ethylenically unsaturated group, the measurement can be replaced by calculating from the amount of the raw material charged.
When the curable composition contains a plurality of types of resins and the C = C value of each resin is clear, the total mass of the resins contained in the curable composition can be determined from the blending ratio of each resin. C = C value of may be calculated and obtained.

As a method for measuring the ethylenically unsaturated group content of the resin, when the ethylenically unsaturated group is a (meth) acryloyl group, it is measured by the following method.
First, a solid component (black pigment or the like) in the curable composition is precipitated by a centrifugation method, and the remaining liquid component is separated. Further, a component having a weight average molecular weight of more than 2000 is fractionated from the obtained liquid component by the GPC method, and this is used as the resin to be measured.
Next, 0.25 mg of the resin to be measured is dissolved in 50 mL of THF (tetrahydrofuran), and 15 mL of methanol is further added to prepare a solution.
Add 10 mL of 4N aqueous sodium hydroxide solution to the prepared solution to obtain a mixed solution. Next, the mixed solution is stirred at a liquid temperature of 40 ° C. for 2 hours. Further, 10.2 mL of a 4N methanesulfonic acid aqueous solution is added to the mixture, and the mixture is stirred. Further, 5 mL of demineralized water is added to the mixed solution, and then 2 mL of methanol is added to prepare a measurement solution.
The content of (meth) acrylic acid in the measurement solution is measured by an HPLC (high performance liquid chromatography) method (absolute calibration curve method), and the ethylenically unsaturated group content is calculated.
HPLC measurement condition column: Synergy 4μ Polar-RP 80A (4.6mm × 250mm) manufactured by Phenomenex.
Column temperature: 40 ° C
Flow velocity: 1.0 mL / min
Detector wavelength: 210 nm
Eluent: THF (tetrahydrofuran, for HPLC) 55 / buffer water 45 * Buffer water ... 0.2% -phosphoric acid, 0.2% -triethylamine aqueous solution Injection amount: 5 μL

As a method for measuring the ethylenically unsaturated group content of a resin, the ethylenically unsaturated group is a group other than the (meth) acryloyl group, or a (meth) acryloyl group and a group other than the (meth) acryloyl group are used in combination. In some cases, a method of measuring bromination of the resin to be measured separated by the above method can be mentioned. The bromine value is measured according to JIS K2605: 1996.
Here, ethylenically unsaturated group content, bromine was added to the resin 100g of measurements obtained in bromine number (Br ₂₎ grams of _(gBr 2 / 100g), the resin per 1g It is a value converted into the number of moles of the added bromine (Br ₂ ).

<Polymerization initiator>
The curable composition preferably contains a polymerization initiator.
The polymerization initiator is not particularly limited, and a known polymerization initiator can be used. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, and a photopolymerization initiator is preferable. As the polymerization initiator, a so-called radical polymerization initiator is preferable.
The content of the polymerization initiator in the curable composition is not particularly limited, but is preferably 0.5 to 20% by mass with respect to the total solid content of the curable composition. As the polymerization initiator, one type may be used alone, or two or more types may be used in combination. When two or more kinds of polymerization initiators are used in combination, the total content is preferably within the above range.

(Thermal polymerization initiator)
Examples of the thermal polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalenonitrile, and dimethyl- (2,2') -azobis (2). -Methylpropionate) [V-601] and other azo compounds, and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and potassium persulfate can be mentioned.
Specific examples of the polymerization initiator include the polymerization initiator described on pages 65-148 of "Ultraviolet Curing System" by Kiyomi Kato (published by General Technology Center Co., Ltd .: 1989). ..

(Photopolymerization initiator)
The curable composition preferably contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as the polymerization of the polymerizable compound can be initiated, and a known photopolymerization initiator can be used. As the photopolymerization initiator, for example, a photopolymerization initiator having photosensitivity from an ultraviolet region to a visible light region is preferable. Further, it may be an activator that causes some action with a photoexcited sensitizer to generate an active radical, or may be an initiator that initiates cationic polymerization depending on the type of the polymerizable compound.
Further, the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least 50 in the range of 300 to 800 nm (more preferably 330 to 500 nm).

The content of the photopolymerization initiator in the curable composition is not particularly limited, but is preferably 0.5 to 20% by mass with respect to the total solid content of the curable composition. As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination. When two or more kinds of photopolymerization initiators are used in combination, the total content is preferably within the above range.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton, those containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and the like. Examples thereof include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone.
As a specific example of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

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

-Oxime compound As the photopolymerization initiator, an oxime ester-based polymerization initiator (oxime compound) is more preferable. In particular, an oxime compound is preferable because it has high sensitivity, high polymerization efficiency, a high content of black pigment in the curable composition, and is easy to design.
As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-80068, or the compound described in JP-A-2006-342166 can be used.
Examples of the oxime compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, and the like. 2-Acetoxyimimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxy Examples thereof include carbonyloxyimino-1-phenylpropane-1-one.
In addition, J. C. S. Perkin II (1979) pp. 1653-1660), J. Mol. C. S. Perkin II (1979) pp. 156-162, Journal
of Photopolymer Science and Technology (1995) pp. 202-232, the compounds described in JP-A-2000-66385, the compounds described in JP-A-2000-80068, JP-A-2004-534977, and JP-A-2006-342166 are also listed. Be done.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF) is also preferable. In addition, TR-PBG-304 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUDS NCI-831, ADEKA ARCULDS NCI-930 (manufactured by ADEKA), or N-1919 (carbazole / oxime ester skeleton-containing light). An initiator (manufactured by ADEKA) can also be used.

Further, as an oxime compound other than the above, the compound described in JP-A-2009-5199004 in which an oxime is linked to the N-position of carbazole; the compound described in US Pat. No. 7,626,957 in which a heterosubstituted group is introduced at a benzophenone moiety; Compounds described in JP-A-2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into a dye moiety; ketooxime compounds described in International Publication Patent No. 2009-131189; and triazine skeleton and oxime skeleton. The compound described in US Pat. No. 7,556,910, which is contained in the same molecule; the compound described in JP-A-2009-221114, which has an absorption maximum at 405 nm and has good sensitivity to a g-ray light source; Good.
For example, paragraphs 0274 to 0275 of JP2013-29760A can be referred to, the contents of which are incorporated herein by reference.
Specifically, as the oxime compound, a compound represented by the following formula (OX-1) is preferable. It should be noted that the NO bond of the oxime compound may be the (E) -form oxime compound, the (Z) -form oxime compound, or a mixture of the (E) -form and the (Z) -form. Good.

In the formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metal atomic group.
Examples of the monovalent non-metal atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, an arylthiocarbonyl group and the like. Moreover, these groups may have one or more substituents. Moreover, the above-mentioned substituent may be further substituted with another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, an aryl group and the like.
In the formula (OX-1), as the monovalent substituent represented by B, an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group is preferable, and an aryl group or a heterocyclic group is used. preferable. These groups may have one or more substituents. Examples of the substituent include the above-mentioned substituents.
In the formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-mentioned substituents.

An oxime compound containing a fluorine atom can also be used as the photopolymerization initiator. Specific examples of the oxime compound containing a fluorine atom include the 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); and the like. This content is incorporated herein.

As the photopolymerization initiator, compounds represented by the following general formulas (1) to (4) can also be used.

In the formula (1), R ¹ and R ² are independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Represents an arylalkyl group having 7 to 30 carbon atoms, and when R ¹ and R ² are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R ³ and R ⁴ are independent of each other. It represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X is a direct bond or carbonyl. Indicates a group.

In the formula ^{(2), R 1, R} 2, R 3 and, ^{R 4} is, ^{R 1,} R 2, ^{R 3} in the formula (1), and has the same meaning as ^{R 4, R 5} are, -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 , -CSO R ⁶ , -CN, a halogen atom, or a hydroxyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or 4 to 4 carbon atoms. It represents 20 heterocyclic groups, where X represents a direct bond or carbonyl group and a represents an integer of 0-4.

In the formula (3), R ¹ is an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl having 7 to 30 carbon atoms. Representing an alkyl group, R ³ and R ⁴ independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryl alkyl group having 7 to 30 carbon atoms, or a carbon. It represents a heterocyclic group of the number 4 to 20, and X represents a direct bond or a carbonyl group.

In the formula ^(4), R 1, ^{R 3} and, ^{R 4} is, ^R 1, ^{R 3} in the formula (3), and has the same meaning as ^{R 4, R 5 are,} -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 , -COR ⁶ , -CN, halogen atom, Alternatively, it represents a hydroxyl group, and R ⁶ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms. Represented, X represents a direct bond or a carbonyl group, and a represents an integer from 0 to 4.

In the above formulas (1) and (2), R ¹ and R ² are preferably methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or phenyl group, respectively. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xsilyl group. R ⁴ is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a naphthyl group. Direct binding is preferable for X.
Further, in the above formulas (3) and (4), R ¹ is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group, respectively. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a xsilyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group, or a naphthyl group. Direct binding is preferable for X.
Specific examples of the compounds represented by the formulas (1) and (2) include the compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. This content is incorporated herein by reference.

Specific examples of the oxime compound preferably used in the curable composition are shown below. Further, as the oxime compound, the compound described in Table 1 of International Publication No. 2015-036910 can also be used, and the above contents are incorporated in the present specification.

The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 to 480 nm, and further preferably has high absorbance at wavelengths of 365 nm and 405 nm. ..
From the viewpoint of sensitivity, the molar extinction coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200, It is more preferably 000.
The molar extinction coefficient of the compound can be measured by a known method, for example, with an ultraviolet-visible spectrophotometer (Varian Cary-5 spctrophotometer) using an ethyl acetate solvent at a concentration of 0.01 g / L. Is preferable.
Two or more kinds of photopolymerization initiators may be used in combination, if necessary.

Further, as the photopolymerization initiator, the compounds described in paragraphs 0052 of JP-A-2008-260927, paragraphs 0033 to 0037 of JP-A-201097210, and paragraph 0044 of JP-A-2015-68893 are also used. Yes, the above is incorporated herein.

<Polymerization inhibitor>
The curable composition preferably contains a polymerization inhibitor.
The polymerization inhibitor is not particularly limited, and a known polymerization inhibitor can be used. Examples of the polymerization inhibitor include phenolic polymerization inhibitors (eg, p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-ditert-butyl-4-methylphenol, etc. 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4-methoxynaphthol, etc.); Hydroquinone-based polymerization inhibitors (eg, , Hydroquinone, 2,6-di-tert-butylhydroquinone, etc.); Kinone-based polymerization inhibitor (eg, benzoquinone, etc.); Free radical-based polymerization inhibitor (eg, 2,2,6,6-tetramethylpiperidin 1- Oxyl-free radicals, 4-hydroxy-2,2,6,6-tetramethylpiperidin1-oxyl-free radicals, etc.); Nitrobenzene-based polymerization inhibitors (eg, nitrobenzene, 4-nitrotoluene, etc.); and phenothiazine-based polymerization inhibitors (For example, phenothiazine, 2-methoxyphenothiazine, etc.); and the like.
Among them, a phenol-based polymerization inhibitor or a free radical-based polymerization inhibitor is preferable because the curable composition has a more excellent effect.

The effect of the polymerization inhibitor is remarkable when used together with a resin containing a curable group.
The content of the polymerization inhibitor in the curable composition is not particularly limited, but is preferably 0.0001 to 0.5% by mass, preferably 0.001 to 0.2, based on the total solid content of the curable composition. More preferably by mass. The polymerization inhibitor may be used alone or in combination of two or more. When two or more kinds of polymerization inhibitors are used in combination, the total content is preferably within the above range.

<Surfactant>
The curable composition may contain a surfactant. The surfactant contributes to improving the coatability of the curable composition.
When the curable composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the curable composition.
As the surfactant, one type may be used alone, or two or more types may be used in combination. When two or more kinds of surfactants are used in combination, the total amount is preferably within the above range.

Examples of the surfactant include fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, silicone-based surfactants, and the like.

For example, when the curable composition contains a fluorine-based surfactant, the liquid properties (particularly, fluidity) of the curable composition are further improved. That is, when a film is formed using a curable composition containing a fluorine-based surfactant, the wettability to the surface to be coated is improved by reducing the interfacial tension between the surface to be coated and the coating liquid. , The applicability to the surface to be coated is improved. Therefore, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.

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

Examples of the fluorine-based surfactant include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, and F479. F482, F554, and F780 (all manufactured by DIC Corporation); Florard FC430, FC431, and FC171 (all manufactured by Sumitomo 3M Ltd.); Surfron S-382, SC-101. , SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by Asahi Glass Co., Ltd.) ); And PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like.
A block polymer can also be used as the fluorine-based surfactant, and specific examples thereof include compounds described in JP-A-2011-89090.

<UV absorber>
The curable composition may contain an ultraviolet absorber. As a result, the shape of the pattern of the cured film can be made into a more excellent (fine) shape.
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 JP2012-068418A (corresponding paragraphs 027 to 0254 of US2012 / 0068292) can be used, and these contents can be incorporated and incorporated in the present specification. ..
In addition, a diethylamino-phenylsulfonyl UV absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) and the like are also preferably used.
Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
The content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, further preferably 0.1 to 5% by mass, based on the total solid content of the curable composition. preferable.

<Silane coupling agent>
The curable composition may contain a silane coupling agent.
The silane coupling agent is a compound containing a hydrolyzable group and other functional groups in the molecule. A hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
The hydrolyzable group is a substituent that is directly linked to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group contains a carbon atom, the number of carbon atoms thereof is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
When forming a cured film on a substrate, the silane coupling agent improves the adhesion between the substrate and the cured film, so that fluorine atoms and silicon atoms (excluding silicon atoms to which a hydrolyzable group is bonded). It is preferable not to contain fluorine atom, silicon atom (excluding silicon atom to which a hydrolyzable group is bonded), alkylene group substituted with silicon atom, linear alkyl group having 8 or more carbon atoms, and It is desirable that the branched alkyl group having 3 or more carbon atoms is not contained.

The content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, based on the total solid content in the curable composition. More preferably 1.0 to 6% by mass.
The curable composition may contain one type of silane coupling agent alone, or may contain two or more types. When the curable composition contains two or more kinds of silane coupling agents, the total may be within the above range.

Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and the like. Examples thereof include vinyl trimethoxysilane and vinyl triethoxysilane.

<Solvent>
The curable composition preferably contains a solvent.
The solvent is not particularly limited, and a known solvent can be used.
The content of the solvent in the curable composition is not particularly limited, but it is preferably adjusted so that the solid content of the curable composition is 10 to 90% by mass, and 15 to 90% by mass. It is more preferable to be adjusted.
One type of solvent may be used alone, or two or more types may be used in combination. When two or more kinds of solvents are used in combination, it is preferable that the total solid content of the curable composition is adjusted to be within the above range.

Examples of the solvent include water and an organic solvent.
Examples of the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and acetyl acetone. , Cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, butyl acetate, methyl lactate, N -Methyl-2-pyrrolidone, ethyl lactate and the like, but are not limited thereto.

[Method for producing curable composition]
As the curable composition, it is preferable to first produce a dispersion composition in which a black pigment and a colorant are dispersed, and then mix the obtained dispersion composition with other components to obtain a curable composition.
The dispersion composition is preferably prepared by mixing a black pigment, a colorant, a resin (preferably a dispersant), and a solvent. It is also preferable to include a polymerization inhibitor in the dispersion composition.

The dispersion composition can be prepared by mixing each of the above components by a known mixing method (for example, a mixing method using a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser, or the like).

In preparing the curable composition, each component may be blended all at once, or each component may be dissolved or dispersed in a solvent and then sequentially blended. In addition, the order of feeding and working conditions at the time of blending are not particularly limited.

The curable composition is preferably filtered through a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, and a polyolefin resin (including high density and ultrahigh molecular weight) such as polyethylene and polypropylene (PP) can be mentioned. .. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.
The pore size of the filter is preferably 0.1 to 7.0 μm, more preferably 0.2 to 2.5 μm, further preferably 0.2 to 1.5 μm, and particularly preferably 0.3 to 0.7 μm. Within this range, fine foreign substances such as impurities and agglomerates contained in the pigment can be reliably removed while suppressing filtration clogging of the pigment (including the black pigment).
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or twice or more. When filtering is performed twice or more by combining different filters, it is preferable that the pore diameters of the second and subsequent filters are the same or larger than the pore diameter of the first filtering. Further, first filters having different pore diameters within the above-mentioned range may be combined. For the hole diameter here, the nominal value of the filter manufacturer can be referred to. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), Kitts Micro Filter Co., Ltd., and the like.
As the second filter, a filter formed of the same material as the first filter described above can be used. The pore size of the second filter is preferably 0.2 to 10.0 μm, more preferably 0.2 to 7.0 μm, and even more preferably 0.3 to 6.0 μm.
The curable composition preferably does not contain impurities such as metals, metal salts containing halogens, acids and alkalis. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, further preferably 100 pt or less, particularly preferably 10 pt or less, and substantially not contained (below the detection limit of the measuring device). That) is the most preferable.
The impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs type).

[Manufacturing method of cured film]
The curable composition layer (composition layer) formed by using the above photocurable composition can be cured to obtain a patterned cured film.
More specifically, in the production method of the present invention, the above-mentioned curable composition is used, the optical density A at a wavelength of 365 nm per 1.5 μm film thickness is 2.60 to 10.00, and the film thickness is 2.60 to 10.00. A step of forming a curable composition layer having an optical density B of 2.00 to 10.00 at a wavelength of 550 nm per 1.5 μm (curable composition layer forming step).
A step of exposing the curable composition layer under a condition of an oxygen concentration of 30 to 50% by volume (exposure step), and
A step of developing the curable composition layer after the exposure to form a cured film (development step), and
Contains.
Further, if desired, post-baking may be performed after the developing step.
Hereinafter, each of the above steps will be described.

[Curable composition layer forming step]
In the curable composition layer forming step, prior to exposure, a curable composition is applied onto a support or the like to form a curable composition layer (curable composition layer). As the support, for example, a substrate for a solid-state image sensor in which an image sensor (light receiving element) such as a CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor) is provided on a substrate (for example, a silicon substrate) is used. it can. Further, if necessary, an undercoat layer may be provided on the support in order to improve the adhesion with the upper layer, prevent the diffusion of substances, flatten the surface of the substrate, and the like.

As a method of applying the curable composition onto the support, various coating methods such as a slit coating method, an inkjet method, a rotary coating method, a casting coating method, a roll coating method, and a screen printing method can be applied. The film thickness of the curable composition layer is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and even more preferably 0.2 to 3 μm. The curable composition layer applied on the support can be dried (prebaked) in a hot plate, an oven or the like at a temperature of 50 to 140 ° C. for 10 to 300 seconds.

<Curable composition layer>
In the production method of the present invention, the curable composition layer (preferably a dried (prebaked) curable composition layer or an naturally dried curable composition layer) has an optical density A of 2.60 to 10 It is .00, and it is preferably 2.80 to 4.00, and more preferably 2.90 to 3.50, from the viewpoint that the rectangularity of the cross-sectional shape of the obtained cured film is more excellent.
Similarly, the optical density B is 2.00 to 10.00, and 2.50 to 7.00 is preferable, and 2.80 to 6.00 is preferable from the viewpoint that the rectangularity of the cross-sectional shape of the obtained cured film is more excellent. 50 is more preferable.
The ratio of the optical density B to the optical density A (optical density B / optical density A) is preferably 0.3 to 3.5, more preferably 0.5 to 2.0, and 0.8 to 1.2. More preferred.

In the present specification, as a method for measuring the optical density A and the optical density B, first, a dried curable composition layer is formed on a glass substrate, and a transmission densitometer (X-rite 361T (visual)) is used. The measurement is performed using a densiometer), the film thickness at the measurement point is also measured, and the optical density per 1.5 μm film thickness is calculated.
When the film thickness of the curable composition layer is 1.5 μm, the value measured by the transmission densitometer can be used as it is.

[Exposure process]
In the exposure step, it is sufficient that the curable composition layer can be exposed under the condition of an oxygen concentration of 30 to 50% by volume. For example, a curable composition is used through a mask having a predetermined mask pattern using an exposure device such as a stepper. An embodiment in which the layer is pattern-exposed can be mentioned.
Examples of the light during exposure include light selected from g-line, h-line, i-line, KrF line (excimer laser line), and ArF line (excimer laser line).
Irradiance is preferably 20000~50000W / ^{m 2,} more preferably 25000~40000W / ^{m 2.}

The exposure step is performed under the condition that the oxygen concentration is 30 to 50% by volume.
By performing the exposure under such conditions, the rectangularity of the cross-sectional shape of the obtained cured film becomes good.
This oxygen concentration can be controlled by a conventional method. For example, the oxygen concentration in the room can be adjusted by supplying a desired ratio of oxygen gas and nitrogen gas to the device room containing the exposure device as a closed structure. Alternatively, a predetermined flow rate of oxygen gas and nitrogen gas may be circulated in the room of the exposure apparatus so that the exposure atmosphere has a predetermined oxygen concentration.

Here, in the production method of the present invention, when the optical density A is X, the oxygen concentration (volume fraction) at the time of exposure is Y, and the irradiance (W / m ² ) is Z, the calculation is performed by the following formula (1). The value to be obtained is preferably 1.60 × ^{10-5 to} 10.00 × ^10-5, and more preferably 2.80 × ^{10-5 to} 5.20 × ^10-5 .
Equation (1) X × Y ÷ Z

When the optical density A and X in the formula (1) are large, the light irradiated in the exposure step is easily blocked by the surface layer portion of the curable composition layer, and the curing reaction in the lower layer portion is difficult to proceed.
When Y, which is the oxygen concentration at the time of exposure, is large, the curing reaction at the surface layer portion of the curable composition layer is easily suppressed by oxygen.
When Z, which is the irradiance (W / m ² ), is large, the curing reaction is promoted in both the surface layer portion and the lower layer portion of the curable composition layer.
When the value calculated by the formula (1) in which X, Y, and Z are combined, which is closely related to the progress of curing of these curable composition layers, is within the above range, the curing is performed. The rectangularity of the film is improved.
Further, even when a curable composition that has been prepared for a long period of time (for example, one month) is used, it is produced if the value calculated by the formula (1) falls within the above range. The rectangularity of the cross-sectional shape of the cured film is unlikely to deteriorate.

The specific calculation based on the equation (1) is as follows, for example.
When the curable composition layer having an optical density A of 3.00 is exposed under the conditions of an oxygen concentration of 30% by mass and an irradiance of 30,000 W / m ² , X = 3.00 and Y = 0. 30, Z = 30000, and the calculated value of the equation (1) is 3.00 × ^10-5 .

[Development process]
The developing step is a step of developing the curable composition layer after exposure to form a cured film. By this step, the curable composition layer of the light-unirradiated portion in the exposure step is eluted, and only the photocured portion remains, and a patterned cured film can be obtained.
The type of developer used in the developing process is not particularly limited, but an alkaline developer that does not damage the underlying image sensor and circuit is desirable.
The developing temperature is, for example, 20 to 30 ° C.
The development time is, for example, 20 to 90 seconds. In recent years, it may be carried out for 120 to 180 seconds in order to remove more residue. Further, in order to further improve the residue removability, the step of shaking off the developer every 60 seconds and further supplying a new developer may be repeated several times.

As the alkaline developer, an alkaline aqueous solution prepared by dissolving an alkaline compound in water so as to have a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass) is preferable.
Alkaline compounds include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropyl. Examples thereof include ammonium hydroxide, tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo [5.4.0] -7-undecene (of which organic alkali is used. preferable.).
When used as an alkaline developer, it is generally washed with water after development.

[Post-bake]
After the exposure step, it is preferable to perform heat treatment (post-baking). Post-baking is a post-development heat treatment to complete the cure. The heating temperature is preferably 240 ° C. or lower, more preferably 220 ° C. or lower. There is no particular lower limit, but in consideration of efficient and effective treatment, 50 ° C. or higher is preferable, and 100 ° C. or higher is more preferable.
Post-baking can be performed continuously or in batch using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater.

The above post-baking is preferably performed in an atmosphere having a low oxygen concentration. The oxygen concentration is preferably 19% by volume or less, more preferably 15% by volume or less, further preferably 10% by volume or less, particularly preferably 7% by volume or less, and 3 volumes. Most preferably, it is% or less. There is no particular lower limit, but 10 volume ppm or more is practical.

Further, the curing may be completed by UV (ultraviolet) irradiation instead of the post-baking by the above heating.
In this case, the curable composition described above preferably further contains a UV curing agent. The UV curing agent is preferably a UV curing agent capable of curing at a wavelength shorter than 365 nm, which is the exposure wavelength of the polymerization initiator added for the lithography process by ordinary i-ray exposure. Examples of the UV curing agent include Cibayl Gacure 2959 (trade name). When UV irradiation is performed, it is preferable that the curable composition layer is a material that cures at a wavelength of 340 nm or less. There is no particular lower limit for the wavelength, but it is generally 220 nm or more. The exposure amount of UV irradiation is preferably 100 to 5000 mJ, more preferably 300 to 4000 mJ, and even more preferably 800 to 3500 mJ. It is preferable that this UV curing step is performed after the lithography step in order to perform low temperature curing more effectively. It is preferable to use an ozoneless mercury lamp as the exposure light source.

[Physical properties of cured film and use of cured film]
[Physical properties of cured film]
The cured film obtained by the production method of the present invention preferably has an optical density of 2.60 to 10.00 at a wavelength of 365 nm per 1.5 μm film thickness, more preferably 2.80 to 4.00, and 2.90. ~ 3.50 is more preferable.
The optical density of the cured film obtained by the production method of the present invention at a wavelength of 550 nm per 1.5 μm film thickness is preferably 2.00 to 10.00, more preferably 2.50 to 7.00, and 2.80. ~ 6.50 is more preferable.
Further, the cured film preferably has an optical density of more than 2.00 per 1.5 μm film thickness in the wavelength region of 400 to 1200 nm in that the cured film is more excellent in performance when used as a light-shielding film described later. More than 3.00 is more preferable. The upper limit is not particularly limited, but is preferably 10 or less. Such a cured film can be preferably used as a light-shielding film.
In the present specification, as a method for measuring the optical density of a cured film, first, a cured film is formed on a glass substrate, and the film is measured and measured using a transmission densitometer (X-rite 361T (visual) densiometer). The film thickness of the portion is also measured, and the optical density per predetermined film thickness is calculated.
Further, in the present specification, the optical density per 1.5 μm film thickness in the wavelength region of 400 to 1200 nm is more than 2.00, the optical density per 1.5 μm film thickness in the entire wavelength range of 400 to 1200 nm. Intended to be over 2.00.

Further, it is also preferable that the cured film has a surface uneven structure. By doing so, the reflectance of the cured film can be reduced when the cured film is used as a light-shielding film. The surface of the cured film itself may have an uneven structure, or another layer may be provided on the cured film to impart the uneven structure. The shape of the surface uneven structure is not particularly limited, but the surface roughness is preferably in the range of 0.55 μm or more and 1.5 μm or less.
The reflectance of the cured film is preferably 5% or less, more preferably 3% or less, still more preferably 2% or less.
The method for producing the surface uneven structure is not particularly limited, but a method in which an organic filler and / or an inorganic filler is contained in the cured film or other layers, a lithography method using exposure development, or an etching method, a sputtering method and nanoimprint. A method of roughening the surface of the cured film or other layers by a method or the like may be used.
In addition to the above, methods for reducing the reflectance of the cured film include a method of providing a low refractive index layer on the cured film, a method of providing a plurality of layers having different refractive indexes (for example, a high refractive index layer), and a method of providing a plurality of layers having different refractive indexes. , A method for forming a low optical density layer and a high optical density layer, which is described in JP-A-2015-1654.

The cured film is a portable device such as a personal computer, a tablet, a mobile phone, a smartphone, and a digital camera; a multifunction printer, and an OA (Official Automation) device such as a scanner; a surveillance camera, a bar code reader, and cash. Industrial equipment such as automatic depository machines (ATMs: automated teller machines), high-speed cameras, and equipment that has a personal authentication function using face image authentication; in-vehicle camera equipment; endoscopes, capsule endoscopes, And medical camera equipment such as catheters; and biosensors, biosensors, military reconnaissance cameras, stereoscopic map cameras, meteorological and oceanographic observation cameras, land resource exploration cameras, and space astronomical and deep space targets. It is suitable for light-shielding members and light-shielding films of optical filters and modules used in space equipment such as exploration cameras, and also for antireflection members and antireflection films.

The cured film can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). The cured film is suitable for optical filters and optical films used for micro LEDs and micro OLEDs, as well as members for imparting a light shielding function or an antireflection function.
Examples of the micro LED and the micro OLED include those described in the special table 2015-500562 and the special table 2014-533890.

The cured film is also suitable as an optical filter and an optical film used in a quantum dot sensor and a quantum dot solid-state image sensor. Further, it is suitable as a member for imparting a light-shielding function and an antireflection function. Examples of the quantum dot sensor and the quantum dot solid-state image sensor include those described in US Patent Application Publication No. 2012/37789 and International Publication No. 2008/131313.

[Light-shielding film, solid-state image sensor and solid-state image sensor]
The cured film obtained by the production method of the present invention is also preferably used as a so-called light-shielding film. Such a light-shielding film is also preferably used for a solid-state image sensor.
The light-shielding film is one of the preferable uses in the cured film obtained by the production method of the present invention, and the method for producing the light-shielding film of the present invention is the same as the method described as the above-mentioned method for producing the cured film. You can. Specifically, a curable composition can be applied to a substrate to form a curable composition layer, which can be exposed and developed to produce a light-shielding film.
Further, the method for manufacturing a solid-state image sensor of the present invention includes a step of manufacturing a cured film (light-shielding film) through the above-mentioned manufacturing method of the present invention, and the solid-state image sensor having the above-mentioned cured film (light-shielding film) is used. It is a method of manufacturing.
As described above, the solid-state image sensor according to the manufacturing method of the present invention contains the cured film (light-shielding film). The form in which the solid-state image sensor contains a cured film (light-shielding film) is not particularly limited. For example, a plurality of photodiodes constituting a light receiving area of the solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) on a substrate. And those having a light receiving element made of polysilicon or the like and having a cured film on the light receiving element forming surface side of the support (for example, a portion other than the light receiving portion and / or a pixel for color adjustment) or on the opposite side of the forming surface. Can be mentioned.
The solid-state image sensor contains the solid-state image sensor.

A configuration example of the solid-state image pickup device and the solid-state image pickup device will be described with reference to FIGS. In addition, in FIGS. 1 and 2, in order to clarify each part, the mutual thickness and / or width ratio is ignored and a part is exaggerated.
As shown in FIG. 1, the solid-state image sensor 100 includes a rectangular solid-state image sensor 101 and a transparent cover glass 103 that is held above the solid-state image sensor 101 and seals the solid-state image sensor 101. There is. Further, a lens layer 111 is provided on the cover glass 103 so as to be overlapped with the spacer 104. The lens layer 111 is composed of a support 113 and a lens material 112. The lens layer 111 may have a structure in which the support 113 and the lens material 112 are integrally molded. When stray light is incident on the peripheral region of the lens layer 111, the effect of condensing the light on the lens material 112 is weakened due to the diffusion of the light, and the light reaching the image pickup unit 102 is reduced. In addition, noise is generated due to stray light. Therefore, the peripheral region of the lens layer 111 is provided with a light-shielding film 114 to block light. The cured film obtained by the production method of the present invention can also be used as the light-shielding film 114.

The solid-state image sensor 101 photoelectrically converts the optical image imaged by the image pickup unit 102, which is the light receiving surface thereof, and outputs the image signal. The solid-state image sensor 101 includes a laminated substrate 105 in which two substrates are laminated. The laminated substrate 105 is composed of a rectangular chip substrate 106 and a circuit board 107 of the same size, and the circuit board 107 is laminated on the back surface of the chip substrate 106.

The material of the substrate used as the chip substrate 106 is not particularly limited, and a known material can be used.

An imaging unit 102 is provided at the center of the surface of the chip substrate 106. Further, when stray light is incident on the peripheral region of the imaging unit 102, dark current (noise) is generated from the circuit in the peripheral region, so that the peripheral region is shielded by a light-shielding film 115. The cured film obtained by the production method of the present invention is preferably used as the light-shielding film 115.

A plurality of electrode pads 108 are provided on the surface edge of the chip substrate 106. The electrode pad 108 is electrically connected to the imaging unit 102 via a signal line (or a bonding wire) (not shown) provided on the surface of the chip substrate 106.

On the back surface of the circuit board 107, external connection terminals 109 are provided at positions substantially below each electrode pad 108. Each external connection terminal 109 is connected to the electrode pad 108 via a through electrode 110 that vertically penetrates the laminated substrate 105. Further, each external connection terminal 109 is connected to a control circuit that controls the drive of the solid-state image sensor 101, an image processing circuit that performs image processing on the image pickup signal output from the solid-state image sensor 101, and the like via wiring (not shown). Has been done.

As shown in FIG. 2, the imaging unit 102 is composed of each unit provided on the substrate 204 such as the light receiving element 201, the color filter 202, and the microlens 203. The color filter 202 has a blue pixel 205b, a red pixel 205r, a green pixel 205g, and a black matrix 205bm. The cured film obtained by the production method of the present invention can also be used as a black matrix 205 bm.

As the material of the substrate 204, the same material as the chip substrate 106 described above can be used. A p-well layer 206 is formed on the surface layer of the substrate 204. In the p-well layer 206, light receiving elements 201, which are composed of n-type layers and generate and store signal charges by photoelectric conversion, are arranged in a square lattice pattern.

A vertical transfer path 208 made of an n-type layer is formed on one side of the light receiving element 201 via a read-out gate portion 207 on the surface layer of the p-well layer 206. Further, a vertical transfer path 208 belonging to an adjacent pixel is formed on the other side of the light receiving element 201 via an element separation region 209 made of a p-type layer. The read gate unit 207 is a channel region for reading the signal charge accumulated in the light receiving element 201 into the vertical transfer path 208.

A gate insulating film 210 made of an ONO (Oxide-Nitride-Oxide) film is formed on the surface of the substrate 204. On the gate insulating film 210, a vertical transfer electrode 211 made of polysilicon or amorphous silicon is formed so as to cover substantially directly above the vertical transfer path 208, the read gate portion 207, and the element separation region 209. The vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to perform charge transfer and a read electrode that drives the read gate unit 207 to perform signal charge reading. The signal charge is sequentially transferred from the vertical transfer path 208 to the horizontal transfer path and the output unit (floating diffusion amplifier) (not shown), and then output as a voltage signal.

A light-shielding film 212 is formed on the vertical transfer electrode 211 so as to cover the surface thereof. The light-shielding film 212 has an opening at a position directly above the light-receiving element 201, and shields the other regions from light. The cured film obtained by the production method of the present invention can also be used as a light-shielding film 212.
A transparent intermediate layer made of an insulating film 213 made of BPSG (borophossilicate glass), an insulating film (passion film) 214 made of P-SiN, and a flattening film 215 made of a transparent resin or the like is provided on the light-shielding film 212. ing. The color filter 202 is formed on the intermediate layer.

[Image display device]
The image display device manufactured by the manufacturing method of the present invention contains a cured film obtained by the manufacturing method of the present invention.
Further, the method for manufacturing an image display device of the present invention is a method for manufacturing an image display device having the above-mentioned cured film, which comprises a step of manufacturing a cured film through the above-mentioned manufacturing method of the present invention.
Examples of the form in which the image display device has a cured film include a form in which the cured film is contained in a black matrix and a color filter containing such a black matrix is used in the image display device.
Next, a black matrix and a color filter containing the black matrix will be described, and further, as a specific example of the image display device, a liquid crystal display device containing such a color filter will be described.

<Black Matrix>
The cured film obtained by the production method of the present invention is preferably contained in a black matrix. The black matrix may be contained in a color filter, a solid-state image sensor, and an image display device such as a liquid crystal display device.
The black matrix has already been described above; a black edge provided on the peripheral edge of an image display device such as a liquid crystal display device; a grid pattern and / or a stripe between red, blue, and green pixels. A black portion in the shape of a dot; a dot-shaped and / or a linear black pattern for light-shielding a TFT (thin film transistor); and the like. For the definition of this black matrix, for example, Taihei Sugano, "Liquid Crystal Display Manufacturing Equipment Glossary", 2nd Edition, Nikkan Kogyo Shimbun, 1996, p. There is a description in 64.
The black matrix has high light-shielding properties (at optical density OD) in order to improve the display contrast and, in the case of an active matrix-driven liquid crystal display device using a thin film transistor (TFT), to prevent image quality deterioration due to light current leakage. It is preferable to have 3 or more).

The method for producing the black matrix is not particularly limited, but the black matrix can be produced by the same method as the above-mentioned method for producing the cured film. Specifically, a curable composition can be applied to a substrate to form a curable composition layer, which can be exposed and developed to produce a patterned cured film (black matrix). The film thickness of the cured film used as the black matrix is preferably 0.1 to 4.0 μm.

The material of the substrate is not particularly limited, but preferably has a transmittance of 80% or more with respect to visible light (wavelength 400 to 800 nm). Specific examples of such a material include glass such as soda lime glass, non-alkali glass, quartz glass, and borosilicate glass; plastics such as polyester resin and polyolefin resin; and the like. From the viewpoint of chemical resistance and heat resistance, non-alkali glass, quartz glass and the like are preferable.

<Color filter>
The cured film obtained by the production method of the present invention is preferably contained in a color filter.
The form in which the color filter contains the cured film is not particularly limited, and examples thereof include a color filter including a substrate and the black matrix. That is, a color filter including red, green, and blue colored pixels formed in the openings of the black matrix formed on the substrate can be exemplified.

A color filter containing a black matrix (cured film) can be produced, for example, by the following method.
First, a coating film (resin composition layer) of a resin composition containing a pigment corresponding to each colored pixel of a color filter is formed in an opening of a patterned black matrix formed on a substrate. The resin composition for each color is not particularly limited, and a known resin composition can be used. However, in the curable composition described in the present specification, the black pigment is replaced with a colorant corresponding to each pixel. It is preferable to use one.
Next, the resin composition layer is exposed through a photomask having a pattern corresponding to the opening of the black matrix. Next, after removing the unexposed portion by a developing process, colored pixels can be formed in the opening of the black matrix by baking. A color filter having red, green, and blue pixels can be produced by performing a series of operations using, for example, a resin composition for each color containing red, green, and blue pigments.

<Liquid crystal display device>
The cured film obtained by the production method of the present invention is preferably contained in a liquid crystal display device. The form in which the liquid crystal display device contains a cured film is not particularly limited, and examples thereof include a form containing a color filter containing a black matrix (cured film) described above.

Examples of the liquid crystal display device according to the present embodiment include a pair of substrates arranged so as to face each other and a liquid crystal compound enclosed between the substrates. The above-mentioned substrate is as described above as a substrate for a black matrix.

As a specific form of the liquid crystal display device, for example, from the user side, a polarizing plate / substrate / color filter / transparent electrode layer / alignment film / liquid crystal layer / alignment film / transparent electrode layer / TFT (Thin Film Transistor) Examples thereof include a laminate containing an element / substrate / polarizing plate / backlight unit in this order.

The liquid crystal display device is not limited to the above, and is not limited to the above, for example, "electronic display device (written by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990)", "display device (written by Junaki Ibuki, Sangyo Tosho Co., Ltd.)" The liquid crystal display device described in "(issued in 1989)" can be mentioned. Further, for example, the liquid crystal display device described in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994)" can be mentioned.

[Infrared sensor]
The cured film obtained by the production method of the present invention is preferably contained in an infrared sensor.
The infrared sensor according to the above embodiment will be described with reference to FIG. In the infrared sensor 300 shown in FIG. 3, FIG. 310 is a solid-state image sensor.
The image pickup region provided on the solid-state image sensor 310 is formed by combining an infrared absorption filter 311 and a color filter 312.
The infrared absorption filter 311 transmits light in the visible light region (for example, light having a wavelength of 400 to 700 nm), and transmits light in the infrared region (for example, light having a wavelength of 800 to 1300 nm, preferably light having a wavelength of 900 to 1200 nm, and more. It is preferably a film that shields light having a wavelength of 900 to 1000 nm), and a cured film containing an infrared absorber (the form of the infrared absorber is as described above) can be used as the colorant.
The color filter 312 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed, and for example, red (R), green (G), and blue (B) pixels are formed. A color filter or the like is used, and its form is as described above.
A resin film 314 (for example, a transparent resin film or the like) capable of transmitting light having a wavelength transmitted through the infrared transmission filter 313 is arranged between the infrared transmission filter 313 and the solid-state image sensor 310.
The infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared rays of a specific wavelength, and is a colorant (for example, a perylene compound and / or bisbenzo) that absorbs light in the visible light region. A cured film obtained by the production method of the present invention containing an infrared absorber (for example, a pyrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, a polymethine compound, etc.) and an infrared absorber (for example, a furanone compound) can be used. The infrared transmission filter 313 preferably blocks light having a wavelength of 400 to 830 nm and transmits light having a wavelength of 900 to 1300 nm, for example.
A microlens 315 is arranged on the incident light hν side of the color filter 312 and the infrared transmission filter 313. A flattening film 316 is formed so as to cover the microlens 315.
In the form shown in FIG. 3, the resin film 314 is arranged, but an infrared transmission filter 313 may be formed instead of the resin film 314. That is, the infrared transmission filter 313 may be formed on the solid-state image sensor 310.
Further, in the form shown in FIG. 3, the film thickness of the color filter 312 and the film thickness of the infrared transmission filter 313 are the same, but the film thicknesses of both may be different.
Further, in the form shown in FIG. 3, the color filter 312 is provided on the incident light hν side of the infrared absorption filter 311. However, the order of the infrared absorption filter 311 and the color filter 312 is changed to obtain an infrared absorption filter. The 311 may be provided on the incident light hν side of the color filter 312.
Further, in the form shown in FIG. 3, the infrared absorption filter 311 and the color filter 312 are laminated adjacent to each other, but both filters do not necessarily have to be adjacent to each other, and even if another layer is provided between them. Good. The cured film obtained by the production method of the present invention can be used as a light-shielding film such as the edge and / or side surface of the surface of the infrared absorption filter 311, and can be used for the inner wall of the infrared sensor to internally reflect and / or receive light. It is possible to prevent unintended light from entering the part and improve the sensitivity.
Since this infrared sensor can simultaneously capture image information, it is possible to perform motion sensing that recognizes an object for which motion is detected. Furthermore, since distance information can be acquired, it is possible to take an image including 3D information.

Next, a solid-state image sensor to which the infrared sensor is applied will be described.
The solid-state image sensor includes a lens optical system, a solid-state image sensor, an infrared light emitting diode, and the like. For each configuration of the solid-state image sensor, paragraphs 0032 to 0036 of JP2011-233983A can be referred to, and the contents thereof are incorporated in the present specification.

The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the invention should not be construed as limiting by the examples shown below.

[Preparation of dispersion composition]
A dispersion composition used for the preparation of the curable composition was prepared.
Table 1 below shows the composition ratio (part by mass ratio) of each component in each dispersion composition. The dispersion compositions 1, 13, and 14 have the same composition.

The details of the components corresponding to the descriptions in Table 1 are shown below.

<Pigment>
The pigments shown below were used.
Ti, Zr, V, Nb, CB, inorganic black pigment (A), inorganic black pigment (B), and inorganic black pigment (C) are black pigments, and PG58 and PY185 are pigments other than black pigments. ..

-Ti: Titanium nitride-containing particles produced by the method for producing metal nitride-containing particles shown below.

For the production of the metal nitride-containing particles (titanium nitride-containing particles), the apparatus described in paragraph 0042 of JP-A-2005-343784 and FIG. 1 was used. Specifically, in FIG. 1 of the above publication, a metal nitride is used by using an apparatus (hereinafter referred to as “nanoparticle manufacturing apparatus”) in which the discharge container 1 is a stainless steel vacuum chamber (manufactured by Fukushin Kogyo Co., Ltd.). Containing particles (titanium nitride-containing particles) were prepared. First, the air in the vacuum chamber was exhausted by an exhaust pump. Next, in the vacuum chamber, a mixed gas of helium (He) gas (purity 99.99%) and argon gas (mixing ratio 50/50% by volume in the standard state) was added to a pressure of 600 Torr (79.99 kPa). Supplied until it became.

As the discharge electrode of the nanoparticle manufacturing apparatus, a tungsten having a length of 500 mm, a diameter of 12 mm, and a hollow diameter of 6 mm formed into a rod shape having a hollow structure was used. The arrangement of the discharge electrodes was the same as in FIG. 1 of JP-A-2005-343784. Specifically, 12 discharge electrodes were arranged in 2 stages of 6 each. The distance between the upper and lower tiers was set to about 160 mm.
The hollow structure discharge electrode is connected to the raw material supply device so that the raw material gas can be supplied into the vacuum chamber from the hollow portion of the discharge electrode.

The discharge is started in a state where the tips of the respective discharge electrodes are in contact with each other while applying alternating current (voltage 20 to 40 V, current 70 to 100 A) having a phase difference to each discharge electrode. After the arc discharge was generated, the tips of each discharge electrode were moved outward so as to be separated from each other, and the arc discharge was continued by setting the distance between the tips of the adjacent discharge electrodes to be 5 to 10 mm. ..

After performing the arc discharge for 15 minutes, the supply tank of the raw material supply device was heated to introduce the raw material gas into the vacuum chamber. First, NH ₃ gas (liquefied ammonium ECOAN, manufactured by Showa Denko) is 0.5 atm, H ₂ gas (hydrogen gas, Showa Denko Gas Products) is 0.1 atm, Ar gas (argon gas, Taiyo Nisshi). Was introduced at 0.4 atm. Subsequently, the supply tank was heated to 210 ° C., and TiCl ₄ gas (TLT-1, Toho Titanium Co., Ltd.) was introduced from the discharge electrode at 600 atm. At the same time as the introduction of TiCl ₄ gas, sulfur fine powder (fine powder sulfur 325 mesh, manufactured by Tsurumi Chemical Industry Co., Ltd.) was supplied by nitrogen gas using a powder supply device TP-99010FDR (manufactured by JEOL Ltd.). The amount of supply is determined by fluorescent X-ray analysis, where the mass-based content of sulfur atoms detected by X-ray photoelectron spectroscopic analysis in the obtained metal nitride-containing particles (titanium nitride-containing particles) is set to _TE (mass%). the ratio of both the content of the mass of sulfur atoms to be detected was T _{X (mass%)} of _(T E _/ T _X) was adjusted to be less than 1.1. After introducing TiCl ₄ gas and nitrogen gas mixed with sulfur fine powder into the vacuum chamber for 1 hour, the voltage application from the AC power supply was stopped, and the supply of the gas was stopped. Next, the particles adhering to the inner wall of the vacuum chamber were collected.

Next, the obtained particles were placed in a closed container into which nitrogen (N ₂ ) gas having an O ₂ content and a water content controlled to 100 ppm or less was introduced, and allowed to stand for 24 hours.

The particles obtained above were heated at 200 ° C. using a vacuum oven VAC-101P (manufactured by ESPEC) to obtain metal nitride-containing particles (titanium nitride-containing particles). The internal pressure of the decompression oven during heating was 1.0 × 10 ³ Pa.

· Zr: TiCl ₄ in place of the introduction of the gas, zirconium powder (manufactured by Wako Pure Chemical Industries, zirconium powder) powder feeder TP-99010FDR same method as described above the titanium nitride-containing particles except introduced in (manufactured by JEOL) Zirconium nitride-containing particles produced in.

· V: in place of the introduction of TiCl ₄ gas, vanadium powder (Taiyo ore Engineering metallic vanadium powder VHO) a powder supplying device TP-99010FDR except introduced in (Nippon Denshi) similar to the above-mentioned titanium nitride-containing particles Vanadium nitride-containing particles produced by the method.

· Nb: in place of the introduction of TiCl ₄ gas, the above-described nitride except introduced in niobium powder (Mitsuwa Chemicals Ltd. niobium (powder) <100-325mesh>) a powder feeder TP-99010FDR (manufactured by JEOL) Niobium nitride-containing particles produced in the same manner as titanium-containing particles.

Incidentally, each metal nitride-containing particles described above (titanium nitride-containing particles, zirconium nitride-containing particles, vanadium nitride-containing particles, and, niobium-containing particles) T _{E /} T _X of were measured by the following methods.
Each metal nitride-containing particle was molded into pellets using a press to prepare a sample. For the sample, X-ray photoelectron spectrometer, and, using a fluorescent X-ray analyzer, the following measurement conditions, was measured T _{E /} T _X of the metal nitride-containing particles.

X-ray photoelectron spectrometer (Measurement of _{T E)}
Equipment: PHI Quantera-SXM (trade name) equipment X-ray source: Monochromatic Al Kα ray (1486.6 ev, 25W, 15kV, beam diameter 200μmφ)
Measurement area: 200 μmφ
Measurement conditions: Pass Energy = 140 eV, step = 0.1 eV, number of integrations 4 to 8 times Measurement method: The sample was set in the apparatus, and the photoelectron extraction angle was set to 10 degrees.

X-ray fluorescence spectrometer (Measurement of _{T X)}
Equipment Rigaku ZSM Primus II type XRF
X-ray Rh 30-50 kV, 48-80 mA
Measurement area 10 μmφ
Measurement time 10-240 deg / min

Further, in each metal nitride-containing particle (titanium nitride-containing particle, zirconium nitride-containing particle, vanadium nitride-containing particle, and niobite-containing particle), the transition metal atom (titanium, zirconium, vanadium, or titanium nitride, zirconium, vanadium, or niobite-containing particle) contained in the nitride is contained. The ratio of the number of atoms in the nitrogen atom to the content of niob) X, the ratio of the number of atoms in the oxygen atom to the content of the transition metal atom contained in the nitride, and the transition contained in the nitride. The ratio Z of the number of atoms contained in the sulfur atom to the content of the metal atom was set to X = 0.8, Y = 0.1, and Z = 0.1, respectively.
The content of each atom in each of the obtained metal nitride-containing particles was measured using a fluorescent X-ray analyzer. Specifically, as a sample, each metal nitride-containing particle was prepared into pellets using a press machine, and the sample was measured under the following conditions using a fluorescent X-ray analyzer.
Equipment Rigaku ZSM Primus II type XRF
X-ray Rh 30-50 kV, 48-80 mA
Measurement area 10 μmφ
Measurement time 10-240 deg / min

The average primary particle diameter of each metal nitride-containing particle (titanium nitride-containing particle, zirconium nitride-containing particle, vanadium nitride-containing particle, and niobium nitride-containing particle) was less than 80 nm.

-CB: Carbon black (trade name "Color Black S170", manufactured by Degussa, average primary particle diameter 17 nm, BET specific surface area 200 m ² / g)
・ PG58: Pigment Green 58
・ PY185: Pigment Yellow 185
-Inorganic black pigment (A): trade name "NITRBLACK (night black) UB-1", manufactured by Mitsubishi Materials Co., Ltd.-Inorganic black pigment (B): Zirconium nitride powder according to Example 1 of JP-A-2017-222559. Inorganic black pigment (C): Fine particle low-order zirconium oxide / zirconium nitride composite according to Example 1 of Japanese Patent No. 4931011.

In the dispersion composition 11, PG58 and PY185 are used in combination to make the dispersion green as a whole.

<Dispersant>
Dispersant A (resin having no ethylenically unsaturated group): Synthesized by the method shown below.

(Synthesis Example A1: Synthesis of Macromonomer A-1)
Ε-Caprolactone (1044.2 g), δ-valerolactone (184.3 g), and 2-ethyl-1-hexanol (71.6 g) were introduced into a three-necked flask having a capacity of 3000 mL to obtain a mixture. The mixture was then stirred while blowing nitrogen. Next, Disperbyk111 (12.5 g, manufactured by Big Chemie, phosphoric acid resin) was added to the mixture, and the obtained mixture was heated to 90 ° C. After 6 hours, ¹ H-NMR (nuclear magnetic resonance) was used to confirm that the signal derived from 2-ethyl-1-hexanol in the mixture had disappeared, and then the mixture was heated to 110 ° C. After continuing the polymerization reaction at 110 ° C. for 12 hours under nitrogen, the disappearance of the signals derived from ε-caprolactone and δ-valerolactone was confirmed by ¹ H-NMR, and the molecular weight of the obtained compound was measured by the GPC method. Was done. After confirming that the molecular weight of the compound reached a desired value, 2,6-dit-butyl-4-methylphenol (0.35 g) was added to the mixture containing the above compound, and further obtained. 2-Methylyloxyethyl isocyanate (87.0 g) was added dropwise to the mixture over 30 minutes. Six hours after the completion of the dropping, ¹ H-NMR confirmed that the signal derived from 2-methacryloyloxyethyl isocyanate (MOI) had disappeared, and then propylene glycol monomethyl ether acetate (PGMEA) (1387.0 g) was mixed. To obtain a macromonomer A-1 solution (2770 g) having a concentration of 50% by mass. The weight average molecular weight of the obtained macromonomer A-1 was 6,000.

(Synthesis of Dispersant A)
In a three-necked flask having a capacity of 1000 mL, the above macromonomer A-1 solution (200.0 g), methacrylic acid (hereinafter, also referred to as “MAA”, 60.0 g), benzyl methacrylate (hereinafter, also referred to as “BzMA”, 40.0 g), PGMEA (propylene glycol 1-monomethyl ether 2-acetate, 366.7 g) was introduced to obtain a mixture. The mixture was stirred while blowing nitrogen. The mixture was then warmed to 75 ° C. while flowing nitrogen into the flask. Next, dodecyl mercaptan (5.85 g) and then 2,2'-azobis (methyl 2-methylpropionate) (1.48 g, hereinafter also referred to as "V-601") were added to the mixture for polymerization. The reaction was initiated. After heating the mixture at 75 ° C. for 2 hours, an additional V-601 (1.48 g) was added to the mixture. After 2 hours, an additional V-601 (1.48 g) was added to the mixture. After a further reaction for 2 hours, the mixture was heated to 90 ° C. and stirred for 3 hours. By the above operation, the polymerization reaction was completed, and then the solid content was purified to obtain a dispersant A.
Then, the dispersant A was used as a 30 mass% solution (solvent: PGMEA) in the preparation of the dispersion composition.

Dispersant B (resin having an ethylenically unsaturated group): Synthesized by the method shown below.

(Synthesis of Dispersant B)
The macromonomer A-1 solution (200.0 g), MAA (60.0 g), BzMA (40.0 g), and PGMEA (366.7 g) were introduced into a three-necked flask having a capacity of 1000 mL to obtain a mixture. The mixture was stirred while blowing nitrogen. The mixture was then warmed to 75 ° C. while flowing nitrogen into the flask. Next, dodecyl mercaptan (5.85 g) and then V-601 (1.48 g) were added to the mixture to initiate a polymerization reaction. After heating the mixture at 75 ° C. for 2 hours, an additional V-601 (1.48 g) was added to the mixture. After 2 hours, an additional V-601 (1.48 g) was added to the mixture. After a further reaction for 2 hours, the mixture was heated to 90 ° C. and stirred for 3 hours. The polymerization reaction was completed by the above operation.
After completion of the reaction, tetrabutylammonium bromide (TBAB, 7.5 g) and p-methoxyphenol (MEHQ, 0.13 g) were added in air, and then glycidyl methacrylate (hereinafter, also referred to as “GMA”, 66.1 g). ) Was dropped. After completion of the dropping, the reaction was continued in air for 7 hours, and then the completion of the reaction was confirmed by acid value measurement. PGMEA (643.6 g) was added to the obtained mixture to obtain a 20% by mass solution of dispersant B. The weight average molecular weight of the obtained dispersant B was 35,000, and the acid value was 50 mgKOH / mg.

Dispersant C (resin having an ethylenically unsaturated group): Synthesized by the method shown below.

(Synthesis of Dispersant C)
The macromonomer A-1 solution (100.0 g), MAA (200.0 g), and PGMEA (366.7 g) were introduced into a three-necked flask having a capacity of 1000 mL to obtain a mixture. From this point onward, a 20% by mass solution of the dispersant C was prepared in the same manner as in the synthesis of the dispersant B. The weight average molecular weight of the obtained dispersant C was 28,000, and the acid value was 55 mgKOH / mg.

<Solvent>
-PGMEA: Propylene glycol monomethyl ether acetate

<Preparation method of dispersion composition>
Each component was mixed so as to have a composition ratio (part by mass ratio) shown in Table 1, and the obtained mixture was dispersed under the following conditions using NPM-Pilot manufactured by Simmal Enterprises Co., Ltd. , A dispersion composition was obtained.

(Dispersion condition)
-Bead diameter: φ0.05 mm, (Nikkato zirconia beads, YTZ)
-Bead filling rate: 65% by volume
・ Mill peripheral speed: 10 or 12 m / sec
・ Separator peripheral speed: 13 m / s
・ Amount of mixed liquid to be dispersed: 15 kg
・ Circulation flow rate (pump supply amount): 90 kg / hour
-Treatment liquid temperature: 19 to 21 ° C
・ Cooling water: Water ・ Treatment time: 22 hours

[Preparation of curable composition]
The above-mentioned dispersion composition and other components shown below were mixed to obtain each curable composition used in Examples and Comparative Examples.
Table 2 below shows the composition ratio (part by mass ratio) of each component in each curable composition.
The description of "green" in the "type of pigment contained" column means that PG58 and PY185 are used in combination, and the composition is a curable composition because it forms a green cured film as a whole. To do.
The descriptions of "pigment (A)", "pigment (B)", and "pigment (C)" are "inorganic black pigment (A)", "inorganic black pigment (B)", and "inorganic black pigment (C), respectively." Means.
The column of "C = C value of resin" means the ethylenically unsaturated group content (C = C value) (mmol / g) with respect to the total mass of the resin contained in each curable composition.
The C = C value was determined by the following method. First, using a resin solution of each resin (a 20% by mass solution of dispersant B, etc.), the C = C value of each resin is determined by an HPLC method (absolute calibration method), and then each curable composition is obtained. The C = C value of the entire resin contained in each curable composition was calculated and obtained from the blending ratio of each resin blended in.

The details of the components corresponding to the descriptions in Table 2 are shown below.

<Dispersion composition>
The dispersion composition prepared by the method described above was used.
For each numbered curable composition, the corresponding numbered dispersion composition was used.

<Alkali-soluble resin>

-A-1 (resin containing an ethylenically unsaturated group): Acrycure RD-F8, manufactured by Nippon Catalyst Co., Ltd., solid content 40%, (solvent: propylene glycol monomethyl ether)

The alkali-soluble resin A-1 was used as a resin-containing solution (resin solution).

<Polymerization initiator>
-I-1: The compound represented by the following formula (I-1).

<Polymerizable compound>
-M1: KAYARAD DPHA, manufactured by Nippon Kayakusha, a hexafunctional polymerizable compound (amount of ethylenically unsaturated groups: 10.4 mmol / g), and a pentafunctional polymerizable compound (amount of ethylenically unsaturated groups: 9). .5 mmol / g) mixture)
-M2: A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd., a hexafunctional polymerizable compound (amount of ethylenically unsaturated groups: 5.41 mmol / g)
-M3: A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd., a trifunctional polymerizable compound (amount of ethylenically unsaturated groups: 7.09 mmol / g)

<Polymerization inhibitor>
PI-1: p-methoxyphenol

<Surfactant>
1: Surfactant represented by the following formula (weight average molecular weight (Mw) = 15311)
However, in the following formula, the structural units represented by (A) and (B) in the formula are 62 mol% and 38 mol%, respectively. In the structural unit represented by the formula (B), a satisfies the relationship of a + c = 14 and b = 17, respectively.

<Solvent>

-PGMEA: Propylene glycol monomethyl ether acetate

[Evaluation]
[Optical density of each curable composition layer]
Each curable composition was applied by a spin coating method on a glass substrate (EagleXG, manufactured by Corning Inc.) having a thickness of 0.7 mm and a size of 10 cm square to obtain a curable composition layer. At this time, the spin coater was rotated so that the film thickness of the curable composition layer after being heat-treated (pre-baked) for 150 seconds using a hot plate at 90 ° C. and dried was 1.5 μm. Adjusted the number.
The obtained curable composition layer after drying was measured for optical densities at a wavelength of 365 nm and a wavelength of 550 nm using a transmission densitometer (X-rite 361T (visual) densiometer).
The results are shown in Table 3.

[Rectangularity evaluation (initial)]
The composition for forming each cured film immediately after preparation was applied to a 200 mm (8 inch) silicon wafer (substrate) sprayed with hexamethyldisilazane in advance by a spin coating method to form a curable composition layer. At this time, the spin coater was rotated so that the film thickness of the curable composition layer after being heat-treated (pre-baked) for 150 seconds using a hot plate at 90 ° C. and dried was 1.5 μm. Adjusted the number.
For the dried curable composition layer having a film thickness of 1.5 μm, an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) was used to measure a pattern of 3.0 μm square at a wavelength of 365 nm. Exposure was made through an Island pattern mask.
In each Example and Comparative Example, the oxygen concentration at the time of exposure was in the range of 25 to 55% by volume, the irradiance was in the range of 1500 to 55000 W / m ² , and the exposure was performed at the optimum exposure amount.
The exposure was performed within 10 minutes after the prebaking.

Then, the silicon wafer on which the exposed curable composition layer is formed is placed on a horizontal rotary table of a spin shower developer (DW-30 type, manufactured by Chemitronics), and CD-2000 (organic alkali) is placed. Paddle development was performed at 23 ° C. for 60 seconds using a developing solution (manufactured by Fujifilm Electronics Materials Co., Ltd.).
In this way, a pattern (a cured film in the form of a 3.0 μm square square pixel pattern) was formed on the silicon wafer with the undercoat layer. The silicon wafer on which the pattern is formed is fixed to a horizontal rotary table by a vacuum chuck method, and while the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, pure water is ejected from above the center of rotation into a shower shape. It was supplied and rinsed. Then, the silicon wafer was dried. The obtained silicon wafer was further heated (post-baked) at 200 ° C. for 300 seconds to obtain a silicon wafer with a patterned cured film.

The cross section of the obtained silicon wafer was observed with a scanning electron microscope, and the angle of the side wall of the 3.0 μm square square pixel pattern (side wall of the square cured film) with respect to the surface of the silicon wafer was measured, and the pattern was measured according to the following evaluation criteria. The rectangularness of was evaluated.
The results are shown in Table 3.

"AA": Side wall angle is 80 ° or more and less than 100 ° "A": Side wall angle is 75 ° or more and less than 80 °, or 100 ° or more and less than 105 ° "B": Side wall angle is 70 ° or more and less than 75 ° Less than, or 105 ° or more and less than 110 ° "C": Side wall angle is 60 ° or more and less than 70 °, or 110 ° or more and less than 120 ° "D": Side wall angle is 50 ° or more and less than 60 °, or 120 ° or more and less than 130 ° "E": The angle of the side wall is less than 50 ° or 130 ° or more

[Evaluation of pattern rectangleness (1 week after prebaking)]
Except that the exposure was performed after prebaking and leaving it for one week, the rectangularity evaluation was carried out in the same manner as described above, and the evaluation was performed according to the same criteria.
The results are shown in Table 3.

[Rectangle evaluation of pattern (1 month after liquid time)]
Similar to the above, except that the curable composition layer was formed using the curable composition after being prepared and stored at room temperature (23 ° C., relative humidity 50%) for 1 month. (Initial)] was carried out and evaluated according to the same criteria.
The results are shown in Table 3.

[result]
Table 3 below shows the test results.
In Table 3, the column of "pigment" indicates the type of black pigment contained in the curable composition used. The abbreviations described in this column are the same as described in [Preparation of Dispersion Composition]. The description of "green" means that PG58 and PY185 are used in combination to form a green cured film as a whole. The descriptions of "pigment (A)", "pigment (B)" and "pigment (C)" are "inorganic black pigment (A)", "inorganic black pigment (B)" and "inorganic black pigment (C)", respectively. Means.
The column of "C = C value of resin" means the ethylenically unsaturated group content (mmol / g) of the entire resin contained in the curable composition used.
The column of "dispersor mill peripheral speed" means the mill peripheral speed when preparing the dispersion composition used for producing the curable composition.
The column of "Equation (1) value" is a value obtained by applying each test condition to the above-mentioned equation (1) (X × Y ÷ Z). The calculation method is as described above.
In the "rectangularity" column, the "initial", "1 week", and "1 month" columns are [rectangularity evaluation (initial)] and [pattern rectangularity evaluation (1 week after prebaking), respectively). ] [Evaluation of rectangularity of pattern (1 month after aging of liquid)] The evaluation result of the test is described.

As shown in Table 3, according to the production method of the present invention, a cured film (patterned cured film) having an excellent rectangular cross-sectional shape can be produced, and even when a reserved curable composition layer is used. It was confirmed that the tendency to maintain excellent rectangularness (the evaluation of rectangularity is C or higher) was confirmed.
When titanium nitride or oxynitride, zirconium nitride or oxynitride, vanadium nitride or oxynitride, or niobium nitride or oxynitride is used as the black pigment, the retention period is set. Even so, it was confirmed that the rectangularity of the obtained pattern was less likely to deteriorate (comparison between Example 10 and other examples).
When titanium nitride or oxynitride, or zirconium nitride or oxynitride is used as the black pigment, it has been confirmed that a cured film having more rectangularity can be obtained (Examples 1, 3 and 3). And the result of 7).
When the content of the ethylenically unsaturated group with respect to the entire resin contained in the curable composition was 0.10 to 3.00 mmol / g, it was confirmed that a cured film having more rectangularity could be obtained (implementation). Comparison of Examples 1, 13, and 14).
When the optical density A of the curable composition layer formed by using the curable composition is 2.80 to 4.00 and the optical density B is 2.50 to 7.00, the rectangularity becomes more rectangular. It was confirmed that an excellent cured film was obtained (results of Examples 1, 2, and 6).
When the irradiance at the time of exposure is 20000 to 50000 W / m ² , a cured film having more rectangularity can be obtained, and when the irradiance at the time of exposure is 2500 to 40,000 W / m ² , the cured film having further excellent rectangularness can be obtained. It was confirmed that the results tend to be obtained (results of Examples 1, 4, 5, 11 and 12).
When the inorganic black pigments (A), (B), and (C) were used as the black pigment, it was confirmed that a cured film having a more rectangular property could be obtained as in Example 1 (Example 1, Results of 18, 19, and 20).
When the value calculated by the formula (1) was in the range of 2.80 × ^{10-5 to} 5.20 × ^10-5 , the room temperature (23 ° C., relative humidity 50%) was stored for one month. Even when the later curable composition was used, deterioration of the rectangular cross-sectional shape of the produced cured film was suppressed as compared with the case where the curable composition that had not undergone storage treatment was used for evaluation. (Results of Examples 1 to 4, 7 to 9, and 13 to 17).

100 ... Solid-state image sensor 101 ... Solid-state image sensor 102 ... Imaging unit 103 ... Cover glass 104 ... Spacer 105 ... Laminated substrate 106 ... Chip substrate 107 ... Circuit board 108 ... Electrode pad 109 ... External connection terminal 110 ... Through electrode 111 ... Lens layer 112 ... Lens material 113 ... Support 114, 115 ... Hardened film 201 ... Light receiving element 202 ... Color filter 201 ... Light receiving element 202 ... Color filter 203 ... Micro lens 204 ... Substrate 205b ... Blue pixel 205r ... Red pixel 205g ... Green pixel 205bm ...・ Black matrix 206 ・ ・ ・ p-well layer 207 ・ ・ ・ Read gate part 208 ・ ・ ・ Vertical transfer path 209 ・ ・ ・ Element separation region 210 ・ ・ ・ Gate insulating film 211 ・ ・ ・ Vertical transfer electrode 212 ・ ・ ・ Curing Films 213, 214 ... Insulating film 215 ... Flattening film 300 ... Infrared sensor 310 ... Solid image sensor 311 ... Infrared absorption filter 312 ... Color filter 313 ... Infrared transmission filter 314 ... Resin film 315 ... Microlens 316 ... Flattening film

Claims (16)

Using a curable composition containing a black pigment and a polymerizable compound, the optical density A at a wavelength of 365 nm per 1.5 μm film thickness is 2.60 to 10.00, and the thickness per 1.5 μm film thickness. A step of forming a curable composition layer having an optical density B of 2.00 to 10.00 at a wavelength of 550 nm, and
The step of exposing the curable composition layer under the condition of an oxygen concentration of 30 to 50% by volume, and
The step of developing the curable composition layer after the exposure to form a cured film, and the like.
A method for producing a cured film. The production of the cured film according to claim 1, wherein the black pigment is a nitride or oxynitride of a group 4 metal element, a nitride or oxynitride of a group 5 metal element, or carbon black. Method. Claim that the black pigment is titanium nitride or oxynitride, zirconium nitride or oxynitride, vanadium nitride or oxynitride, niobium nitride or oxynitride, or carbon black. The method for producing a cured film according to 1 or 2. Claims 1 to 3 wherein the black pigment is a titanium nitride or oxynitride, a zirconium nitride or oxynitride, a vanadium nitride or oxynitride, or a niobium nitride or oxynitride. The method for producing a cured film according to any one of the above items. The method for producing a cured film according to any one of claims 1 to 4, wherein the black pigment is a nitride or oxynitride of titanium, or a nitride or oxynitride of zirconium. The method for producing a cured film according to any one of claims 1 to 5, wherein the irradiance in the exposure is 20000 to 50000 W / m ² . The method for producing a cured film according to any one of claims 1 to 6, wherein the irradiance in the exposure is 2500 to 40,000 W / m ² . The method for producing a cured film according to any one of claims 1 to 7, wherein the optical density A is 2.80 to 4.00 and the optical density B is 2.50 to 7.00. .. The method for producing a cured film according to any one of claims 1 to 8, wherein the ratio of the optical density B to the optical density A is 0.5 to 2.0. The curable composition further contains a resin and
The resin contains a resin containing an ethylenically unsaturated group.
The method for producing a cured film according to any one of claims 1 to 9, wherein the content of the ethylenically unsaturated group with respect to the total mass of the resin is 0.10 to 3.00 mmol / g. The method for producing a cured film according to any one of claims 1 to 10, wherein the curable composition further contains a polymerization initiator. The method for producing a cured film according to any one of claims 1 to 11, wherein the curable composition further contains a polymerization inhibitor. When the optical density A is X, the oxygen concentration at the time of exposure is Y, and the irradiance is Z, the values calculated by the following formula (1) are 2.80 × 10 ^{-5 to} 5.20 × 10. ^The method for producing a cured film according to any one of claims 1 to 12, which is ⁻⁵ .
Equation (1) X × Y ÷ Z The method for producing a cured film according to any one of claims 1 to 13, wherein the cured film is a light-shielding film. A method for manufacturing a solid-state image sensor, wherein the solid-state image sensor having a cured film is manufactured through the manufacturing method according to any one of claims 1 to 14. A method for manufacturing an image display device, wherein the image display device having a cured film is manufactured through the manufacturing method according to any one of claims 1 to 13.