JP7109565B2 - Light-shielding composition, cured film, light-shielding film, solid-state imaging device - Google Patents

Description

The present invention relates to a light-shielding composition, a cured film, a light-shielding film, and a solid-state imaging device.

A cured film used as a light-shielding film applied to a solid-state imaging device or the like is generally produced by forming a light-shielding composition layer on a substrate and then curing the layer. In this case, the light-shielding composition layer is typically exposed to light through a predetermined mask pattern, and then developed.

For example, in Patent Document 1, "A coating film containing at least one component selected from (a) a resin, (b) a coloring material, (c) inorganic fine particles, (d) a surfactant and an oil. and (d) a light-shielding coating film characterized in that the concentration of at least one component selected from surfactants and oils in the coating film is higher in the surface layer than in the lower layer (Claim 1). As an example of the above oil, dimethyl silicone oil is used.

JP 2011-141493 A

In recent years, there have been various demands for a cured film that is also used as a light-shielding film, in addition to good light-shielding properties. For example, as solid-state imaging devices become smaller, thinner, and more sensitive, there is a demand for a cured film with even lower reflection. In addition, the cured film can maintain excellent low reflectivity even when exposed to light for a long period of time (hereinafter, such characteristics are also referred to as "the cured film (or light-shielding film) has excellent light resistance"). It has been demanded.

Accordingly, an object of the present invention is to provide a light-shielding composition capable of forming a cured film having excellent light-shielding properties, low reflectivity, and light resistance. Another object of the present invention is to provide a cured film, a light-shielding film, and a solid-state imaging device.

As a result of intensive studies, the inventors have found that the above problems can be solved by the following configuration.

[1]

A black coloring material, a polymerizable compound, a photopolymerization initiator, and a light-shielding composition containing a resin,

The resin contains a polymerizable group and a group represented by general formula (1),

The resin has a number average molecular weight of 100 to 15,000,

A light-shielding composition, wherein the content of the resin is 2.0 to 15.0% by mass with respect to the total mass of the solid content of the light-shielding composition.

*-(SiR ¹ R ² -O) _na -* (1)

In general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

na represents an integer from 1 to 200;

* represents a binding position.

[2]

The light-shielding composition according to [1], wherein the resin is a compound represented by formula (2).

R ³ —(SiR ¹ R ² —O) _nb —SiR ¹ R ² —R ³ (2)

In general formula (2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

R ³ represents a group containing an ethylenically unsaturated group.

nb represents an integer from 3 to 200;

[3]

The light-shielding composition according to [2], wherein at least one of R ³ has an acid group.

[4]

The light-shielding composition according to [2] or [ ³ ], wherein at least one of R3 has at least one selected from the group consisting of an ether bond, an ester bond, a urethane bond and a thioether bond.

[5]

The light-shielding composition according to any one of [1] to [4], wherein the black colorant is at least one selected from the group consisting of metal nitrides and metal oxynitrides.

[6]

A cured film obtained using the light-shielding composition according to any one of [1] to [5].

[7]

The cured film contains a black layer and a coating layer disposed on the surface of the black layer,

The coating layer has a thickness of 20 to 200 nm,

The cured film according to [6], wherein the coating layer contains a cured product of the resin.

[8]

The cured film according to [6] or [7], which is a light shielding film.

[9]

[6] A solid-state imaging device comprising the cured film according to any one of [8].

ADVANTAGE OF THE INVENTION According to this invention, the light-shielding composition which can form the cured film which is excellent in light-shielding property, low reflectivity, and light resistance can be provided. A cured film, a light-shielding film, and a solid-state imaging device can also be provided.

1 shows a cross-sectional view of a preferred embodiment of the cured film of the present invention. FIG. It is a schematic sectional drawing which shows the structural example of a solid-state imaging device. FIG. 3 is a schematic cross-sectional view showing an enlarged imaging unit of FIG. 2 ; It is a schematic sectional drawing which shows the structural example of an infrared sensor.

The present invention will be described in detail below.

The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

In this specification, a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.

In addition, in the notation of a group (atomic group) in this specification, a notation that does not describe substituted or unsubstituted includes a group containing a substituent as well as a group not containing a substituent, as long as it does not contradict the spirit of the present invention. contain. For example, the term “alkyl group” includes not only alkyl groups containing no substituents (unsubstituted alkyl groups) but also alkyl groups containing substituents (substituted alkyl groups).

In addition, "actinic rays" or "radiation" in this specification means, for example, deep ultraviolet rays, extreme ultraviolet lithography (EUV), X-rays, electron beams, and the like. Moreover, in this specification, light means actinic rays and radiation. Unless otherwise specified, “exposure” in this specification 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.

Moreover, in this specification, "(meth)acrylate" represents acrylate and methacrylate. Moreover, in this specification, "(meth)acryl" represents acryl and methacryl. Moreover, in this specification, "(meth)acryloyl" represents acryloyl and methacryloyl. Moreover, in this specification, "(meth)acrylamide" represents acrylamide and methacrylamide. Moreover, in this specification, the terms "monomer" and "monomer" are synonymous.

As used herein, the weight average molecular weight (Mw) and number average molecular weight (Mn) are polystyrene equivalent values obtained by GPC (Gel Permeation Chromatography).

In the present specification, the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) as columns, and THF (tetrahydrofuran) as an eluent. ) based on the method using

[Light-shielding composition]

The light-shielding composition of the present invention (hereinafter also simply referred to as "composition") contains a black colorant, a polymerizable compound, a photopolymerization initiator, and a resin.

The above resin is a resin having a number average molecular weight of 100 to 15,000 and containing a polymerizable group and a group represented by general formula (1) described later (this resin is hereinafter also referred to as "specific resin"). .

The content of the specific resin is 2.0 to 15.0% by mass with respect to the total mass of the solid content of the light-shielding composition.

The mechanism by which the composition having the structure described above solves the problems of the present invention is not necessarily clear, but the present inventors speculate as follows.

The (poly)siloxane group represented by general formula (1) contained in the specific resin exhibits low surface free energy. Moreover, since the molecular weight is 100 to 15,000, it can move relatively freely in the composition. Therefore, for example, in a composition layer formed by coating a composition on a substrate, the specific resin tends to be concentrated and present in the vicinity of the surface of the composition layer on the side opposite to the substrate. As a result, as shown in FIG. 1, the cured film 10 obtained by curing the composition layer on the substrate 16 is composed of a black layer (lower layer) 12 containing a black coloring material and a cured product of a specific resin. It has a two-layer structure with a coating layer (upper layer) 14 that it contains. When such a two-layer structure is formed, the light reflected by the surface of the coating layer and the light reflected by the interface between the coating layer and the black layer are canceled by interference, thereby realizing low reflectivity. . In addition, since the specific resin contains a polymerizable group, the coating layer is not removed from the cured film even when the cured film is developed during the process of forming the cured film, and excellent low reflectivity is realized. Furthermore, it is speculated that the (poly)siloxane group contained in the specific resin has a rigid structure, and thus is resistant to deterioration even when exposed to light, thus improving the light resistance.

First, the components of the composition of the present invention will be explained.

[Black coloring material]

The light-shielding composition contains a black colorant.

The content of the black coloring material in the composition is preferably 10 to 90% by mass, more preferably 30 to 80% by mass, and even more preferably 50 to 70% by mass, based on the total mass of the solid content of the composition.

The term "light shielding" in which a cured film formed from the composition of the present invention is used as a light shielding film is a concept that includes the attenuation of light passing through a cured film (light shielding film) while attenuating light. When a cured film (light-shielding film) is used as the light-attenuating film having such functions, the content of the black colorant in the composition is preferably less than the preferred range described above.

One kind of black coloring agent may be used alone, or two or more kinds thereof may be used.

In the present specification, the solid content of the composition refers to all components other than the solvent when the composition contains a solvent (organic solvent, water, etc.). Even liquid ingredients are regarded as solids.

The black colorant includes one or more selected from the group consisting of black pigments and black dyes.

In addition, a plurality of coloring agents that cannot be used alone as a black coloring agent may be combined and adjusted so as to be black as a whole, and used as a black coloring agent.

For example, in addition to using a pigment that exhibits black color by itself as a black pigment, a plurality of pigments that individually have a color other than black may be used in combination as a black pigment. Similarly, in addition to using a black dye as a dye that expresses black color by itself, a plurality of dyes having a color other than black alone may be used in combination as a black dye.

In addition, by using a colorant that cannot be used as a black colorant by itself, it is easy to adjust the light shielding properties of the cured film. For example, when a cured film is used as a light-attenuating film, each wavelength tends to be uniformly attenuated with respect to light containing a wide range of wavelength components.

The black colorant is a colorant that absorbs light over the entire wavelength range of 400 to 700 nm.

More specifically, for example, a black colorant that meets the evaluation criteria Z described below is preferable.

First, a composition containing a coloring material, a transparent resin matrix (acrylic resin or the like), and a solvent, and having a coloring material content of 60% by mass relative to the total solid content is prepared. The obtained composition is applied onto a glass substrate so that the thickness of the coating film after drying is 1 μm to form a coating film. The light shielding property of the dried coating film is evaluated using a spectrophotometer (UV-3600 manufactured by Hitachi, Ltd., etc.). If the maximum transmittance of the dried coating film at a wavelength of 400 to 700 nm is less than 10%, the coloring material can be judged to be a black coloring material that meets the evaluation criteria Z.

(black pigment)

The black colorant is preferably a black pigment such as a metal nitride and/or a metal oxynitride, since a cured film with better low reflectivity can be obtained.

Various known black pigments can be used as the black pigment. The black pigment may be an inorganic pigment or an organic pigment.

As the black pigment, a pigment that expresses black color by itself is preferable.

Various known black pigments can be used as the black pigment. The black pigment may be an inorganic pigment or an organic pigment.

As the black inorganic pigment, for example, one or more selected from the group consisting of metal nitrides, metal oxynitrides, and metal oxides is preferable, and selected from the group consisting of metal nitrides and metal oxynitrides. more preferably one or more.

As metal nitrides, metal oxynitrides, and metal oxides, more specifically, for example, Group 4 metal elements such as titanium (Ti) and zirconium (Zr), vanadium (V) and niobium (Nb ) and other Group 5 metal elements, cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), ruthenium (Ru), iron (Fe), nickel (Ni), tin (Sn), and metal nitrides, metal oxynitrides and metal oxides containing one or more metal elements selected from the group consisting of silver (Ag).

The inorganic pigment may be subjected to surface modification treatment. Examples thereof include inorganic particles surface-modified with a surface-treating agent having both a silicone group and an alkyl group, such as the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., Ltd.). Metal nitrides, metal oxynitrides, and metal oxides may also be used as particles in which other atoms are mixed. For example, they may be used as metal nitrides, metal oxynitrides and metal oxides further containing atoms (preferably sulfur atoms) selected from Groups 13 to 17 of the periodic table.

Black pigments also include carbon black. As the carbon black, carbon black whose surface is coated with a resin may be used. As a black pigment, commercially available C.I. I. Pigment Black 1 and organic pigments such as Irgaphor Black S 0100 CF and C.I. I. Inorganic pigments such as Pigment Black 7 are also included.

In the present specification, titanium nitride means TiN, and may contain oxygen atoms that are unavoidable in manufacturing (for example, the surface of TiN particles is unintentionally oxidized, etc.).

In the present specification, titanium nitride means a compound having a diffraction angle 2θ of a peak derived from the (200) plane of 42.5° to 42.8° when CuKα rays are used as an X-ray source.

In the present specification, titanium oxynitride means a compound having a diffraction angle 2θ of a peak derived from the (200) plane exceeding 42.8° when CuKα rays are used as an X-ray source. Although the upper limit of the diffraction angle 2θ of titanium oxynitride is not particularly limited, it is preferably 43.5° or less.

Titanium oxynitride includes, for example, titanium black, etc. More specifically, for example, TiO ₂ , Ti _n O _2n−1 (1≦n≦20), and/or low order titanium oxide represented by A form containing titanium oxynitride represented by TiN _x O _y (0<x<2.0, 0.1<y<2.0) is exemplified. In the following description, titanium nitride (the diffraction angle 2θ is 42.5° to 42.8°) and titanium oxynitride (the diffraction angle 2θ is greater than 42.8°) are collectively referred to as titanium nitrides. The form will be described.

Titanium nitride may also be used as particles in which other atoms are mixed. For example, titanium nitride may be used as titanium nitride-containing particles that further contain atoms selected from elements of groups 13-17 of the periodic table (preferably sulfur atoms). The same applies to other metal nitrides, and metal nitrides collectively referred to as metal nitrides and metal oxynitrides may be used as particles in which other atoms are mixed. For example, metal nitrides may be used as metal nitrides further containing atoms selected from elements of Groups 13-17 of the periodic table (preferably sulfur atoms).

When the X-ray diffraction spectrum of titanium nitride is measured using CuKα rays as an X-ray source, the peak derived from the (200) plane of TiN is near 2θ = 42.5° as the peak with the strongest intensity, and that of TiO is ( 200) plane is observed near 2θ=43.4°. On the other hand, although it is not the strongest peak, the peak derived from the (200) plane for anatase-type TiO ₂ is near 2θ = 48.1°, and the peak derived from the (200) plane for rutile-type TiO ₂ is 2θ = 39°. Observed near 0.2°. Therefore, as the titanium oxynitride contains more oxygen atoms, the peak position shifts to the higher angle side with respect to 42.5°.

When titanium nitride contains titanium oxide TiO ₂ , the peak derived from anatase-type TiO ₂ (101) as the strongest peak is near 2θ=25.3°, derived from rutile-type TiO ₂ (110). A peak is seen near 2θ=27.4°. However, since TiO ₂ is white and causes a decrease in the light-shielding property of the cured film obtained by curing the composition, it is preferably reduced to such an extent that no peak is observed.

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

The crystallite size constituting titanium nitride is preferably 50 nm or less, and preferably 20 nm or more. When the crystallite size is 20 to 50 nm, the cured film formed using the composition tends to have a higher transmittance of ultraviolet light (especially i-line (wavelength: 365 nm)), and a composition with higher photosensitivity can be obtained. be done.

Although the specific surface area of titanium nitride is not particularly limited, it can be determined by the BET (Brunauer, Emmett, Teller) method. The specific surface area of titanium nitride is preferably 5 to 100 m ² /g, more preferably 10 to 60 m ² /g.

The method for producing the black pigment is not particularly limited, and known production methods can be used, for example, a gas phase reaction method. The gas phase reaction method includes an electric furnace method, a thermal plasma method, and the like, but the thermal plasma method is preferable in terms of less impurity contamination, easier particle diameter uniformity, and higher productivity.

In the thermal plasma method, the method for generating thermal plasma is not particularly limited, and includes direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, hybrid plasma, etc., and there is little contamination of impurities from the electrode. High frequency plasma is more preferred.

A specific method for producing a black pigment by a thermal plasma method is not particularly limited. For example, as a method for producing titanium nitride, a method of reacting titanium tetrachloride and ammonia gas in a plasma flame (JP-A-2-22110 JP-A-61-11140), a method in which titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced as a carrier gas, and nitridation is performed in the cooling process (JP-A-61-11140), and ammonia gas is added to the periphery of the plasma. A blowing method (JP-A-63-85007) and the like can be mentioned.

However, the method for producing the 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 (oxy)nitride of the metal atom may be coated with a silicon-containing compound to form a black pigment.

The method for coating the (oxy)nitride of metal atoms is not particularly limited, and known methods can be used. A method (using a metal atom (oxy)nitride instead of titanium oxide), a method described in paragraphs 0015 to 0043 of JP-A-2008-69193 (instead of fine particle titanium dioxide, a metal atom (acid) Nitrides), paragraphs 0020 and paragraphs 0124 to 0138 of JP-A-2016-74870 (in place of the metal oxide fine particles, a metal atom (oxy)nitride is used). , the contents of which are incorporated herein.

Furthermore, when the light-shielding composition contains titanium black, it is also preferable to contain titanium black as a dispersant containing titanium black and Si atoms.

In this form, titanium black is contained as a dispersed material in the composition, and the content ratio (Si/Ti) of Si atoms and Ti atoms in the dispersed material is 0.05 or more in terms of mass. is preferred, 0.05 to 0.5 is more preferred, and 0.07 to 0.4 is even more preferred.

Here, the material to be dispersed includes both titanium black in the state of primary particles and titanium black in the state of aggregates (secondary particles).

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

First, titanium oxide and silica particles are dispersed using a disperser to obtain a dispersion, and this dispersion is subjected to a reduction treatment at a high temperature (for example, 850 to 1000 ° C.), so that titanium black particles are mainly A dispersion object containing Si and Ti as components can be obtained. The reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia.

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

Commercial products of silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name: manufactured by Evonik).

A dispersant may be used to disperse the titanium oxide and silica particles. Examples of the dispersant include those described below as dispersants.

The above dispersion may be carried out in a solvent. Examples of solvents include water and organic solvents. Examples thereof include those described in the column of the organic solvent described later.

Titanium black in which Si/Ti is adjusted to, for example, 0.05 or more can be produced, for example, by the method described in paragraphs 0005 and 0016 to 0021 of JP-A-2008-266045.

By adjusting the content ratio (Si/Ti) of Si atoms and Ti atoms in the dispersed material containing titanium black and Si atoms to a suitable range (for example, 0.05 or more), a composition containing this dispersed material When a cured film is formed using a material, residue derived from the composition outside the cured film formation region is reduced. The residue contains components derived from the composition, such as titanium black particles and resin components.

The reason why the residue is reduced is not yet clear, but the particles to be dispersed tend to have a small particle size (for example, the particle size is 30 nm or less), and furthermore, the Si atoms of the particles to be dispersed It is surmised that the increase in the content of the components reduces the adsorptivity of the film as a whole to the substrate, and this contributes to the improvement in the development removability of the uncured composition (especially titanium black) in the formation of the cured film. there is

In addition, titanium black is excellent in light shielding properties against light in a wide wavelength range from ultraviolet light to infrared light, so the above-described titanium black and a dispersed body containing Si atoms (preferably Si / Ti in terms of mass 0.05 or more) exhibits excellent light shielding properties.

The content ratio (Si/Ti) of Si atoms and Ti atoms in the material to be dispersed is, for example, the method (1-1) or method (1-2) described in paragraph 0033 of JP-A-2013-249417. ) can be measured using

Also, regarding the substance to be dispersed contained in the cured film obtained by curing the composition, whether the content ratio (Si/Ti) of Si atoms and Ti atoms in the substance to be dispersed is 0.05 or more To determine, the method (2) described in paragraph 0035 of JP-A-2013-249417 is used.

In the dispersed material containing titanium black and Si atoms, the above titanium black can be used.

Materials used for introducing Si atoms into the dispersed material are described below. When Si atoms are introduced into the substance to be dispersed, a Si-containing substance such as silica may be used.

Silica that can be used includes precipitated silica, fumed silica, colloidal silica, synthetic silica, and the like, and these may be appropriately selected and used.

Furthermore, when the particle size of the silica particles is smaller than the film thickness of the cured film, the light shielding properties are more excellent, so it is preferable to use fine particle type silica as the silica particles. Examples of particulate type silica include silica described in paragraph 0039 of JP-A-2013-249417, the contents of which are incorporated herein.

It is also preferable to use zirconium nitride and zirconium oxynitride. Zirconium nitride and zirconium oxynitride are preferably coated with an inorganic compound. By coating with an inorganic compound, the photocatalytic activity of the light-shielding pigment is suppressed without impairing the light-shielding properties of the light-shielding pigment due to the surface coating, and deterioration of the light-shielding composition can be easily prevented. Specific examples of inorganic compounds include titanium dioxide, zirconia, silica and alumina, with silica and alumina being preferred. Combinations of titanium black and zirconium nitride, titanium black and zirconium oxynitride, titanium black and silica-coated zirconium nitride, and titanium black and alumina-coated zirconium nitride are also preferred.

Furthermore, as described above, a plurality of pigments having a color other than black alone may be used in combination as a black pigment.

Such a pigment that alone has a color other than black may be either an inorganic pigment or an organic pigment. As a pigment having a color other than black by itself, for example, chromatic color pigments (chromatic pigments) such as R (red), G (green), and B (blue) can also be used.

The inorganic pigment which alone has a color other than black is not particularly limited, and known inorganic pigments can be used.

Examples of the inorganic pigments include titanium oxide, chromium oxide, iron oxide, red lead, iron oxide red, yellow lead, zinc yellow (zinc yellow type 1, zinc yellow type 2), ultramarine blue, Prussian blue (ferrocyan Potassium oxide) Zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, Victoria green, Prussian blue (unrelated to Prussian blue), vanadium zirconium blue, chrome tin pink, pottery red, salmon pink, etc. .

The inorganic pigment may be subjected to a surface modification treatment. Examples thereof include inorganic pigments surface-modified with a surface-treating agent having both a silicone group and an alkyl group, such as the "KTP-09" series (manufactured by Shin-Etsu Chemical Co., Ltd.).

The organic pigment having a color other than black by itself is selected from, for example, the following organic pigments.

Color Index (C.I.) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214 etc.,

C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ,

C. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, 294 (xanthene , Organo Ultamarine, Bluish Red), 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 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,29,60,64,66,79,80,87 (monoazo), 88 (methine/polymethine system) and the like;

A pigment may be used in combination with a dye, which will be described later.

In order to adjust the color and to enhance the light-shielding property in the desired wavelength region, for example, a pigment that alone expresses black and / or a pigment that alone has a color other than black, red, green, Chromatic pigments such as yellow, orange, purple, and blue or dyes described later may be mixed.

It is also preferable to mix a red pigment or dye, or a violet pigment or dye to a pigment that absorbs infrared rays and expresses black by itself, and more preferably a red pigment.

Furthermore, an infrared absorbing agent, which will be described later, may be added.

Further, as a pigment which alone has a color other than black and which absorbs infrared rays, a tungsten compound, a metal boride, or the like can also be used. Among them, tungsten compounds are preferable from the viewpoint of excellent light-shielding properties at wavelengths in the infrared region. Tungsten compounds are excellent in the light absorption wavelength region of the oxime polymerization initiator, which is related to the curing efficiency by exposure, and in the visible light region.

Considering 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. When the black pigment is a combination of a plurality of types of pigments, it is preferable that one or more of the pigments that constitute the black pigment are within the above range, and that all the pigments that constitute the black pigment are within the above range. more preferred.

The average primary particle size of the pigment can be measured using a transmission electron microscope (TEM). As a transmission electron microscope, for example, a transmission electron microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.

The maximum length of the particle image obtained using a transmission electron microscope (Dmax: the maximum length at two points on the contour of the particle image) and the maximum vertical length (DV-max: two straight lines parallel to the maximum length When the image is sandwiched between the two straight lines, the shortest length that connects the two straight lines perpendicularly) is measured, and the geometric mean value (Dmax×DV-max) ^1/2 is taken as the particle diameter. The particle diameters of 100 particles are measured by this method, and the arithmetic average value is taken as the average particle diameter, which is the average primary particle diameter of the pigment.

(black dye)

As the black dye, a dye that expresses black by itself can be used. Furthermore, as described above, a plurality of dyes having a color other than black alone may be used in combination as a black dye.

Examples of such colored dyes include, for example, R (red), G (green), and B (blue), and other chromatic dyes (chromatic dyes). 0200 can also be used.

Further, as dyes, for example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-A-2592207, US Pat. No., US Pat. No. 5667920, US Pat. Dyes disclosed in publications and the like can be used. Classified by chemical structure, pyrazole azo compounds, pyrromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, or pyrrolopyrazole azomethine compounds and the like can be used. Moreover, you may use a dye multimer as a dye. Examples of dye multimers include compounds described in JP-A-2011-213925 and JP-A-2013-041097. Moreover, a polymerizable dye having polymerizability in the molecule may be used, and commercially available products thereof include, for example, the RDW series manufactured by Wako Pure Chemical Industries, Ltd.

(Infrared absorber)

The composition may further contain an infrared absorber as a colorant that alone has a color other than black.

An infrared absorbing agent means a compound having absorption in the wavelength region of the infrared region (preferably wavelength of 650 to 1300 nm). As the infrared absorber, a compound having a maximum absorption wavelength in the wavelength range of 675 to 900 nm is preferred.

Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, and quaterrylene. compounds, dithiol metal complex compounds, croconium compounds, and the like.

Phthalocyanine compounds, naphthalocyanine compounds, iminium compounds, cyanine compounds, squarylium compounds, and croconium compounds may use the compounds disclosed in paragraphs 0010 to 0081 of JP-A-2010-111750, the contents of which are described herein. incorporated into the book. For the cyanine compound, for example, "Functional Dyes, Shin Okawara/Ken Matsuoka/Teijiro Kitao/Tsunesuke Hirashima, Kodansha Scientific" can be referred to, the contents of which are incorporated herein.

As the colorant having the above spectral characteristics, compounds disclosed in paragraphs 0004 to 0016 of JP-A-07-164729 and/or compounds disclosed in paragraphs 0027-0062 of JP-A-2002-146254, JP-A-2011-164583 It is also possible to use near-infrared absorbing particles composed of crystallites of an oxide containing Cu and/or P disclosed in paragraphs 0034 to 0067 of the publication and having a number average aggregate particle size of 5 to 200 nm.

The compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferably at least one selected from the group consisting of cyanine compounds, pyrrolopyrrole compounds, squarylium compounds, phthalocyanine compounds, and naphthalocyanine compounds.

In addition, the infrared absorbing agent 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. Solvent resistance is improved by using such a compound.

Pyrrolopyrrole compounds can be referred to paragraphs 0049 to 0062 of JP-A-2010-222557, the contents of which are incorporated herein. The cyanine compound and the squarylium compound are described in paragraphs 0022 to 0063 of WO 2014/088063, paragraphs 0053 to 0118 of WO 2014/030628, paragraphs 0028 to 0074 of JP 2014-59550, and WO 2012/ Paragraphs 0013 to 0091 of 169447, paragraphs 0019 to 0033 of JP 2015-176046, paragraphs 0053 to 0099 of JP 2014-63144, paragraphs 0085 to 0150 of JP 2014-52431, JP Paragraphs 0076 to 0124 of 2014-44301, paragraphs 0045 to 0078 of JP 2012-8532, paragraphs 0027 to 0067 of JP 2015-172102, paragraphs 0029 to 0067 of JP 2015-172004, Paragraphs 0029 to 0085 of JP-A-2015-40895, paragraphs 0022-0036 of JP-A-2014-126642, paragraphs 0011-0017 of JP-A-2014-148567, paragraphs 0010- of JP-A-2015-157893 0025, paragraphs 0013 to 0026 of JP 2014-095007, paragraphs 0013 to 0047 of JP 2014-80487, and paragraphs 0007 to 0028 of JP 2013-227403 can be considered, and this content is incorporated herein.

[Resin (specific resin)]

The resin of the present invention contains a specific resin.

The content of the specific resin in the composition is 2.0 to 15.0% by mass with respect to the total solid content of the composition, and the resulting cured film has excellent light-shielding properties and low reflectivity in a well-balanced manner. 2.0 to 10.0% by mass is more preferable from the point of view.

In addition, when the composition contains a main chain type specific resin described later as a specific resin, the content of the main chain type specific resin is 2.0 to 6.0% by mass relative to the total solid content of the composition. is more preferred.

When the composition contains a side chain type specific resin described later as the specific resin, the content of the side chain type specific resin is more preferably more than 3.0 and 10 or less relative to the total solid content of the composition.

When two or more specific resins are used, the total content is preferably within the above range.

The mass ratio of the content of the specific resin to the black colorant in the composition is preferably 0.02 to 0.9, more preferably 0.02 to 0.3, even more preferably 0.02 to 0.2, 0.02 to 0.1 is particularly preferred. In addition, the mass ratio of the content represents (content of the specific resin)/(content of the black colorant) in the composition.

A specific resin contains a polymerizable group. As the polymerizable group, an ethylenically unsaturated group (a group containing an ethylenically unsaturated bond, such as a (meth)acryloyl group, a vinyl group, an allyl group, and a styryl group), and a cyclic ether group (eg, epoxy group, oxetanyl group, etc.) and the like, but are not limited thereto.

Among them, the polymerizable group is preferably an ethylenically unsaturated group, and more preferably a (meth)acryloyl group, because polymerization can be controlled by a radical reaction.

The specific resin has a number average molecular weight of 100-15,000. Among them, 200 to 15000 are preferable.

The weight average molecular weight of the specific resin is preferably 500-40,000.

The specific resin contains a group represented by general formula (1).

*-(SiR ¹ R ² -O) _na -* (1)

In general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.

When there are multiple R ¹ 's, the multiple R ¹ 's may be the same or different. When multiple R ² are present, the multiple R ² may be the same or different.

As the alkyl group, an alkyl group having 1 to 8 carbon atoms is preferable, and examples thereof include methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group and octyl group. . Among them, a methyl group is preferred.

The cycloalkyl group may be monocyclic or polycyclic. The monocyclic ring is preferably a cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and the like. The polycyclic ring is preferably a cycloalkyl group having 6 to 20 carbon atoms, such as adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinene group, tricyclodecanyl group, tetracyclododecyl group. , and androstanyl group.

The aryl group is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group, and anthryl group.

In general formula (1), na represents an integer of 1 to 200, preferably 5 to 100, more preferably 5 to 70.

* represents a binding position.

There is no restriction on the form in which the group represented by general formula (1) exists in the specific resin, and the group represented by general formula (1) may exist as a main chain in the specific resin, and general formula (1 ) may exist as a side chain in the specific resin.

In addition, let the longest chain|strand in a specific resin be a main chain, and let the chain|strand couple|bonded with a main chain be a side chain.

<Specific resin having a group represented by general formula (1) as a main chain (main chain type specific resin)>

In the specific resin in which the group represented by the general formula (1) exists as a main chain (hereinafter also referred to as "main chain type specific resin"), only one group represented by the general formula (1) is present. may exist, or two or more may exist. In the main chain type specific resin, when there are a plurality of groups represented by general formula (1), for example, between a plurality of groups represented by general formula (1), A group other than a group is present as a linking group.

The number of groups represented by general formula (1) contained in the main chain type specific resin is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1.

The main chain type specific resin may be branched or linear, and preferably linear.

Moreover, the main chain-type specific resin preferably contains a group containing a polymerizable group (preferably an ethylenically unsaturated group) at least one (preferably two or more) ends thereof. Among them, it is preferable that the main chain-type specific resin is linear and contains a group containing a polymerizable group (preferably an ethylenically unsaturated group) at both ends thereof.

Also, one or more of the terminal groups of the backbone-type specific resin may contain an acid group such as a carboxylic acid group, a sulfonic acid group, and/or a phosphonic acid group. One or more of the terminal groups of the main chain type specific resin may contain both an acid group and a polymerizable group (preferably an ethylenically unsaturated group).

The weight average molecular weight of the main chain type specific resin is preferably from 500 to 20,000, more preferably from 500 to 10,000, even more preferably from 600 to 10,000.

The number average molecular weight of the main chain type specific resin is preferably 200 to 10,000, more preferably 300 to 7,500, even more preferably 350 to 7,500.

The dispersion degree (weight average molecular weight/number average molecular weight) of the main chain type specific resin is preferably 8 or less, more preferably 4 or less. The lower limit of the dispersity is usually 1 or more.

The main chain type specific resin is preferably, for example, a compound represented by general formula (2).

R ³ —(SiR ¹ R ² —O) _nb —SiR ¹ R ² —R ³ (2)

In general formula (2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. R ¹ and R ² in general formula (2) are the same as R ¹ and R ² in general formula (1), respectively.

In general formula ( ² ), R3 represents a group containing an ethylenically unsaturated group.

A plurality of R ³ may be the same or different.

R ³ may partially contain an ethylenically unsaturated group, or R ³ may be an ethylenically unsaturated group itself.

Examples of ethylenically unsaturated groups include (meth)acryloyl groups, vinyl groups, allyl groups, and styryl groups, with (meth)acryloyl groups being preferred.

The structure of R ³ is not particularly limited as long as it contains an ethylenically unsaturated group, but the carbon number of R ³ is preferably 40 or less, more preferably 30 or less. The lower limit of the number of carbon atoms in R3 is usually ² or more.

The number of ethylenically unsaturated groups possessed by R ³ is preferably 1-5, more preferably 1-2.

At least one R ³ may contain a heteroatom (an oxygen atom, a sulfur atom, and/or a nitrogen atom, etc.), for example, a (meth)acryloyl group is a (meth)acryloyloxy group together with an oxygen atom may form Also, at least one R ³ preferably contains at least one of an ether bond, an ester bond, a carbonate bond, an amide bond, a urethane bond, a urea bond, and a thioether bond, an ether bond, an ester More preferably, it contains at least one of a bond, a urethane bond, and a thioether bond.

Also, at ^least one R3 may further contain an acid group such as a carboxylic acid group, a sulfonic acid group and/or a phosphonic acid group, and preferably contains a carboxylic acid group.

When the main chain type specific resin has an acid value, the acid value is preferably 100 mgKOH/g or less, more preferably 10 to 50 mgKOH/g. Within this range, the main chain type specific resin that has not been fixed during exposure is easily removed from the cured film during development. The acid value is the mass [mg] of potassium hydroxide required to neutralize 1 g of sample, and the unit is expressed as mgKOH/g in this specification.

In addition, the main chain type specific resin preferably has an ethylenically unsaturated group content of 0.001 to 10.0 mmol/g, more preferably 0.1 to 6.0 mmol/g, relative to the total mass of the resin. more preferred.

In general formula (2), nb represents an integer of 5 to 200, preferably 5 to 100, more preferably 5 to 70.

<Specific resin having a group represented by general formula (1) as a side chain (side chain type specific resin)>

The weight-average molecular weight of the specific resin in which the group represented by the general formula (1) exists as a side chain (hereinafter also referred to as "side chain type specific resin") is more preferably 500 to 40,000, more preferably 500 to 20,000, 500 to 10,000 are more preferred.

The number average molecular weight of the side chain type specific resin is preferably 500 to 15,000, more preferably 500 to 8,000.

The degree of dispersion (weight average molecular weight/number average molecular weight) of the side chain type specific resin is preferably 8 or less, more preferably 4 or less. The lower limit of the dispersity is usually 1 or more.

The side chain type specific resin preferably contains, for example, a group represented by general formula (3).

*-(SiR ¹ R ² -O) _nc -SiR ¹ R ² -R ⁴ (3)

In general formula (3), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. R ¹ and R ² in general formula (3) are the same as R ¹ and R ² in general formula (1), respectively.

In general formula (3), R ⁴ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms. When R ⁴ is an organic group, it may contain a heteroatom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.). Among them, R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

In general formula (3), nc represents an integer of 1-200, preferably 2-100.

The side chain type specific resin preferably further contains a side chain containing an acid group such as an alkali-soluble group. This facilitates removal of the side chain type specific resin that has not been cured during exposure during development. The side chain type specific resin may contain side chains containing two or more acid groups.

Acid groups contained in the side-chain type specific resin are not particularly limited, but carboxylic acid groups, phenolic hydroxyl groups, sulfonic acid groups, and the like are preferable.

The side chain type specific resin preferably has an acid value of 100 mgKOH/g or less, more preferably 10 to 50 mgKOH/g. Within this range, the side-chain type specific resin that has not been immobilized during exposure is easily removed from the cured film during development.

Side chains containing acid groups may be formed directly by the polymerization reaction or by chemical transformation after the polymerization reaction.

The side chain type specific resin is, for example, a monomer containing a group represented by general formula (1) (preferably a group represented by general formula (3)), a monomer containing a reactive group, If necessary, a copolymer obtained by copolymerizing a monomer containing an acid group and/or other monomers, a functional group capable of bonding to a reactive group, and a polymerizable group (preferably can be synthesized by reacting it with a compound containing an ethylenically unsaturated group).

The monomer containing the group represented by the general formula (1), which is used for the synthesis of the side chain type specific resin, is preferably the monomer represented by the general formula (4).

CH ₂ =CR ^s -COO-Z-(SiR ¹ R ² -O) _nc -SiR ¹ R ² -R ⁴ (4)

In general formula (4), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. R ⁴ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms.

R ¹ , R ² and R ⁴ in general formula (4) are the same as R ¹ , R ² and R ⁴ in general formula (3), respectively.

In general formula (4), R ^s represents a hydrogen atom or a methyl group.

In general formula (4), Z represents a single bond or a divalent organic group having 1 to 6 carbon atoms. Z is preferably a divalent hydrocarbon group having 1 to 6 carbon atoms, such as -CH ₂ -, -CH ₂ CH ₂ -, -CH(CH ₃ )-, -CH ₂ CH ₂ CH ₂ -, -C(CH ₃ ) ₂ -, -CH(CH ₂ CH ₃ )-, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH(CH ₂ CH ₂ CH ₃ )-, -CH ₂ (CH2) ₃ CH ₂ — and —CH(CH ₂ CH(CH ₃ ) ₂ )— are included.

The monomer containing a reactive group is not particularly limited, but for example, a monomer containing a hydroxyl group, an acid anhydride containing an ethylenic double bond, a monomer containing a carboxylic acid group, and , epoxy group-containing monomers, and two or more of them may be used. In addition, it is preferable that the monomer containing a reactive group does not contain the group represented by the general formula (1).

Examples of hydroxyl-containing monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5- Hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono ( meth)acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl (meth)acrylamide, and N,N-bis(hydroxymethyl) (meth) ) acrylamide.

Further, the hydroxyl-containing monomer may contain a polyoxyalkylene group having a terminal hydroxyl group. Examples of such hydroxyl _- containing _monomers include _{CH2 = CHOCH2C6H10CH2O ( CH2CH2O} ) _kH , _{CH2 = CHOC4H8O ( CH2CH2} O) kH, _{CH2 = CHCOOCH2CH2O} ( _CH2CH2O ) kH, _{CH2 = C} ( _CH3 ) _{COOCH2CH2O ( CH2CH2O} ) _kH , _{CH2 = CHCOOCH 2CH2O ( CH2CH2O} )m( _C3H6O ) _{jH , CH2 = C ( CH3} ) _{COOC2H4O ( CH2CH2O} ) _m ( _C3H6O ) _j H (k is an integer of 1 to 100, m is an integer of 0 to 100, j is an integer of 1 to 100, m+j is 1 to 100.) and the like. . C ₆ H ₁₀ is a cyclohexylene group, C ₄ H ₈ is an n-butylene group, and C ₃ H ₆ is a 2-propylene group.

Examples of acid anhydrides containing ethylenic double bonds include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, 3,4,5,6 -tetrahydrophthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, and 2-buten-1-yl succinic anhydride.

Examples of monomers containing carboxylic acid groups include acrylic acid, methacrylic acid, vinylacetic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, and salts thereof.

Examples of epoxy group-containing monomers include glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl acrylate.

Examples of monomers containing an acid group include monomers containing a carboxylic acid group, monomers containing a phenolic hydroxyl group, and monomers containing a sulfonic acid group. More than one seed may be used. When a monomer containing a carboxylic acid group is used as a monomer containing an acid group, and a monomer containing a carboxylic acid group is used as a monomer containing a reactive group, the final A monomer in which an ethylenic double bond is not essentially introduced and which remains as a carboxylic acid group is regarded as a monomer containing an acid group.

Monomers containing a phenolic hydroxyl group include, for example, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, and one or more hydrogen atoms on the benzene ring of these are methyl group, ethyl group, Alkyl groups such as n-butyl groups, alkoxy groups such as methoxy groups, ethoxy groups, n-butoxy groups, halogen atoms, haloalkyl groups containing one or more halogen atoms, nitro groups, cyano groups, and/or amides A compound substituted by a group or the like can be mentioned.

Examples of monomers containing a sulfonic acid group include vinylsulfonic acid, styrenesulfonic acid, (meth)allylsulfonic acid, 2-hydroxy-3-(meth)allyloxypropanesulfonic acid, (meth)acrylic acid 2 -sulfoethyl, 2-sulfopropyl (meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropanesulfonic acid, and 2-(meth)acrylamido-2-methylpropanesulfonic acid.

Other monomers include, for example, hydrocarbon-based olefins, vinyl ethers, isopropenyl ethers, allyl ethers, vinyl esters, allyl esters, (meth)acrylic acid esters, (meth)acrylamides, Examples thereof include aromatic vinyl compounds, chloroolefins, and conjugated dienes. Considering the heat resistance of the cured film, (meth)acrylic acid esters or (meth)acrylamides are preferred. These compounds may contain functional groups such as carbonyl groups and alkoxy groups.

The ratio of the mass of the monomer containing the group represented by general formula (1) to the total mass of the monomers to be copolymerized is preferably 20 to 80% by mass, more preferably 30 to 60% by mass. Within the above mass range, the balance between the low reflectivity of the cured film and the adhesion between the cured film and the substrate is good.

The mass ratio of the reactive group-containing monomer to the total mass of the monomers to be copolymerized is preferably 20 to 70% by mass, more preferably 30 to 50% by mass. Within this range, the immobilization and developability of the side chain type specific resin are improved.

The mass ratio of the monomer containing an acid group to the total mass of the monomers to be copolymerized is preferably 2 to 20%, more preferably 4 to 12%. Within this range, the development property of the side chain type specific resin which is not cured at the time of exposure is improved.

The mass ratio of the other monomers to the total mass of the monomers to be copolymerized is preferably 70% by mass or less, more preferably 50% by mass or less, from the viewpoint of excellent developability.

A copolymer containing a side chain containing a group represented by the general formula (1), a side chain containing a reactive group, and optionally a side chain containing an acid group is represented by the general formula (1) A monomer containing a group represented by, a monomer containing a reactive group, optionally, a monomer containing an acid group and / or other monomers are dissolved in a solvent and heated Then, a polymerization initiator is added for copolymerization. In addition, it is preferable to add a chain transfer agent, if necessary, during the copolymerization. Alternatively, the monomer, polymerization initiator, solvent and chain transfer agent may be added continuously.

As the polymerization initiator, solvent and chain transfer agent, those described in paragraphs 0053 to 0056 of WO 2007/69703 can be used.

Examples of the combination of a compound containing a functional group capable of bonding to the reactive group and a polymerizable group (preferably an ethylenically unsaturated group) for the reactive group include the following combinations.

(1) an acid anhydride containing an ethylenically unsaturated group relative to the hydroxyl group;

(2) a compound containing an isocyanate group and an ethylenically unsaturated group relative to a hydroxyl group;

(3) a compound containing an acyl chloride group and an ethylenically unsaturated group relative to a hydroxyl group;

(4) a compound containing a hydroxyl group and an ethylenically unsaturated group for an acid anhydride;

(5) a compound containing an epoxy group and an ethylenically unsaturated group relative to a carboxylic acid group;

(6) A compound containing a carboxylic acid group and an ethylenically unsaturated group relative to the epoxy group.

Examples of compounds containing an isocyanate group and an ethylenically unsaturated group include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate. Among them, the side chain type specific resin containing a side chain having two or more ethylenically unsaturated groups is easily immobilized near the upper surface of the cured film, so 1,1-bis ((meth) acryloyloxymethyl) ethyl Isocyanates are preferred.

Examples of compounds containing an acyl chloride group and an ethylenically unsaturated group include (meth)acryloyl chloride.

As the acid anhydride containing an ethylenically unsaturated group, for example, the compounds exemplified in the above-mentioned monomer containing a reactive group can be used.

As the compound containing a hydroxyl group and an ethylenically unsaturated group, for example, the compounds exemplified above as the monomer containing a hydroxyl group can be used.

As the compound containing an epoxy group and an ethylenically unsaturated group, for example, the compounds exemplified above as the monomer containing an epoxy group can be used.

As the compound containing a carboxylic acid group and an ethylenically unsaturated group, for example, the compounds exemplified above as the monomer containing a carboxylic acid group can be used.

In addition, a side chain containing a group represented by the general formula (1) and a side chain containing a reactive group, and, if necessary, a copolymer containing a side chain containing an acid group are reacted. When reacting a compound containing a functional group capable of bonding to a functional group and a polymerizable group (preferably an ethylenically unsaturated group), the functionality of the compound with respect to the reactive group of the copolymer The equivalent ratio of the groups is preferably from 0.5 to 2.0, more preferably from 0.8 to 1.5, from the viewpoint of achieving an excellent balance between the appearance of the cured film and the low reflectivity.

The side chain type specific resin is a copolymer containing a side chain containing a group represented by the general formula (1), a side chain containing a reactive group, and optionally a side chain containing an acid group. , a functional group capable of bonding to a reactive group, and a compound containing an ethylenically unsaturated group are dissolved in a solvent and allowed to react.

As described above, the acid group-containing side chains in the side chain type specific resin can also be formed by chemical conversion after the polymerization reaction. For example, a side chain containing a group represented by the general formula (1), and a copolymer containing a side chain containing a reactive group, a functional group capable of bonding to the reactive group, and Acid groups may be formed after reaction with compounds containing ethylenically unsaturated groups. Specifically, when the combination of (6) above is adopted, the hydroxyl group generated by the reaction with the epoxy group and the carboxylic acid group is reacted with a polybasic acid anhydride (such as maleic anhydride), A carboxylic acid group may be introduced into the chain type specific resin.

The content of polymerizable groups (preferably ethylenically unsaturated groups) relative to the total resin mass of the side chain type specific resin is not limited.

Among them, the side chain type specific resin preferably has an ethylenically unsaturated group content of 0.001 to 10.0 mmol/g, more preferably 0.1 to 2 mmol/g, relative to the total mass of the resin. .

In this specification, the ethylenically unsaturated group content may be referred to as "C=C value".

As used herein, the ethylenically unsaturated group content (C=C value) intends a value measured by the following method. In addition, when synthesizing a resin containing an ethylenically unsaturated group, it may be calculated from the charged amounts of raw materials instead of measurement.

Further, when the composition contains a plurality of types of resins, and the C=C value of each resin is clear, from the blending ratio of each resin, C=C as the total mass of the resin contained in the composition You can calculate the value.

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, solid components (black pigment, etc.) in the composition are precipitated by centrifugal separation, and the remaining liquid component is separated. Further, from the obtained liquid component, a component having a weight-average molecular weight within a predetermined range is fractionated by GPC method, and this is used as a 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 added to prepare a solution.

10 mL of 4N sodium hydroxide aqueous solution is added to the prepared solution to obtain a mixed solution. Next, the mixed liquid is stirred at a liquid temperature of 40° C. for 2 hours. Further, 10.2 mL of 4N methanesulfonic acid aqueous solution is added to the mixed solution and stirred. Furthermore, 5 mL of demineralized water is added to the mixed liquid, and subsequently 2 mL of methanol is added to prepare a measurement solution.

The content of (meth)acrylic acid in the measurement solution is measured by HPLC (high performance liquid chromatography) method (absolute calibration curve method), and the ethylenically unsaturated group content is calculated.

HPLC measurement conditions Column: Phenomenex Synergi 4μ Polar-RP 80A (4.6 mm × 250 mm)

Column temperature: 40°C

Flow rate: 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 volume: 5 μL

As a method for measuring the ethylenically unsaturated group content of the resin, the ethylenically unsaturated group is other than the (meth)acryloyl group, or the (meth)acryloyl group and the (meth)acryloyl group are used in combination with a group other than the acryloyl group. In some cases, there is a method of measuring the bromination of the resin to be measured which has been fractionated by the method described above. A bromine number is measured based on JISK2605:1996.

Here, the ethylenically unsaturated group content is calculated from the number of grams (gBr ₂ /100 g) of bromine (Br ₂ ) added to 100 g of the resin to be measured, which is obtained by the above bromine number, per 1 g of the resin. It is a value converted into the number of moles of added bromine (Br ₂ ).

[Polymerizable compound]

The composition of the invention preferably contains a polymerizable compound.

In the present specification, the polymerizable compound intends a compound that polymerizes under the action of a polymerization initiator, which will be described later, and intends a component different from the dispersant and the alkali-soluble resin, which will be described later.

In addition, the polymerizable compound intends a component different from the epoxy group-containing compound described below.

The content of the polymerizable compound in the composition is not particularly limited, relative to the total solid content of the composition, preferably 1 to 35% by mass, more preferably 4 to 25% by mass, 10 to 20% by mass. More preferred. A polymerizable compound may be used individually by 1 type, and may use 2 or more types. When using two or more polymerizable compounds, the total content is preferably within the above range.

The mass ratio of the content of the specific resin to the polymerizable compound in the composition is preferably 0.1 to 50, more preferably 0.1 to 20, still more preferably 0.1 to 2, and 0.2 to 2. Especially preferred, 0.2 to 1 is most preferred. The mass ratio of the content represents (content of the specific resin)/(content of the polymerizable compound) in the composition.

A polymerizable compound is preferably a low-molecular-weight compound. The low-molecular-weight compound referred to here is preferably a compound having a molecular weight of 2,000 or less.

The polymerizable compound preferably does not contain a repeating unit represented by formula (1), and more preferably does not contain a (poly)siloxane structure.

The polymerizable compound is preferably a compound containing an ethylenically unsaturated group.

In other words, the composition of the present invention preferably contains a low-molecular-weight compound containing an ethylenically unsaturated group as a polymerizable compound.

The polymerizable compound is preferably a compound containing one or more ethylenically unsaturated bonds, more preferably a compound containing two or more, more preferably a compound containing three or more, and particularly preferably a compound containing five or more. The upper limit is, for example, 15 or less. Examples of ethylenically unsaturated groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.

As the polymerizable compound, for example, the compounds described in paragraph 0050 of JP-A-2008-260927 and paragraph 0040 of JP-A-2015-68893 can be used, and the above contents are incorporated herein. be

The polymerizable compound may be in any chemical form such as monomers, prepolymers, oligomers, mixtures thereof, and multimers thereof.

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

The polymerizable compound is also preferably a compound containing one or more ethylenically unsaturated groups and having a boiling point of 100° C. or higher under normal pressure. For example, the compounds described in paragraph 0227 of JP-A-2013-29760 and paragraphs 0254 to 0257 of JP-A-2008-292970 can be considered, and the contents thereof are incorporated herein.

The polymerizable compound includes dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), Pentaerythritol penta (meth) acrylate (as a commercial product KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH- 12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth)acryloyl groups are via ethylene glycol residues or propylene glycol residues (for example, SR454 and SR499, commercially available from Sartomer) are preferred. . These oligomeric types can also be used. In addition, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040, KAYARAD DPEA-12LT, KAYARAD DPHA LT, KAYARAD RP-3060, KAYARAD DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.) Also, Viscoat #802 (manufactured by Osaka Organic Industry Co., Ltd.) or the like may be used.

Preferred embodiments of the polymerizable compound are shown below.

The polymerizable compound may have acid groups such as carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups. The polymerizable compound containing an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. A group-attached polymerizable compound is more preferable, and in this ester, a compound in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol is more preferable. Examples of commercially available products include Aronix TO-2349, M-305, M-510 and M-520 manufactured by Toagosei Co., Ltd.

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

A preferred embodiment of the polymerizable compound is a compound containing a caprolactone structure.

The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule. Examples include ε-caprolactone-modified polyfunctional (meth)acrylates obtained by esterifying polyhydric alcohols such as erythritol, glycerin, diglycerol, or trimethylolmelamine with (meth)acrylic acid and ε-caprolactone. Among them, a compound containing a caprolactone structure represented by the following formula (Z-1) is preferable.

In formula (Z-1), all six R are groups represented by the following formula (Z-2), or 1 to 5 of the six R are the following formula (Z-2) and the remainder 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 the number of 1 or 2, and "*" represents a bond.

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

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

A compound represented by the following formula (Z-6) can also be used as the polymerizable compound.

In formula (Z-6), each E independently represents -((CH ₂ ) _y CH ₂ O)- or ((CH ₂ ) _y CH(CH ₃ )O)-, and y is each Each independently represents an integer of 0 to 10, and each X independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxylic acid group.

In formula (Z-6), each p independently represents an integer of 0 to 10, and q represents an integer of 0 to 3.

In formula (Z-6), the total number of (meth)acryloyl groups is preferably (3+2t) or (4+2t).

In formula (Z-6), the sum of each p is preferably 0 to (40+20t).

p is preferably an integer of 0-6, more preferably an integer of 0-4.

The sum of each p is preferably 0 to (16+8t), more preferably 0 to (12+6t).

-((CH ₂ ) _y CH ₂ O)- or ((CH ₂ ) _y CH(CH ₃ )O)- in formula (Z-6) is a form in which the end on the oxygen atom side is bound to X is preferred.

The compounds represented by formula (Z-6) may be used singly or in combination of two or more. In particular, when t=1, a preferred embodiment is a mixture of a compound in which all six X's are acryloyl groups and a compound in which at least one of the six X's is a hydrogen atom. By adopting such a configuration, the developability can be further improved.

It is also preferable to use a mixture of compounds represented by formula (Z-6) each having a different value of t. In such a mixture, the content of the compound at t = 1, the compound at t = 2, and the compound at t = 3 is 5 to 35% by mass, 30 to 75% by mass, and 3 to 35% by mass, respectively. % by weight is preferred.

The total content of the compound represented by formula (Z-6) in the polymerizable compound is preferably 20% by mass or more, more preferably 50% by mass or more.

Among the compounds represented by formula (Z-6), pentaerythritol derivatives, dipentaerythritol derivatives, tripentaerythritol derivatives, and/or tetrapentaerythritol derivatives are more preferred.

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 preferred.

Examples of the cardo skeleton-containing polymerizable compound include, but are not limited to, Oncoat EX series (manufactured by Nagase & Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemicals Co., Ltd.).

The polymerizable compound is also preferably a compound containing an isocyanuric acid skeleton as a central nucleus. Examples of such polymerizable compounds include NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

The content of ethylenically unsaturated groups in the polymerizable compound (the number of ethylenically unsaturated groups in the polymerizable compound is intended to be the value obtained by dividing the molecular weight (g/mol) of the polymerizable compound) is 5.0 mmol/ g or more is preferred. Although the upper limit is not particularly limited, it is generally 20.0 mmol/g or less.

In addition, when the composition contains a plurality of types of polymerizable compounds and the respective double bond equivalents are not the same, the mass ratio of each polymerizable compound in all polymerizable compounds and the weight ratio of each polymerizable compound The sum of the products with double bond equivalents is preferably within the above range.

[Photopolymerization initiator]

The composition contains a photoinitiator.

The photopolymerization initiator is not particularly limited as long as it can initiate polymerization of the polymerizable compound, and known photopolymerization initiators can be used. As the photopolymerization initiator, for example, a photopolymerization initiator having photosensitivity from the ultraviolet region to the visible light region is preferable. Further, it may be an activator that produces some action with a photoexcited sensitizer to generate an active radical, or an initiator that initiates cationic polymerization depending on the type of the polymerizable compound.

Since the photopolymerization initiator can obtain a cured film with more excellent low reflectivity, the absorbance of a solution obtained by dissolving 0.001% by mass of the photopolymerization initiator in acetonitrile at a wavelength of 340 nm at an optical path length of 10 mm is 0.00. 45 or more is preferable.

In this specification, the absorbance of the solution of the photopolymerization initiator is measured using an ultraviolet-visible-near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation).

The content of the photopolymerization initiator in the composition is not particularly limited, but is preferably 0.5 to 20% by mass, more preferably 1.0 to 10% by mass, based on the total solid content of the composition. 0.5 to 8 mass % is more preferred. A photoinitiator may be used individually by 1 type, and may use 2 or more types. When using two or more photopolymerization initiators, the total content is preferably within the above range.

Examples of photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds containing a triazine skeleton, compounds containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, Examples include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, aminoacetophenone compounds, and hydroxyacetophenone.

Specific examples of the photopolymerization initiator can be referred to, for example, paragraphs 0265 to 0268 of JP-A-2013-29760, the contents of which are incorporated herein.

As the photopolymerization initiator, more specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine-based initiator described in Japanese Patent No. 4225898 can also be used.

Examples of hydroxyacetophenone compounds that can be used include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF).

As the aminoacetophenone compound, for example, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF) can be used. As the aminoacetophenone compound, the compound described in JP-A-2009-191179, whose absorption wavelength is matched to a long-wave light source such as a wavelength of 365 nm or a wavelength of 405 nm, can also be used.

As the acylphosphine compound, commercially available products IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

(oxime compound)

As the photopolymerization initiator, an oxime ester polymerization initiator (oxime compound) is more preferable. In particular, oxime compounds are preferred because they have high sensitivity and high polymerization efficiency, and are easy to design so that the content of the black colorant in the composition is high.

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

Examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxy and carbonyloxyimino-1-phenylpropan-1-one.

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

IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF) are also preferable as commercially available products. In addition, TR-PBG-304 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Arkles NCI-831, Adeka Arkles NCI-930 (manufactured by ADEKA), or N-1919 (carbazole-oxime ester skeleton-containing light An initiator (manufactured by ADEKA) can also be used.

In addition, as oxime compounds other than those described above, compounds described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the carbazole N-position; compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced at the benzophenone moiety; Compounds described in JP-A-2010-15025 and US Patent Publication 2009-292039 in which a nitro group is introduced into the dye site; ketoxime compounds described in WO 2009-131189; and triazine skeleton and oxime skeleton are the same The compound described in US Pat. No. 7,556,910 contained in the molecule; the compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source; .

For example, paragraphs 0274 to 0275 of Japanese Patent Application Laid-Open No. 2013-29760 can be referred to, the contents of which are incorporated herein.

Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). Further, even if the NO bond of the oxime compound is the (E)-isomer oxime compound, the (Z)-isomer oxime compound, or the mixture of the (E)-isomer and the (Z)-isomer. good.

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

Examples of monovalent nonmetallic atomic groups include alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, heterocyclic groups, alkylthiocarbonyl groups, and arylthiocarbonyl groups. Moreover, these groups may have one or more substituents. Moreover, the substituents described above may be further substituted with other substituents.

Examples of substituents include halogen atoms, aryloxy groups, alkoxycarbonyl groups or aryloxycarbonyl groups, acyloxy groups, acyl groups, alkyl groups, and aryl groups.

In formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group, and an aryl group or a heterocyclic group is preferable. These groups may have one or more substituents. Examples of the substituent include the substituents described above.

In 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 substituents described above.

An oxime compound containing a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound containing a fluorine atom include compounds described in JP-A-2010-262028; compounds 24, 36 to 40 described in JP-A-2014-500852; compound (C-3); and the like. The contents of which are incorporated herein.

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

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

In formula (2), R ¹ , R ² , R ³ and R ⁴ have the same definitions as R ¹ , R ² , R ³ and R ⁴ in formula (1), and R ⁵ is -R ⁶ , -OR ⁶ , -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , —CN, a halogen atom, or a hydroxyl group, and R ⁶ 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 an arylalkyl group having 7 to 30 carbon atoms, or 4 to 4 carbon atoms 20 represents a heterocyclic group, X represents a direct bond or a carbonyl group, and a represents an integer of 0-4.

In 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 group having 7 to 30 carbon atoms. represents an alkyl group, and R ³ and R ⁴ are each independently 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 carbon It represents a heterocyclic group of numbers 4 to 20, and X represents a direct bond or a carbonyl group.

In formula (4), R ¹ , R ³ and R ⁴ have the same definitions as R ¹ , R ³ and R ⁴ in formula (3), R ⁵ is -R ⁶ , -OR ⁶ , —SR ⁶ , —COR ⁶ , —CONR ⁶ R ⁶ , —NR ⁶ COR ⁶ , —OCOR ⁶ , —COOR ⁶ , —SCOR ⁶ , —OCSR ⁶ , —COSR ⁶ , —CSOR ⁶ , —CN, halogen atoms, Alternatively, a hydroxyl group is represented, 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. , X represents a direct bond or a carbonyl group, and a represents an integer of 0-4.

In formulas (1) and (2) above, R ¹ and R ² are each independently preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group. R3 is preferably a methyl group ^, an ethyl group, a phenyl group, a tolyl group, or a xylyl group.

R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. ^R5 is preferably a methyl group, ethyl group, phenyl group, tolyl group or naphthyl group. X is preferably a direct bond.

In the above formulas (3) and (4), each 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. R3 is preferably a methyl group ^, an ethyl group, a phenyl group, a tolyl group, or a xylyl group. R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. ^R5 is preferably a methyl group, ethyl group, phenyl group, tolyl group or naphthyl group. X is preferably a direct bond.

Specific examples of the compounds represented by formulas (1) and (2) include compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466. The contents of which are incorporated herein.

Specific examples of oxime compounds preferably used in the composition are shown below. Among the oxime compounds shown below, the oxime compound represented by general formula (C-13) is more preferable.

In addition, as the oxime compound, compounds described in Table 1 of WO 2015-036910 can also be used, and the above contents are incorporated herein.

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

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, more preferably 5,000 to 200, from the viewpoint of sensitivity. 000 is more preferred.

The molar extinction coefficient of the compound can be measured by a known method, for example, with a UV-visible spectrophotometer (Varian Cary-5 spectrophotometer), using ethyl acetate, and measuring at a concentration of 0.01 g/L. is preferred.

You may use a photoinitiator in combination of 2 or more types as needed.

Further, as the photopolymerization initiator, the compounds described in paragraph 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. and the contents of the above are incorporated herein.

[Other resins]

The composition of the present invention may contain other resins than the specific resins described above.

Other resins preferably do not contain repeating units represented by formula (1), and more preferably do not contain a (poly)siloxane structure.

Other resins include, for example, dispersants and alkali-soluble resins.

The content of other resins in the composition is not particularly limited, but is preferably 3 to 60% by mass, more preferably 10 to 40% by mass, more preferably 15 to 35% by mass, based on the total solid content of the composition. More preferred. Other resin may be used individually by 1 type, and may use 2 or more types. For example, as other resins, a dispersant described later and an alkali-soluble resin described later may be used. When using two or more other resins, the total content is preferably within the above range.

The other resin is preferably a substance dissolved in the composition and having a molecular weight of more than 2000. In addition, when the molecular weight of other resins is polydisperse, it is preferable that the weight average molecular weight is more than 2000.

<Dispersant>

The composition preferably contains a dispersant. In addition, in this specification, a dispersing agent intends a compound different from the alkali-soluble resin mentioned later.

The content of the dispersant in the composition is not particularly limited, but is preferably 3 to 40% by mass, more preferably 5 to 35% by mass, and even more preferably 10 to 30% by mass, based on the total solid content of the composition. .

A dispersant may be used individually by 1 type, and may use 2 or more types. When two or more dispersants are used, the total content is preferably within the above range.

Further, in the composition, the mass ratio of the content of the dispersant (preferably graft type polymer) to the content of the pigment (content of dispersant/content of pigment) is 0.05 to 1.00. It is preferably 0.05 to 0.35, even more preferably 0.20 to 0.35.

As the dispersant, for example, a known dispersant can be appropriately selected and used. Among them, polymer compounds are preferred.

Dispersants include polymeric dispersants [e.g., polyamidoamine and its salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylic copolymer, formalin condensate of naphthalene sulfonate], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, and pigment derivatives.

Polymer compounds can be further classified into straight-chain polymers, terminal-modified polymers, graft-type polymers, and block-type polymers according to their structures.

・Polymer compound

The polymer compound adsorbs to the surface of the dispersed material such as a black pigment and other pigments used in combination as desired (hereinafter, the black pigment and other pigments are collectively referred to as "pigments"), and the like. It acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft-type (containing a polymer chain) polymer, or a block-type polymer containing an anchor site to the pigment surface is preferable.

The polymer compound may contain a curable group.

Examples of curable groups include ethylenically unsaturated groups (e.g., (meth)acryloyl groups, vinyl groups, and styryl groups), and cyclic ether groups (e.g., epoxy groups, oxetanyl groups, etc.). including, but not limited to:

Among them, the curable group is preferably an ethylenically unsaturated group, and more preferably a (meth)acryloyl group, because polymerization can be controlled by a radical reaction.

Resins containing curable groups (other resins) preferably contain at least one selected from the group consisting of polyester structures and polyether structures. 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 chains may contain polyester structures and/or polyether structures.

As for the resin (other resin), it is more preferable that the polymer chain contains a polyester structure.

The polymeric compound preferably contains a structural unit containing a graft chain. In addition, in this specification, a "structural unit" is synonymous with a "repeating unit."

A polymer compound containing a structural unit containing such a graft chain has an affinity with a solvent due to the graft chain, so that the dispersibility of pigments and the like and the dispersion stability after time (time stability) Excellent for Moreover, 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 resins (specific resins, etc.) that can be used together. As a result, residue is less likely to be generated in alkali development.

The longer the graft chain, the higher the steric repulsion effect and the better the dispersibility of pigments. On the other hand, if the graft chain is too long, the adsorptive power to pigments and the like tends to decrease, and the dispersibility of pigments and the like tends to decrease. For this reason, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and the number of atoms excluding hydrogen atoms is More preferably 60-500.

The term "graft chain" as used herein refers to the length from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.

The graft chain preferably contains a polymeric structure, such polymeric structures include, for example, poly(meth)acrylate structures (e.g., poly(meth)acrylic structures), polyester structures, polyurethane structures, polyurea structures, polyamide structures, polyether structures, and the like.

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 interaction between the graft chain and the solvent, thereby enhancing the dispersibility of the pigment or the like. It is preferably a graft chain containing at least one of these, and more preferably a graft chain containing at least one of a polyester structure and a polyether structure.

The macromonomer containing such a graft chain (a monomer having a polymer structure and forming a graft chain by bonding to the main chain of the copolymer) is not particularly limited, but includes a reactive double bond group. Containing macromonomers can be preferably used.

Commercially available macromonomers corresponding to the structural unit containing the graft chain contained in the polymer compound and suitable for synthesis of the polymer compound include AA-6 (trade name, manufactured by Toagosei Co., Ltd.) and AA-10. (trade name, manufactured by Toagosei Co., Ltd.), AB-6 (trade name, manufactured by Toagosei Co., Ltd.), AS-6 (trade name, manufactured by Toagosei Co., Ltd.), AN-6 (trade name, manufactured by Toagosei Co., Ltd.), AW -6 (trade name, manufactured by Toagosei Co., Ltd.), AA-714 (trade name, manufactured by Toagosei Co., Ltd.), AY-707 (trade name, manufactured by Toagosei Co., Ltd.), AY-714 (trade name, manufactured by Toagosei Co., Ltd.) , AK-5 (trade name, manufactured by Toagosei Co., Ltd.), AK-30 (trade name, manufactured by Toagosei Co., Ltd.), AK-32 (trade name, manufactured by Toagosei Co., Ltd.), Blenmer PP-100 (trade name, NOF company), Blenmer PP-500 (trade name, manufactured by NOF Corporation), Blenmer PP-800 (trade name, manufactured by NOF Corporation), Blenmer PP-1000 (trade name, manufactured by NOF Corporation), Blenmer 55-PET -800 (trade name, manufactured by NOF), Blenmer PME-4000 (trade name, manufactured by NOF), Blenmer PSE-400 (trade name, manufactured by NOF), Blenmer PSE-1300 (trade name, NOF) (manufactured by NOF Corporation), or BLEMMER 43PAPE-600B (trade name, manufactured by NOF Corporation). Among them, AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (trade name, manufactured by Toagosei Co., Ltd.), AB-6 (trade name, manufactured by Toagosei Co., Ltd.), AS-6 (trade name, manufactured by Toagosei Co., Ltd.) Synthetic Co., Ltd.), AN-6 (trade name, Toagosei Co., Ltd.), or Blemmer PME-4000 (trade name, NOF Corporation) are preferable.

The dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyesters, polymethyl acrylate, polymethacrylic acid More preferably, it contains at least one structure selected from the group consisting of methyl and chain polyesters, and a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. It is further preferred to contain at least one structure selected from the group consisting of The dispersant may be a dispersant containing the above structure alone in one dispersant, or 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. A polyvalerolactone structure refers to a structure containing, as a repeating unit, a ring-opened structure of δ-valerolactone.

Specific examples of dispersants containing a polycaprolactone structure include dispersants in which j and k are 5 in the following formulas (1) and (2). Further, specific examples of dispersants containing a polyvalerolactone structure include dispersants in which j and k are 4 in the following formulas (1) and (2).

A specific example of a dispersant containing a polymethyl acrylate structure is a dispersant in which X ⁵ in the following formula (4) is a hydrogen atom and R ⁴ is a methyl group. A specific example of a dispersant containing a polymethyl methacrylate structure is a dispersant in which X ⁵ in the following formula (4) is a methyl group and R ⁴ is a methyl group.

・Structural unit containing a graft chain

The polymer compound preferably contains a structural unit represented by any one of the following formulas (1) to (4) as a structural unit containing a graft chain, and the following formula (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 each independently represent an oxygen atom or NH. W ¹ , W ² , W ³ and W ⁴ are preferably oxygen atoms.

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

In formulas (1) to (4), Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a divalent linking group, and the linking group is not particularly restricted structurally. 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 structures shown below, A and B respectively mean the bonding sites with the left terminal group and the right terminal group in formulas (1) to (4). Among the structures shown below, (Y-2) or (Y-13) is more preferred from the viewpoint of 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 specific examples include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group. etc. Among these, the organic groups represented by Z ¹ , Z ² , Z ³ and Z ⁴ are preferably groups having a steric repulsion effect, particularly from the viewpoint of improving dispersibility, each independently having 5 carbon atoms. ∼24 alkyl groups or alkoxy groups are more preferable, and among them, branched alkyl groups each independently 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 preferred. More preferred. The alkyl group contained in the alkoxy group may be linear, branched, or cyclic.

In formulas (1) to (4), n, m, p, and q are each independently an integer of 1-500.

In formulas (1) and (2), j and k each independently represent an integer of 2-8. j and k in formulas (1) and (2) are preferably integers of 4 to 6, more preferably 5, from the viewpoint of the stability of the composition over time and developability.

In formulas (1) and (2), n and m are preferably integers of 10 or more, and more preferably integers of 20 or more. Further, when the dispersant contains a polycaprolactone structure and a polyvalerolactone structure, the sum of the repeating number of the polycaprolactone structure and the repeating number of the polyvalerolactone is preferably an integer of 10 or more, and 20 or more. Integers are more preferred.

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

In formula (4), ^R4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited structurally. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R ⁴ is an alkyl group, the alkyl group includes a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms. A straight-chain alkyl group having 1 to 20 carbon atoms is preferable, and a straight-chain alkyl group having 1 to 6 carbon atoms is even more preferable. In formula (4), when q is 2 to 500, multiple X ⁵ and R ⁴ present in the graft copolymer may be the same or different.

In addition, the polymer compound can contain two or more different structural units containing grafted chains. That is, the molecule of the polymer compound may contain structural units represented by formulas (1) to (4) having different structures, and in formulas (1) to (4), n, m, p , and q each represents an integer of 2 or more, in formulas (1) and (2), j and k may contain different structures in the side chains, and formulas (3) and (4) ), a plurality of R ³ , R ⁴ , and X ⁵ present in the molecule may be the same or different.

The structural unit represented by formula (1) is more preferably a structural unit represented by formula (1A) below from the viewpoint of the composition's stability over time and developability.

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

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

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

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

The polymer compound more preferably contains a structural unit represented by 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 based on the total mass of the polymer compound in terms of mass. It is preferably contained in the range of , more preferably in the range of 5 to 30% by mass. When the structural unit containing a graft chain is contained within this range, the dispersibility of the pigment is high, and the developability when forming a cured film is good.

・Hydrophobic structural unit

Also, the polymer compound preferably contains a hydrophobic structural unit that is different from the structural unit containing the graft chain (that is, does not correspond to the structural unit containing the graft chain). However, in this specification, a hydrophobic structural unit is a structural unit that does not have an acid group (eg, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).

The hydrophobic structural unit is preferably a (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 preferred. As a result, the effects of the present invention can be exhibited more reliably.

ClogP values were obtained from Daylight Chemical Information System, Inc. It is a value calculated with the program "CLOGP" available from This program provides "calculated logP" values calculated by the fragment approach of Hansch, Leo (see below). The fragment approach is based on the chemical structure of a compound, dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to the fragments to estimate the logP value of the compound. The details are described in the following documents. ClogP values calculated by the program CLOGP v4.82 are used herein.

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

log P means the common logarithm of the partition coefficient P (Partition Coefficient), and is a quantitative measure of how an organic compound is partitioned in a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is shown by the following formula.

log P = log (coil/water)

In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the water phase.

If the value of logP is greater than 0, the oil solubility increases, and if the absolute value becomes negative, the water solubility increases, and there is a negative correlation with the water solubility of the organic compound. widely used as.

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

In formulas (i) to (iii) above, R ¹ , R ² , and R ³ are each independently a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), or It represents an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, etc.).

R ¹ , R ² and R ³ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group. More preferably, R ² and R ³ are hydrogen atoms.

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

L is a single bond or a divalent linking group. The divalent linking group includes a divalent aliphatic group (e.g., alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), divalent aromatic group (e.g., arylene group , substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR ³¹ —, where R ³¹ is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), and combinations thereof.

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

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

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

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

Z is an aliphatic group (e.g., alkyl group, substituted alkyl group, unsaturated alkyl group, substituted unsaturated alkyl group), aromatic group (e.g., aryl group, substituted aryl group, arylene group, substituted arylene group) , heterocyclic groups, and combinations thereof. These groups include an oxygen atom (--O--), a sulfur atom (--S--), an imino group (--NH--), a substituted imino group (--NR ³¹ --, where R ³¹ is an aliphatic group, an aromatic group or heterocyclic group) or a carbonyl group (--CO--).

The aliphatic group may have a cyclic structure or a branched structure. The number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, even more preferably 1-10. Aliphatic groups further include ring-assembled hydrocarbon groups, bridged cyclic hydrocarbon groups, and examples of ring-assembled hydrocarbon groups include bicyclohexyl, perhydronaphthalenyl, biphenyl, and 4 -cyclohexylphenyl group and the like are included. Examples of the bridged cyclic hydrocarbon ring include pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo[2.2.2]octane ring, bicyclo[3.2.1]octane ring, etc.) and the like. Cyclic hydrocarbon rings, tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo[5.2.1.0 ^2,6 ]decane and tricyclo[4.3.1.1 ^2,5 ]undecane rings , as well as tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. Bridged cyclic hydrocarbon rings also include condensed cyclic hydrocarbon rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a perhydrophenalene ring are condensed is also included.

A saturated aliphatic group is preferable to an unsaturated aliphatic group. Moreover, the aliphatic group may have a substituent. Examples of substituents include halogen atoms, aromatic groups and heterocyclic groups. However, an aliphatic group does not have an acid group as a substituent.

The number of carbon atoms in the aromatic group is preferably 6-20, more preferably 6-15, even more preferably 6-10. 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- or 6-membered ring as the heterocyclic ring. The heterocyclic ring may be condensed with another heterocyclic ring, an aliphatic ring or an aromatic ring. Moreover, the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxyl groups, oxo groups (=O), thioxo groups (=S), imino groups (=NH), substituted imino groups (=NR ³² , where R ³² is an aliphatic 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 formula (iii) above, R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), or alkyl having 1 to 6 carbon atoms. represents a group (eg, methyl group, ethyl group, propyl group, etc.), Z, or LZ. Here, L and Z are synonymous with the above groups. R ⁴ , R ⁵ and R ⁶ are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

As the monomer represented by the above formula (i), R ¹ , R ² and R ³ are hydrogen atoms or methyl groups, and L is a single bond or an alkylene group or an oxyalkylene structure A compound having a divalent linking group, X being an oxygen atom or an imino group, and Z being an aliphatic group, a heterocyclic group, or an aromatic group is preferred.

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 Compounds that are radicals are preferred. Further, as the monomer represented by the above formula (iii), R ⁴ , R ⁵ and R ⁶ are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group or an aromatic Compounds that are radicals are preferred.

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

Examples of typical compounds represented by formulas (i) to (iii) include compounds described in paragraphs 0089 to 0093 of JP-A-2013-249417. incorporated into.

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

・Functional groups that can interact with pigments, etc.

A polymer compound can introduce a functional group capable of interacting with a pigment or the like (for example, a black pigment). Here, the polymer compound preferably further contains a structural unit containing a functional group capable of forming an interaction with the pigment or the like.

Examples of the functional group capable of interacting 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 reactive functional group, the structural unit containing the acid group, the structural unit containing the basic group, the coordination group, respectively. It is preferable to contain a structural unit containing a positional group or a structural unit having reactivity.

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, if an alkali-soluble group is introduced into the polymer compound, the above-mentioned composition will contain an alkali-soluble polymer compound as a dispersant that contributes to the dispersion of the pigment or the like. A composition containing such a polymer compound is excellent in the light-shielding property of a cured film formed by exposure, and the alkali developability of an unexposed portion is improved.

In addition, when the polymer compound contains a structural unit containing an acid group, the polymer compound becomes more 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, etc., and the polymer compound stably disperses the pigment, etc., and the viscosity of the polymer compound that disperses the pigment, etc. becomes low. It is presumed that this is because the polymer compound itself tends to be stably dispersed.

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

The acid group, which is a functional group capable of forming an interaction with a pigment or the like, includes, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. , a phosphoric acid group, and more preferably a carboxylic acid group. Carboxylic acid groups have good adsorptive power to pigments and the like, and have 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 does, the content of the structural unit containing an acid group, in terms of mass, is equal to the total mass of the polymer compound. 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 image strength due to alkali development.

The basic group, which is a functional group capable of forming an interaction with a pigment or the like, includes, for example, a primary amino group, a secondary amino group, a tertiary amino group, a heterocyclic ring containing an N atom, and an amide A preferred basic group is a tertiary amino group because of its good adsorptive power to pigments and the like and 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 does, the content of the structural unit containing a basic group is, in terms of mass, the total amount of the polymer compound. 0.01 to 50% by mass is preferable, and 0.01 to 30% by mass is more preferable from the viewpoint of suppressing development inhibition.

Examples of the coordinating group, which is a functional group capable of forming an interaction with a pigment or the like, and the reactive functional group include an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, and an acid Chlorides and the like can be mentioned. A preferable functional group is an acetylacetoxy group because it has good adsorptive power to pigments and the like and high dispersibility of pigments and 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 does, the content of these structural units is preferably 10 to 80% by mass, and more preferably 20 to 60% by mass, in terms of mass conversion, relative to the total mass of the polymer compound, from the viewpoint of suppressing inhibition of developability.

When the polymer compound contains a functional group capable of interacting with a pigment or the like in addition to the graft chain, it may contain a functional group capable of forming an interaction with the various pigments described above. Although there is no particular limitation on how these functional groups are introduced, the polymer compound is one selected from structural units derived from monomers represented by the following formulas (iv) to (vi). It preferably contains more than one species of structural units.

In formulas (iv) to (vi), R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), or have 1 carbon atom 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 each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently a hydrogen atom or A methyl group is more preferred. In general formula (iv), R ¹² and R ¹³ are more preferably each hydrogen atoms.

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

Y in formula (v) represents a methine group or a nitrogen atom.

L ₁ in 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 formula (i) above.

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

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

In formula (vi), R ¹⁴ , R ¹⁵ , and R ¹⁶ each independently represent a hydrogen atom, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), a C 1-6 represents an alkyl group (eg, methyl group, ethyl group, propyl group, etc.), -Z ₁ , or L ₁ -Z ₁ ; Here, L ₁ and Z ₁ are synonymous with L ₁ and Z ₁ above, and preferred examples are also the same. R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

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

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.

Furthermore, as the monomer represented by formula (vi), R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a methyl group, L ₁ is a single bond or an alkylene group, Compounds in which Z ₁ is a carboxylic acid group are preferred.

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

Examples of monomers include methacrylic acid, crotonic acid, isocrotonic acid, reaction of compounds containing addition-polymerizable double bonds and hydroxyl groups in the molecule (e.g., 2-hydroxyethyl methacrylate) with succinic anhydride a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule and phthalic anhydride, a compound containing an addition-polymerizable double bond and a hydroxyl group in the molecule and tetrahydroxyphthalic anhydride a 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 pyromellitic anhydride , acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and 4-hydroxyphenylmethacrylamide.

The content of the structural unit 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 the developer. is preferably 0.05 to 90% by mass, more preferably 1.0 to 80% by mass, and even more preferably 10 to 70% by mass.

・Other structural units

Furthermore, for the purpose of improving various performances such as image strength, the polymer compound does not interact with the structural unit containing the graft chain, the hydrophobic structural unit, the pigment, etc., as long as the effects of the present invention are not impaired. Different from the structural unit containing a functional group that can be formed, it further has other structural units having various functions (for example, a structural unit containing a functional group having affinity with a solvent, etc., which will be described later). good too.

Such other structural units include, for example, structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.

One or more of these other structural units can be used in the polymer compound, 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, in terms of mass. 60% by mass is more preferred. Sufficient pattern formability is maintained when the content is within the above range.

・Physical properties of polymer compounds

The acid value of the polymer compound is preferably 0 to 250 mgKOH/g, more preferably 10 to 200 mgKOH/g, even more preferably 30 to 180 mgKOH/g, particularly preferably 70 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 more effectively suppressed. Moreover, when the acid value of the polymer compound is 10 mgKOH/g or more, the alkali developability is further improved. Further, when the acid value of the polymer compound is 20 mgKOH/g or more, sedimentation of pigments and the like can be further suppressed, the number of coarse particles can be further reduced, and the stability of the composition over time can be further improved.

As used herein, the acid value can be calculated, for example, from the average content of acid groups in the compound. Further, by changing the content of the structural unit containing an acid group, which is a constituent component of the resin (other resins, etc.), a resin having a desired acid value can be obtained.

The weight-average molecular weight of the polymer compound is preferably 4,000 to 300,000, more preferably 5,000 to 200,000, even more preferably 6,000 to 100,000, 10,000 to 50,000 are particularly preferred.

A 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 (polyamideamine phosphate) manufactured by BYK Chemie, 107 (carboxylic acid ester), 110 (copolymer containing an acid group ), 111 (phosphate dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 167, 170, 190 (polymer copolymer)”, “BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)”, manufactured by EFKA “EFKA4047, 4050-4010-4165 (polyurethane system), 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. "Ajisper PB821, PB822, PB880, PB881", Kyoeisha Chemical Co., Ltd. “Floren TG-710 (urethane oligomer)”, “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, 873SN, 874, #2150 (aliphatic polyvalent Carboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725”, Kao Corporation “Demoll RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN -B (aromatic sulfonic acid formalin polycondensate)", "Homogenol L-18 (polymeric polycarboxylic acid)", "Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "acetamine 86 (Stearylamine Acetate)", Nippon Lubrizol "Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (contains a functional part at the end Polymer), 24000, 28000, 32000, 38500 (graft copolymer)”, Nikko Chemicals Co., Ltd. “Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)”, Kawa Ken Fine Chemical Hinoact T-8000E, etc., Shin-Etsu Chemical Co., Ltd. Organosiloxane polymer KP-3 41, Yusho "W001: cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate , polyethylene glycol distearate, nonionic surfactants such as sorbitan fatty acid esters, 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" polymer dispersants, ADEKA's "ADEKA Pluronic 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. Acrybase FFS-6752 and Acrybase FFS-187 can also be used.

It is also preferred to use amphoteric resins containing acid and basic groups. The amphoteric resin preferably has 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-2010 manufactured by BYK-Chemie, DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajinomoto Fine-Techno Co., Ltd. Ajisper PB821, Ajisper PB822, Ajisper PB881, and the like.

These high molecular compounds may be used individually by 1 type, and may use 2 or more types.

As specific examples of the polymer compound, reference can be made to the polymer compounds described in paragraphs 0127 to 0129 of JP-A-2013-249417, the contents of which are incorporated herein.

Further, as the dispersant, in addition to the above polymer compounds, graft copolymers described in paragraphs 0037 to 0115 of JP-A-2010-106268 (paragraphs 0075 to 0133 of corresponding US 2011/0124824) can be used. can be cited and incorporated herein.

In addition to the above, the acid group of paragraphs 0028 to 0084 of JP-A-2011-153283 (paragraphs 0075 to 0133 of corresponding US2011/0279759) contains a side chain structure formed by bonding via a linking group. Polymeric compounds containing constituents such as can be used, the contents of which are incorporated herein by reference.

As the dispersant, resins described in paragraphs 0033 to 0049 of JP-A-2016-109763 can also be used, the contents of which are incorporated herein.

<Alkali-soluble resin>

The composition may contain an alkali-soluble resin. In the present specification, the alkali-soluble resin is intended to be a resin containing a group that promotes alkali solubility (an alkali-soluble group, such as an acid group such as a carboxylic acid group), and is intended to be a resin different from the dispersants already described. do.

The content of the alkali-soluble resin in the composition is not particularly limited, but is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and 5 to 15% by mass, based on the total solid content of the composition. More preferred.

Alkali-soluble resin may be used individually by 1 type, and may use 2 or more types. When using two or more alkali-soluble resins, the total content is preferably within the above range.

Although the acid value of the alkali-soluble resin is not particularly limited, it is generally preferably 30 to 500 mgKOH/g, more preferably 50 to 200 mgKOH/g or more.

Examples of alkali-soluble resins include resins containing at least one alkali-soluble group in the molecule, such as polyhydroxystyrene resins, polysiloxane resins other than specific resins, (meth)acrylic resins, and (meth)acrylamide resins. , (meth)acryl/(meth)acrylamide copolymer resins, epoxy resins, and polyimide resins.

Specific examples of alkali-soluble resins include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds.

The unsaturated carboxylic acid is not particularly limited, but monocarboxylic acids such as (meth)acrylic acid, crotonic acid, and vinylacetic acid; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid; or acid anhydrides thereof. and polyvalent carboxylic acid monoesters such as phthalic acid mono (2-(meth)acryloyloxyethyl); and the like.

Examples of copolymerizable ethylenically unsaturated compounds include methyl (meth)acrylate and the like. In addition, the compounds described in paragraph 0027 of JP-A-2010-97210 and paragraphs 0036 to 0037 of JP-A-2015-68893 can also be used, the contents of which are incorporated herein.

Further, a copolymerizable ethylenically unsaturated compound having an ethylenically unsaturated group in its side chain may be used in combination. A (meth)acrylic acid group is preferred as the ethylenically unsaturated group. An acrylic resin containing an ethylenically unsaturated group in a side chain is obtained by, for example, adding an ethylenically unsaturated compound containing a glycidyl group or an alicyclic epoxy group to a carboxylic acid group of an acrylic resin containing a carboxylic acid group. Let it be obtained.

As the alkali-soluble resin, an alkali-soluble resin containing a curable group is also preferred.

As the curable group, the curable group that may be contained in the polymer compound described above is similarly exemplified, 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 on its side chain, or the like is preferable. Alkali-soluble resins containing a curable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), Viscoat R-264, KS Resist 106 ( Both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cychromer P series (for example, ACA230AA), Praxel CF200 series (both manufactured by Daicel), Ebecryl 3800 (manufactured by Daicel Allnex), and Acrycure RD-F8 (Nippon Shokubai Co., Ltd.) made) and the like.

Examples of alkali-soluble resins include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-54-92723, Radical polymers containing carboxylic acid groups in side chains described in JP-A-59-53836 and JP-A-59-71048; EP 993966, EP 1204000, and , Acetal-modified polyvinyl alcohol-based binder resin containing an alkali-soluble group described in each publication such as JP-A-2001-318463; polyvinylpyrrolidone; polyethylene oxide; alcohol-soluble nylon, and 2,2-bis-( 4-Hydroxyphenyl)-propane and epichlorohydrin reaction products such as polyethers; and polyimide resins described in WO 2008/123097;

As the alkali-soluble resin, for example, compounds described in paragraphs 0225 to 0245 of JP-A-2016-75845 can also be used, the contents of which are incorporated herein.

As the alkali-soluble resin, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition polymerizable vinyl monomer] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid / Other addition-polymerizable vinyl monomers as required] copolymers are preferable because they are excellent in the balance of film strength, sensitivity, and developability.

The other addition-polymerizable vinyl monomers may be used alone or in combination of two or more.

The above copolymer preferably has a curable group (preferably an ethylenically unsaturated group such as (meth)acryloyl group). For example, a monomer having a curable group may be used as the other addition-polymerizable vinyl monomer to introduce a curable group into the copolymer. In addition, one or more of the units derived from (meth)acrylic acid in the copolymer and/or the units derived from the other addition polymerizable vinyl monomers have a curable group (preferably ( meth) ethylenically unsaturated groups such as acryloyl groups) may be introduced.

Examples of the other addition-polymerizable vinyl monomers include methyl (meth)acrylate, styrenic monomers (such as hydroxystyrene), and ether dimers.

Examples of the ether dimer include compounds represented by the following general formula (ED1) and compounds represented by the following general formula (ED2).

In general formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms.

In general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As specific examples of the general formula (ED2), the description in JP-A-2010-168539 can be referred to.

Specific examples of the ether dimer, for example, paragraph 0317 of JP-A-2013-29760 can be referred to, the content of which is incorporated herein. Only one kind of ether dimer may be used, or two or more kinds thereof may be used.

A polyimide precursor can also be used as the alkali-soluble resin. A polyimide precursor is intended to be a resin obtained by addition polymerization reaction of a compound containing an acid anhydride group and a diamine compound at 40 to 100°C.

Examples of polyimide precursors include resins containing repeating units represented by formula (1). As the structure of the polyimide precursor, 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 ring-closed, and the following formula (4) in which the entire imide ring is closed ) include polyimide precursors containing an imide structure represented by.

In this 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 is 1 or 2. represents

Specific examples of the polyimide precursor include, for example, compounds described in paragraphs 0011 to 0031 of JP-A-2008-106250, compounds described in paragraphs 0022-0039 of JP-A-2016-122101, and JP-A 2016-68401, paragraphs 0061 to 0092, and the like, the contents of which are incorporated herein.

The alkali-soluble resin preferably contains at least one selected from the group consisting of polyimide resins and polyimide precursors in that the pattern shape of the patterned cured film obtained using the composition is more excellent. .

The polyimide resin containing an alkali-soluble group is not particularly limited, and known polyimide resins containing an alkali-soluble group can be used. Examples of the polyimide resin include, for example, resins described in paragraph 0050 of JP-A-2014-137523, resins described in paragraph 0058 of JP-A-2015-187676, and JP-A-2014-106326. The resins and the like described in paragraphs 0012 to 0013 are included, the contents of which are incorporated herein.

(Resin containing an ethylenically unsaturated group)

The composition of the present invention may contain other resins containing an ethylenically unsaturated group in addition to the specific resin, in order to improve the rectangularity of the cross-sectional shape of the resulting cured film. Other resins containing ethylenically unsaturated groups may be dispersants or alkali-soluble resins. Further, it may be a resin other than a dispersant or an alkali-soluble resin.

The lower limit of the content of other resins containing ethylenically unsaturated groups in the composition is preferably 30% by mass or more, more preferably 50% by mass or more, relative to the total mass of other resins contained in the composition. It is preferably 65 mass % or more, more preferably 85 mass % or more.

The upper limit of the content of other resins containing ethylenically unsaturated groups in the composition is preferably 100% by mass or less with respect to the total mass of other resins contained in the composition.

Other resins containing ethylenically unsaturated groups may be used alone, or two or more may be used, and when two or more are used, the total content is within the above range. is preferred.

In addition, other resins containing ethylenically unsaturated groups refer to other resins containing one or more ethylenically unsaturated groups in one molecule.

The content of other resins containing ethylenically unsaturated groups may be calculated from the charged amounts of raw materials.

In addition, the content of the ethylenically unsaturated group with respect to the total mass of other resins is not particularly limited, but is preferably 0.001 to 5.00 mmol/g, more preferably 0.10 to 3.00 mmol/g, More preferably 0.26 to 2.50 mmol/g. When the ethylenically unsaturated group content is within the range of 0.10 to 3.00 mmol/g, the cross-sectional rectangularity of the cured film obtained using the composition is more excellent.

In addition, the above-mentioned other resin total mass intends the total mass of other resins contained in the composition, for example, other resins containing ethylenically unsaturated groups and other resins not containing ethylenically unsaturated groups When the composition contains a resin, the total mass of both corresponds to the total mass of the other resins.

Therefore, the content of the ethylenically unsaturated group described above represents the content of the ethylenically unsaturated group in the other resin containing the ethylenically unsaturated group with respect to the total mass of the other resin.

In addition, the content of the ethylenically unsaturated group with respect to the total mass of the resin in the composition, including both the specific resin and other resins, is not particularly limited, but is 0.001 to 5.00 mmol/g. Preferably, 0.10 to 4.00 mmol/g is more preferable.

In addition, the acid value of the entire resin in the composition, including both the specific resin and other resins, is not particularly limited, but is generally preferably 30 to 500 mgKOH/g, more preferably 50 to 200 mgKOH/g or less. .

As a method for measuring the content of ethylenically unsaturated groups, the method for measuring the content of ethylenically unsaturated groups (C=C value) explained in the explanation of the specific resin can be similarly mentioned.

[Polymerization inhibitor]

The composition may contain a polymerization inhibitor.

The polymerization inhibitor is not particularly limited, and known polymerization inhibitors can be used. Examples of polymerization inhibitors include phenol-based polymerization inhibitors (e.g., p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4-methoxynaphthol, etc.); hydroquinone-based polymerization inhibitors (e.g. , hydroquinone, 2,6-di-tert-butylhydroquinone, etc.); quinone polymerization inhibitors (e.g., benzoquinone, etc.); free radical polymerization inhibitors (e.g., 2,2,6,6-tetramethylpiperidine 1- oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, etc.); nitrobenzene-based polymerization inhibitors (e.g., nitrobenzene, 4-nitrotoluene, etc.); and phenothiazine-based polymerization inhibitors (eg, phenothiazine, 2-methoxyphenothiazine, etc.);

Among them, a phenol-based polymerization inhibitor or a free-radical polymerization inhibitor is preferable because the light-shielding 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 light-shielding composition is not particularly limited, but is preferably 0.0001 to 0.5% by mass, more preferably 0.001 to 0.2% by mass, based on the total solid content of the composition. is more preferred, and 0.008 to 0.05% by mass is even more preferred. A polymerization inhibitor may be used individually by 1 type, and may use 2 or more types. When using two or more polymerization inhibitors, the total content is preferably within the above range.

The mass ratio of the content of the polymerization inhibitor to the specific resin in the composition is preferably 0 to 0.006, more preferably 0.001 to 0.005, even more preferably 0.002 to 0.005. The mass ratio of the content represents (content of polymerization inhibitor)/(content of specific resin) in the composition.

[Compound containing epoxy group]

The composition of the present invention may use compounds containing epoxy groups.

Compounds containing an epoxy group include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups in one molecule are preferred. It is preferable to have 1 to 100 epoxy groups in one molecule. The upper limit may be, for example, 10 or less, or 5 or less. The lower limit is preferably two or more.

In addition, the compound containing an epoxy group intends the component different from the above-mentioned specific resin, a dispersing agent, alkali-soluble resin, and a polymerizable compound.

The epoxy group-containing compound preferably has an epoxy equivalent weight (=molecular weight of epoxy group-containing compound/number of epoxy groups) of 500 g/equivalent or less, more preferably 100 to 400 g/equivalent. More preferably ~300 g/equivalent.

The compound containing an epoxy group may be a low-molecular-weight compound (e.g., molecular weight less than 2000) or a macromolecule (e.g., molecular weight 2000 or more, in the case of a polymer, weight-average molecular weight 2000 or more). good. The weight average molecular weight of the epoxy group-containing compound is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, still more preferably 5,000 or less, and particularly preferably 3,000 or less.

A commercially available compound containing an epoxy group may be used. Examples include EHPE3150 (manufactured by Daicel) and EPICLON N-695 (manufactured by DIC). Further, the compound containing an epoxy group, paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147-0156 of JP-A-2014-043556, and paragraphs 0085-0092 of JP-A-2014-089408 You may use the compound described in. The contents of these are incorporated herein.

The content of the epoxy group-containing compound in the 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 composition. 0 to 6% by mass is more preferable.

Epoxy group-containing compounds may be used singly or in combination of two or more. When the composition contains two or more compounds containing an epoxy group, the total content is preferably within the above range.

[Ultraviolet absorber]

The composition may contain an ultraviolet absorber. Thereby, 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. Specific examples thereof include compounds of paragraphs 0137 to 0142 of JP-A-2012-068418 (corresponding paragraphs 0251 to 0254 of US2012/0068292), and the contents thereof can be cited and incorporated herein. .

In addition, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by Daito Kagaku 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 JP-A-2012-32556.

The content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, still more preferably 0.1 to 5% by mass, based on the total solid content of the composition.

[Silane coupling agent (adhesion agent)]

The composition may contain a silane coupling agent.

The silane coupling agent functions as an adhesion agent that improves adhesion between the substrate and the cured film when forming the cured film on the substrate.

A silane coupling agent is a compound containing a hydrolyzable group and other functional groups in its molecule. Hydrolyzable groups such as alkoxy groups are bonded to silicon atoms.

A hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and capable of forming a siloxane bond through a hydrolysis reaction and/or a condensation reaction. Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups, and alkenyloxy groups. When the hydrolyzable group contains carbon atoms, it preferably has 6 or fewer carbon atoms, more preferably 4 or fewer. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.

In addition, when forming a cured film on a substrate, the silane coupling agent is used to improve the adhesion between the substrate and the cured film. ), a fluorine atom, a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, and , preferably does not contain a branched alkyl group having 3 or more carbon atoms.

The silane coupling agent may contain ethylenically unsaturated groups such as (meth)acryloyl groups. When it contains ethylenically unsaturated groups, the number thereof is preferably 1 to 10, more preferably 4 to 8. A silane coupling agent containing an ethylenically unsaturated group (for example, a compound containing a hydrolyzable group and an ethylenically unsaturated group and having a molecular weight of 2000 or less) does not correspond to the polymerizable compound described above.

The content of the silane coupling agent in the 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 composition, and 1.0 to 6% by mass is more preferred.

The silane coupling agent may be used singly or in combination of two or more. When the composition contains two or more silane coupling agents, the total may be within the above range.

Silane coupling agents include, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Examples include vinyltrimethoxysilane and vinyltriethoxysilane.

[Surfactant]

The composition may contain a surfactant. A surfactant contributes to improving the coatability of the composition.

When the composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 0.005%, based on the total solid content of the composition. 5% by mass is more preferable, and 0.01 to 0.1% by mass is even more preferable.

One type of surfactant may be used alone, or two or more types may be used. When two or more surfactants are used, the total amount is preferably within the above range.

Examples of surfactants include fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.

For example, if the composition contains a fluorosurfactant, the liquid properties (particularly fluidity) of the composition are further improved. That is, in the case of forming a film using a composition containing a fluorosurfactant, the interfacial tension between the surface to be coated and the coating liquid is reduced to improve the wettability of the surface to be coated. Improves surface applicability. Therefore, even when a thin film having a thickness of about several μm is formed with a small amount of liquid, it is effective in that a film having a uniform thickness with little unevenness in thickness can be formed more favorably.

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

Examples of fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, and F780 (manufactured by DIC Corporation); Florado FC430, FC431, and FC171 (manufactured by Sumitomo 3M Limited); Surflon S-382, SC-101 , SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (manufactured by Asahi Glass Co., Ltd.) ); and PF636, PF656, PF6320, PF6520, and PF7002 (manufactured by OMNOVA).

A block polymer can also be used as the fluorosurfactant, and specific examples thereof include the compounds described in JP-A-2011-89090.

〔solvent〕

The composition preferably contains a solvent.

The solvent is not particularly limited and known solvents can be used.

The content of the solvent in the composition is not particularly limited, but the amount is preferably such that the solid content of the composition is 10 to 90% by mass, more preferably 10 to 40% by mass, and 15 to 35% by mass. is more preferred.

A solvent may be used individually by 1 type, and may use 2 or more types. When two or more solvents are used, the total solid content of the composition is preferably adjusted within the above range.

Examples of solvents include water and organic solvents.

Examples of organic solvents 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 acetylacetone. , cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol 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, and ethyl lactate, but are not limited to these.

(water)

When the composition contains water, its content is preferably 0.001 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, based on the total mass of the composition. .1 to 1.0% by mass is more preferable.

Among them, if the water content is 3.0% by mass or less (more preferably 1.0% by mass or less) relative to the total mass of the composition, the viscosity over time due to hydrolysis of the components in the composition Degradation of stability can be easily suppressed, and when the content is 0.01% by mass or more (preferably 0.1% by mass or more), sedimentation stability over time can be easily improved.

[Other optional ingredients]

The composition may further contain other optional ingredients than those mentioned above. Examples include sensitizers, co-sensitizers, cross-linking agents, curing accelerators, fillers, thermosetting accelerators, plasticizers, diluents, and sensitizers. agents and other auxiliaries (e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release accelerators, antioxidants, fragrances, surface tension modifiers, chain transfer agents, etc.), etc. known additives may be added as required.

These components are, for example, paragraphs 0183 to 0228 of JP 2012-003225 (paragraphs 0237 to 0309 of corresponding US Patent Application Publication No. 2013/0034812), paragraph 0101 of JP 2008-250074 to 0102, paragraphs 0103 to 0104, paragraphs 0107 to 0109, and paragraphs 0159 to 0184 of Japanese Patent Laid-Open No. 2013-195480, etc., and the contents thereof are incorporated herein.

The composition preferably contains inorganic particles, more preferably silica particles, as a filler. Silica particles may be solid silica, hollow silica, or porous silica.

The content of silica particles in the composition is not particularly limited, but from the viewpoint of excellent low reflectivity, it is preferably 1 to 15% by mass, more preferably 4 to 10% by mass, based on the total solid content of the composition. .

Although the average primary particle size of the silica particles is not particularly limited, it is preferably 40 nm or more and less than 100 nm. The average primary particle size of silica particles can be measured using a transmission electron microscope (TEM) in the same manner as the average primary particle size of pigments.

The silica particles may have their surfaces modified, and silica particles whose surfaces have been modified with functional groups are preferred. Examples of functional groups that modify the surface of silica particles include hydrocarbon groups, (meth)acryloyl groups, vinyl groups, fluorine-containing groups, groups containing siloxane bonds, hydroxyl groups, acid groups, and basic groups. be done.

A method for synthesizing surface-modified silica particles (method for surface modification of silica particles) is not particularly limited, and a known method using a surface modifier can be used. For example, a method of modifying the surface of silica particles using a silane coupling agent containing a hydrolyzable group and the above functional group in the molecule, and an ethylenically unsaturated group (e.g. (meth) acryloyl group and vinyl group) on the surface with a compound having an ethylenically unsaturated group and the above functional group in the presence of a polymerization initiator.

The amount of the surface modifier used in the method for synthesizing surface-modified silica particles is not particularly limited, but the content of the surface modifier with respect to the total solid content of the composition of silica particles is 1 to 70% by mass. Preferably, the amount of 5 to 50% by mass is more preferable. In addition, a surface modifier may be used individually by 1 type, and may use 2 or more types.

[Method for producing composition]

The composition is preferably produced by first producing a dispersion composition in which a black colorant is dispersed, and then mixing the resulting dispersion composition with other components to form a composition.

The dispersion composition is preferably prepared by mixing a black colorant, a resin (either a specific resin or another resin, preferably a dispersant), and a solvent. It is also preferable to incorporate a polymerization inhibitor into 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, homogenizer, high-pressure emulsifying device, wet pulverizer, or wet disperser).

In the preparation of the composition, each component may be blended all at once, or each component may be dissolved or dispersed in a solvent and then blended successively. In addition, there are no particular restrictions on the order of addition and working conditions when blending.

The composition is preferably filtered for purposes such as removing foreign matter and reducing defects.

As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. Examples include filters made of fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high density and ultrahigh molecular weight) such as polyethylene and polypropylene (PP). . Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore size of the filter is preferably 0.1-7.0 μm, more preferably 0.2-2.5 μm, even more preferably 0.2-1.5 μm, and particularly preferably 0.3-0.7 μm. Within this range, fine foreign matter such as impurities and aggregates contained in the pigment can be reliably removed while suppressing filter clogging of the pigment.

When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once, or may be performed twice or more. When filtering is performed twice or more by combining different filters, it is preferable that the pore size of the second and subsequent filtering is the same as or larger than the pore size of the first filtering. Also, the first filters having different pore diameters within the range described above may be combined. The pore size here can refer to the nominal value of the filter manufacturer. Commercially available filters can be selected from various filters provided by Nihon Pall Co., Ltd., Advantech Toyo Co., Ltd., Nihon Entegris Co., Ltd. (formerly Nihon Microlith Co., Ltd.), and Kitz Micro Filter Co., Ltd., for example.

As the second filter, a filter made of the same material as the first filter described above can be used. The pore size of the second filter is preferably 0.2-10.0 μm, more preferably 0.2-7.0 μm, even more preferably 0.3-6.0 μm.

The composition preferably does not contain impurities such as metals, halogen-containing metal salts, acids and alkalis. The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 1 mass ppb or less, still more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and substantially free of ( is below the detection limit of the measuring device) is most preferred.

The above impurities can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent 7500cs).

[Method for producing cured film]

A cured film (including a patterned cured film) can be obtained by curing the composition layer formed using the above composition.

The method for producing a cured film is not particularly limited, but preferably includes the following steps.

・Composition layer forming process

・Exposure process

・Development process

Each step will be described below.

<Composition layer forming step>

In the composition layer forming step, prior to exposure, the composition is applied onto a support or the like to form a composition layer (composition layer). As the support, for example, a substrate for a solid-state imaging device provided with an imaging device (light receiving device) such as CCD (Charge Coupled Device) or CMOS (Complementary Metal-Oxide Semiconductor) on a substrate (eg, silicon substrate) is used. can. Further, if necessary, an undercoat layer may be provided on the support for improving adhesion to the upper layer, preventing diffusion of substances, flattening the surface of the substrate, and the like.

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

[Exposure process]

In the exposure step, the composition layer formed in the composition layer forming step is exposed to actinic rays or radiation, and the irradiated composition layer is cured.

Although the method of light irradiation is not particularly limited, light irradiation through a photomask having patterned openings is preferable.

Exposure is preferably carried out by irradiating with radiation. Radiation that can be used for exposure is particularly preferably ultraviolet rays such as g-line, h-line and i-line, and a high-pressure mercury lamp is preferred as a light source. The irradiation intensity is preferably 5-1500 mJ/cm ² , more preferably 10-1000 mJ/cm ² .

When the composition contains a thermal polymerization initiator, the composition layer may be heated in the exposure step. Although the heating temperature is not particularly limited, it is preferably 80 to 250°C. Although the heating time is not particularly limited, it is preferably 30 to 300 seconds.

In addition, in the case where the composition layer is heated in the exposure step, the post-heating step described below may also be performed. In other words, when the composition layer is heated in the exposure step, post-baking may not be performed.

[Development process]

The developing step is a step of developing the exposed composition layer to form a cured film. In this step, the composition layer in the portion not irradiated with light in the exposure step is eluted, leaving only the photocured portion to obtain a patterned cured film.

The type of developer used in the development process is not particularly limited, but an alkaline developer that does not cause damage to the underlying imaging device, circuits, and the like is desirable.

The developing temperature is, for example, 20 to 30.degree.

The development time is, for example, 20-90 seconds. In order to remove more residue, in recent years there are cases where it is carried out for 120 to 180 seconds. Furthermore, in order to further improve the residue removability, the process of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.

The alkaline developer is preferably an alkaline aqueous solution prepared by dissolving an alkaline compound in water to a concentration of 0.001 to 10% by mass (preferably 0.01 to 5% by mass).

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 ammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene, etc. (of which organic alkali preferable.).

In addition, when it is used as an alkaline developer, it is generally washed with water after development.

[Post-bake]

Heat treatment (post-baking) is preferably performed after the exposure step. A post-bake is a heat treatment after development to complete curing. The heating temperature is preferably 240° C. or lower, more preferably 220° C. or lower. Although there is no lower limit, it is preferably 50° C. or higher, more preferably 100° C. or higher, in consideration of efficient and effective treatment.

Post-baking can be performed continuously or batchwise using heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater.

The above post-baking may be performed in an atmosphere of low oxygen concentration. The oxygen concentration is, for example, preferably 19% by volume or less, more preferably 15% by volume or less, even more preferably 10% by volume or less, and particularly preferably 7% by volume or less, Most preferably, it is 3% by volume or less. Although there is no particular lower limit, 10 ppm by volume or more is practical.

Further, instead of post-baking by heating as described above, UV (ultraviolet) irradiation may be used for complete curing.

In this case, the 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-line exposure. Examples of UV curing agents include Ciba Irgacure 2959 (trade name). When UV irradiation is performed, the composition layer is preferably made of a material that cures at a wavelength of 340 nm or less. Although there is no particular lower limit for the wavelength, 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, even more preferably 800 to 3500 mJ. This UV curing step is preferably performed after the lithography step in order to perform low temperature curing more effectively. It is preferable to use an ozoneless mercury lamp as an exposure light source.

[Physical properties of cured film and use of cured film]

[Physical properties of cured film]

The cured film to be formed comprises a black layer (lower layer) containing a black coloring material and a coating layer (containing a cured product of a specific resin) formed from a specific resin, as described with reference to FIG. The upper layer) is typically a two-layer structure. The coating layer is usually a layer arranged on the opposite side (air side) to the substrate in the cured film arranged on the substrate.

The black layer mainly contains the black colorant described above.

The coating layer is a layer formed by curing a specific resin unevenly distributed near the surface of the coating film obtained by applying the composition. The coating layer may contain an unreacted specific resin.

The coating layer may also contain components other than components derived from the specific resin (cured product of the specific resin, unreacted specific resin, etc.). However, the coating layer preferably does not substantially contain a black colorant. Specifically, the content of the black coloring material in the coating layer is preferably 5% by mass or less, more preferably 1% by mass or less, relative to the total mass of the coating layer.

The refractive index of the coating layer is preferably lower than that of the black layer.

The thickness of the cured film is, for example, preferably 0.1 to 4.0 μm, more preferably 1.0 to 2.5 μm. The cured film may be thinner or thicker than this range depending on the application.

Further, when the cured film is used as the light attenuation film, it is preferable to adjust the light shielding property by making the film thinner than the above range (for example, 0.1 to 0.5 μm).

The thickness of the coating layer depends on the thickness of the entire cured film, but is preferably, for example, 5 to 300 nm, more preferably 10 to 200 nm, even more preferably 20 to 200 nm, and particularly preferably 20 to less than 175 nm.

The film thickness of the cured film and the coating layer can be measured from a cross-sectional SEM (Scanning Electron Microscope) image of the cured film.

The cured film obtained using the composition of the present invention has excellent light-shielding properties, and has an optical density (OD) of 2.0 per 1.0 μm of film thickness in the wavelength range of 400 to 1200 nm. is preferably 3.0 or more, more preferably 3.0 or more. Although the upper limit is not particularly limited, generally 10 or less is preferable. The above cured film can be preferably used as a light shielding film.

Further, when the cured film (light-shielding film) is used as a light-attenuating film, the optical density per 1.0 μm film thickness in the wavelength range of 400 to 1200 nm is preferably, for example, 0.1 to 1.5. 0.2 to 1.0 is more preferred. Further, in this specification, the optical density per 1.0 μm film thickness in the wavelength region of 400 to 1200 nm is 3.0 or more, which means that the optical density per 1.0 μm film thickness is 3.0 or more in the entire wavelength range of 400 to 1200 nm. It is intended to be 3.0 or greater.

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 measured using a transmission densitometer (X-rite 361T (visual) densitometer). The thickness of the film is also measured at the location, and the optical density per predetermined film thickness is calculated.

Moreover, the cured film preferably has an uneven surface 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 an uneven structure. The shape of the uneven surface 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, even more preferably 2% or less.

The method for producing the uneven surface structure is not particularly limited, but a cured film or other layer containing an organic filler and / or an inorganic filler, a lithography method using exposure and development, or an etching method, a sputtering method, and a A method of roughening the surface of a cured film or other layer by a nanoimprint method or the like may also be used.

In addition, as a method for lowering the reflectance of the cured film, in addition to the above, a method of providing a low refractive index layer on the cured film, a method of providing a plurality of layers with different refractive indexes (for example, a high refractive index layer), and , a method of forming a low optical density layer and a high optical density layer described in JP-A-2015-1654.

In addition, the cured film can be used for personal computers, tablets, mobile phones, smartphones, and portable devices such as digital cameras; OA (Office Automation) devices such as printer multifunction devices and scanners; surveillance cameras, barcode readers, cash Industrial equipment such as automatic teller machine (ATM: automated teller machine), high speed camera, and equipment with personal authentication function using face image authentication; vehicle camera equipment; endoscope, capsule endoscope, and medical camera equipment such as catheters; and biosensors, biosensors, military reconnaissance cameras, stereo map cameras, weather and ocean 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, as well as anti-reflection members and anti-reflection films.

The cured film can also be used for applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes). The cured film is suitable for optical filters and optical films used in micro LEDs and micro OLEDs, as well as members imparting a light shielding function or an antireflection function.

Examples of micro LEDs and micro OLEDs include those described in Japanese Patent Publication No. 2015-500562 and Japanese Patent Publication No. 2014-533890.

The cured film is also suitable as an optical filter and an optical film used in quantum dot sensors and quantum dot solid-state imaging devices. Moreover, it is suitable as a member that imparts a light shielding function and an antireflection function. Examples of quantum dot sensors and quantum dot solid-state imaging devices include those described in US Patent Application Publication No. 2012/37789 and International Publication No. 2008/131313.

[Light shielding film, solid-state imaging device, and solid-state imaging device]

The light-shielding film of the present invention is also preferably used for solid-state imaging devices.

A light-shielding film is one of the preferred applications of the cured film of the present invention, and the light-shielding film of the present invention can be produced in the same manner as described above as the method for producing the cured film. Specifically, the composition can be applied to a substrate to form a composition layer, exposed to light, and developed to produce a light-shielding film.

Further, the solid-state imaging device of the present invention is a solid-state imaging device having the cured film (light-shielding film) containing the above-described cured film (light-shielding film) of the present invention.

As described above, the solid-state imaging device according to the present invention contains the cured film (light shielding film). The form in which the solid-state imaging device contains a cured film (light-shielding film) is not particularly limited. and a light-receiving element made of polysilicon or the like, and a cured film on the side of the support on which the light-receiving element is formed (for example, a portion other than the light-receiving portion and/or the pixels for color adjustment, etc.) or on the opposite side of the formation surface. mentioned.

When a cured film (light-shielding film) is used as a light-attenuating film, the solid-state imaging can The dynamic range of the device can be improved.

A solid-state imaging device includes the solid-state imaging device.

Configuration examples of a solid-state imaging device and a solid-state imaging device will be described with reference to FIGS. In addition, in FIGS. 2 and 3, in order to clarify each part, the ratio of thickness and/or width to each other is disregarded and partly exaggerated.

As shown in FIG. 2, the solid-state imaging device 100 includes a rectangular solid-state imaging device 101 and a transparent cover glass 103 that is held above the solid-state imaging device 101 and seals the solid-state imaging device 101. there is Further, a lens layer 111 is provided over the cover glass 103 with spacers 104 interposed therebetween. 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 enters the peripheral area of the lens layer 111 , light diffusion weakens the light-condensing effect of the lens material 112 , thereby reducing the amount of light reaching the imaging unit 102 . Also, 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 shield the light. The cured film of the present invention can also be used as the light shielding film 114 described above.

The solid-state imaging device 101 photoelectrically converts an optical image formed by an imaging unit 102 serving as a light-receiving surface thereof, and outputs it as an image signal. This solid-state imaging device 101 has a laminated substrate 105 in which two substrates are laminated. The laminated board 105 is composed of a rectangular chip board 106 and a circuit board 107 of the same size.

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

An imaging unit 102 is provided in the central portion of the surface of the chip substrate 106 . In addition, when stray light enters the peripheral region of the imaging unit 102, a dark current (noise) is generated from circuits in the peripheral region. The cured film 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 pads 108 are electrically connected to the imaging section 102 via signal lines (not shown) (bonding wires are also possible) provided on the surface of the chip substrate 106 .

External connection terminals 109 are provided on the rear surface of the circuit board 107 at positions substantially below the respective electrode pads 108 . Each external connection terminal 109 is connected to an electrode pad 108 via a penetrating electrode 110 vertically penetrating through the laminated substrate 105 . Each external connection terminal 109 is connected to a control circuit for controlling driving of the solid-state imaging device 101 and an image processing circuit for performing image processing on an imaging signal output from the solid-state imaging device 101 via wiring (not shown). It is connected.

As shown in FIG. 3, the imaging unit 102 is composed of units provided on a substrate 204, such as a light receiving element 201, a color filter 202, and a microlens 203. FIG. The color filter 202 has blue pixels 205b, red pixels 205r, green pixels 205g, and a black matrix 205bm. The cured film of the present invention may be used as the black matrix 205bm.

As the material of the substrate 204, the same material as that of 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 made of an n-type layer and generate and store signal charges by photoelectric conversion are arranged in a square lattice.

A vertical transfer path 208 made of an n-type layer is formed on one side of the light receiving element 201 via a readout gate portion 207 on the surface layer of the p-well layer 206 . 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 isolation region 209 made of a p-type layer. The read gate portion 207 is a channel region for reading signal charges accumulated in the light receiving element 201 to 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 . A vertical transfer electrode 211 made of polysilicon or amorphous silicon is formed on the gate insulating film 210 so as to cover the vertical transfer path 208 , the readout gate portion 207 and the element isolation region 209 . The vertical transfer electrode 211 functions as a drive electrode that drives the vertical transfer path 208 to transfer charges, and a readout electrode that drives the readout gate section 207 to read out signal charges. The signal charges are sequentially transferred from the vertical transfer path 208 to a horizontal transfer path (not shown) and an output section (floating diffusion amplifier), 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 directly above the light receiving element 201 and shields the other region from light. The cured film of the present invention may be used as the light shielding film 212 .

On the light shielding film 212, there is provided a transparent intermediate layer consisting of an insulating film 213 made of BPSG (borophospho silicate glass), an insulating film (passivation film) 214 made of P—SiN, and a flattening film 215 made of a transparent resin or the like. ing. A color filter 202 is formed on the intermediate layer.

[Image display device]

The cured film of the present invention can also be applied to image display devices.

Examples of the mode in which the image display device has a cured film include a mode 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, a liquid crystal display containing such a color filter will be described as a specific example of the image display device.

<Black Matrix>

The cured film of the present invention is also preferably contained in a black matrix. A black matrix may be contained in an image display device such as a color filter, a solid-state imaging device, and a liquid crystal display device.

Examples of the black matrix include those already described above; a black edge provided at the periphery of an image display device such as a liquid crystal display device; grids and/or stripes between red, blue, and green pixels. dot-shaped and/or linear black patterns for TFT (thin film transistor) light shielding; and the like. For the definition of this black matrix, see, for example, Taihei Kanno, "Liquid Crystal Display Manufacturing Equipment Terminology", 2nd Edition, Nikkan Kogyo Shimbun, 1996, p. 64.

The black matrix has a high light shielding property (optical density OD is 3 or more).

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

Although the material of the substrate is not particularly limited, it preferably has a transmittance of 80% or more for visible light (wavelength of 400 to 800 nm). Specific examples of such materials include glasses such as soda lime glass, alkali-free glass, quartz glass, and borosilicate glass; plastics such as polyester resins and polyolefin resins; From the viewpoint of chemical resistance and heat resistance, alkali-free glass, quartz glass, or the like is preferable.

<Color filter>

The cured film of the present invention is also preferably contained in a color filter.

The form in which the color filter contains a cured film is not particularly limited, but includes a color filter comprising a substrate and the black matrix. That is, a color filter having 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 (composition layer) of a composition containing a pigment corresponding to each color pixel of a color filter is formed in the openings of a patterned black matrix formed on a substrate. The composition for each color is not particularly limited, and known compositions can be used. preferably used.

Next, the composition layer is exposed through a photomask having a pattern corresponding to the openings of the black matrix. Then, after removing the unexposed areas by development, the substrate can be baked to form colored pixels in the openings of the black matrix. By performing a series of operations, for example, using compositions for each color containing red, green, and blue pigments, a color filter having red, green, and blue pixels can be produced.

<Liquid crystal display device>

The cured film of the present invention is also preferably contained in a liquid crystal display device. The form in which the liquid crystal display device contains the cured film is not particularly limited, but examples include the form in which the already described color filter containing the black matrix (cured film) is contained.

As a liquid crystal display device according to this embodiment, for example, there is a mode in which a pair of substrates arranged to face each other and a liquid crystal compound sealed between the substrates are provided. As the substrate, the substrate for the black matrix has already been described.

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

The liquid crystal display device is not limited to the above. published in 1989)” and the like. Further, for example, there is a liquid crystal display device described in "Next Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, Published by Kogyo Choukai Co., Ltd., 1994)".

[Infrared sensor]

The cured film of the present invention is also preferably contained in an infrared sensor.

An infrared sensor according to the above embodiment will be described with reference to FIG. In the infrared sensor 300 shown in FIG. 4, reference numeral 310 is a solid-state imaging device.

The imaging area provided on the solid-state imaging device 310 is configured by combining an infrared absorption filter 311 and a color filter 312 according to the embodiment of the present invention.

The infrared absorption filter 311 transmits light in the visible region (for example, light with a wavelength of 400 to 700 nm), and transmits light in the infrared region (for example, light with a wavelength of 800 to 1300 nm, preferably light with a wavelength of 900 to 1200 nm). (preferably light with a wavelength of 900 to 1000 nm), and a cured film containing an infrared absorbing agent (the form of the infrared absorbing agent is as already described) as a coloring agent can be used.

The color filter 312 is a color filter formed with pixels that transmit and absorb light of specific wavelengths in the visible light region. For example, pixels of red (R), green (G), and blue (B) are formed. A color filter or the like is used, and its form is as already explained.

Between the infrared transmission filter 313 and the solid-state imaging device 310, a resin film 314 (for example, a transparent resin film or the like) that allows transmission of the light of the wavelength that has passed through the infrared transmission filter 313 is arranged.

The infrared transmission filter 313 is a filter that has a visible light shielding property and transmits infrared rays of a specific wavelength, and is a colorant that absorbs light in the visible light region (for example, a perylene compound and/or a bisbenzoate Furanone compounds, etc.) and infrared absorbers (eg, pyrrolopyrrole compounds, phthalocyanine compounds, naphthalocyanine compounds, polymethine compounds, etc.) can be used in the cured film of the present invention. The infrared transmission filter 313 preferably blocks light with a wavelength of 400 to 830 nm and transmits light with 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 planarization film 316 is formed to cover the microlenses 315 .

Although the resin film 314 is arranged in the form shown in FIG. That is, the infrared transmission filter 313 may be formed on the solid-state imaging device 310 .

Moreover, in the form shown in FIG. 4, 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.

In the embodiment shown in FIG. 4, the color filter 312 is provided closer to the incident light hv than the infrared absorption filter 311. 311 may be provided on the incident light hν side of the color filter 312 .

In addition, in the embodiment shown in FIG. 4, the infrared absorption filter 311 and the color filter 312 are laminated adjacent to each other. good. The cured film of the present invention can be used as a light shielding film such as the edge and / or side of the surface of the infrared absorption filter 311, and if it is used for the inner wall of the infrared sensor device, internal reflection and / or unintended light to the light receiving part can be prevented from entering, and the sensitivity can be improved.

According to this infrared sensor, since image information can be captured at the same time, it is possible to perform motion sensing, etc., by recognizing an object whose motion is to be detected. Furthermore, since distance information can be acquired, it is also possible to capture an image including 3D information.

Next, a solid-state imaging device to which the above infrared sensor is applied will be described.

The solid-state imaging device includes a lens optical system, a solid-state imaging device, an infrared light emitting diode, and the like. For each configuration of the solid-state imaging device, paragraphs 0032 to 0036 of Japanese Patent Application Laid-Open No. 2011-233983 can be referred to, and the contents thereof are incorporated into the specification of the present application.

The present invention will be described in more detail based on examples below. The materials, amounts used, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limited by the examples shown below.

[Preparation of light-shielding composition]

As shown in Table 4, each component was mixed in each part by mass to prepare compositions 1 to 41.

[Preparation of dispersion composition]

For the preparation of the light-shielding composition (hereinafter also simply referred to as "composition"), first, a dispersion composition was prepared.

<Preparation of titanium black dispersion liquid A (dispersion liquid A)>

The following raw materials were subjected to dispersion treatment using NPM Pilot manufactured by Shinmaru Enterprises to obtain a titanium black dispersion liquid A.

・ Titanium black (T-1) (details will be described later); 25 parts by mass

- Resin (X-1) (details will be described later) PGMEA 30% by mass solution (pigment dispersant); 25 parts by mass

・PGMEA; 23 parts by mass

・Butyl acetate; 27 parts by mass

PGMEA means propylene glycol monomethyl ether acetate.

A 30% by mass solution of resin (X-1) in PGMEA means that resin (X-1) is added to PGMEA so that the content of resin (X-1) is 30% by mass with respect to the total mass of the solution. Dissolved solutions are intended. Hereinafter, the description of "(solvent name) (number) mass % solution of (substance name)" is based on the same intention.

(Preparation of titanium black (T-1))

Titanium oxide MT-150A (trade name: Tayca) (100 g) with an average particle size of 15 nm, silica particles AEROGIL (registered trademark) 300/30 (Evonik) (25 g) with a BET surface area of 300 m ² /g, and a dispersant DISPERBYK-190 (trade name: manufactured by BYK) (100 g) is weighed, ion-exchanged water (71 g) is added, and using KURABO's MAZERSTAR KK-400W, the revolution speed is 1360 rpm and the rotation speed is 1047 rpm. A homogeneous aqueous solution of the mixture was obtained by processing for 1 minute. This aqueous solution is filled in a quartz container, heated to 920° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.), then the atmosphere is replaced with nitrogen, and ammonia gas is supplied at 100 mL/min at the same temperature for 5 hours. Nitriding reduction treatment was carried out by flowing. After completion, the collected powder was pulverized in a mortar to obtain titanium black (T-1) containing Si atoms and having a powdery specific surface area of 73 m ² /g.

(Preparation of resin (X-1))

A resin P containing 15% by mass and 85% by mass of repeating units derived from the following monomer A and repeating units derived from the following monomer B, respectively, relative to the total repeating units of the resin was synthesized. A resin X-1 was prepared by introducing an ethylenically unsaturated group into the obtained resin P using 4-hydroxybutyl acrylate glycidyl ether.

The obtained resin X-1 had a weight average molecular weight of 15,000, an acid value of 70 mgKOH/mg, and a C=C value of 1.1 mmol/g.

- Monomer A (a macromonomer, weight average molecular weight is 3000, the value of 9 attached to the repeating unit is the average value of each monomer)

・ Monomer B (Aronix M5300 (manufactured by Toagosei Co., Ltd.))

CH ₂ ═CHCOO—(C ₅ H ₁₀ COO) _n —Hω-carboxy-polycaprolactone (n≈2) monoacrylate

<Preparation of titanium black dispersion B (dispersion B)>

Dispersion B was prepared in the same manner as dispersion A, except that the resin (X-1) PGMEA 30 mass% solution (pigment dispersant) was changed to the resin (X-2) PGMEA 30 mass% solution (pigment dispersant). made.

The structure of resin (X-2) is as follows. The weight average molecular weight was 33000, the acid value was 60 mgKOH/mg, and the C=C value was 0 mmol/g.

Also, the number attached to each repeating unit indicates the molar ratio of each unit.

<Preparation of carbon black (CB) dispersion liquid C (dispersion liquid C)>

A dispersion obtained by mixing the following raw materials was further thoroughly stirred with a stirrer for premixing. Furthermore, the dispersion was subjected to a dispersion treatment using Ultra Apex Mill UAM015 manufactured by Kotobuki Kogyo Co., Ltd. under the dispersion conditions described below to obtain a dispersion. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to obtain a dispersion liquid C.

・Coated carbon black (details will be described later); 20 parts by mass

・ DISPERBYK-167 (pigment dispersant, manufactured by BYK, solid content 52% by mass); 8.7 parts by mass

- Solsperse 12000 (pigment derivative, manufactured by Lubrizol); 1 part by mass

・PGMEA: Amount that makes the solid content of dispersion C 35% by mass

(Dispersion condition)

Bead diameter: φ0.05mm

Bead filling rate: 65% by volume

Mill peripheral speed: 10m/sec

Separator peripheral speed: 11m/s

Amount of mixed liquid to be dispersed: 15.0 g

Circulating flow rate (pump supply rate): 60 kg/hour

Treatment liquid temperature: 20-25°C

Cooling water: Tap water 5°C

Bead mill annular passage internal volume: 2.2L

Number of passes: 84 passes

(Preparation of coated carbon black)

Carbon black was produced by a conventional oil furnace method. However, ethylene bottom oil with low Na content, Ca content and S content was used as the raw material oil, and gas fuel was used for combustion. Furthermore, pure water treated with an ion exchange resin was used as the water for stopping the reaction.

Using a homomixer, the obtained carbon black (540 g) was stirred with pure water (14500 g) at 5,000 to 6,000 rpm for 30 minutes to obtain a slurry. This slurry was transferred to a container equipped with a screw type stirrer, and toluene (600 g) in which epoxy resin "Epikote 828" (manufactured by Japan Epoxy Resin) (60 g) was dissolved was added little by little while mixing at about 1,000 rpm. In about 15 minutes, all of the carbon black dispersed in water migrated to the toluene side and became particles of about 1 mm.

Next, after draining with a 60-mesh wire mesh, the separated grains were placed in a vacuum dryer and dried at 70° C. for 7 hours to remove toluene and water. The resin coating amount of the obtained coated carbon black was 10% by mass with respect to the total amount of carbon black and resin.

<Preparation of black dispersion D (dispersion D)>

Dispersion D was prepared in the same manner as Dispersion C, except that the coating carbon black was changed to Irgaphor Black S 0100 CF (manufactured by BASF).

<Preparation of black dispersion E (dispersion E)>

Red pigment dispersion liquid R1 and blue pigment dispersion liquid B1 shown below were mixed at a ratio of 1:1 (mass ratio).

to obtain a dispersion liquid E.

(Red pigment dispersion liquid R1)

The following raw materials were subjected to dispersion treatment using NPM Pilot manufactured by Shinmaru Enterprises to obtain Red pigment dispersion liquid R1.

・Pigment Red254; 8.3 parts by mass

・Pigment Yellow 139; 3.7 parts by mass

・ DISPERBYK-161 (dispersant, manufactured by BYK, solid content 30% by mass); 16.0 parts by mass

・PGMEA; 72.0 parts by mass

(Blue pigment dispersion B1)

The following raw materials were subjected to dispersion treatment using NPM Pilot manufactured by Shinmaru Enterprises to obtain Blue Pigment Dispersion B1.

・Pigment Blue 15:6; 9.5 parts by mass

・Pigment Violet 23; 2.4 parts by mass

・ DISPERBYK-161 (dispersant, manufactured by BYK, solid content 30% by mass); 18.7 parts by mass

・PGMEA; 69.4 parts by mass

[Raw material of composition]

The raw materials used to prepare the composition are shown below.

<Dispersion composition>

Dispersions A to E described above were used as dispersion compositions.

<Resin>

· A-1: A polymer synthesized by the following method.

In an autoclave with an internal volume of 1 L equipped with a stirrer, MEK (2-butanone) (420.0 g), X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd., containing a methacrylic group-containing group at one end, straight Linear dimethylpolysiloxane) (5.4 g), MAA (methacrylic acid) (18.0 g), 2-HEMA (2-hydroxyethyl methacrylate) (99.0 g), IBMA (isobornyl methacrylate) (57.6 g) ), and a polymerization initiator V-70 (manufactured by Wako Pure Chemical Industries, Ltd., 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile)) (2.0 g) were charged and stirred under a nitrogen atmosphere. The mixture was polymerized at 30° C. for 24 hours to synthesize a crude copolymer. Heptane was added to the resulting crude copolymer solution for reprecipitation purification, followed by vacuum drying to obtain copolymer 1 (149.2 g). Copolymer 1 had a number average molecular weight of 17,100 and a weight average molecular weight of 50,500.

A thermometer, a stirrer, a glass flask with an internal capacity of 300 mL equipped with a heating device, copolymer 1 (40.0 g), BEI (Karenzu BEI, Showa Denko Co., Ltd., 1,1-bis (acryloyloxymethyl) ethyl isocyanate) (42.0 g), DBTDL (dibutyltin dilaurate) (0.17 g), BHT (2,6-di-t-butyl-p-cresol) (2.1 g), and MEK (115.4 g) ) were charged and reacted at 40° C. for 48 hours while stirring to synthesize a crude polymer. Heptane was added to the resulting crude polymer solution for reprecipitation purification, followed by vacuum drying to obtain Resin (A-1) (66.0 g). Resin (A-1) had a number average molecular weight of 42,300 and a weight average molecular weight of 119,990.

· A-2: X-22-164B (manufactured by Shin-Etsu Chemical Co., Ltd., containing methacrylic group-containing groups at both ends, linear dimethylpolysiloxane)

A-3: X-22-2445 (Shin-Etsu Chemical Co., Ltd., linear dimethylpolysiloxane containing acrylic group-containing groups at both ends)

· A-4: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., containing hydroxyl-containing groups at both ends, linear dimethylpolysiloxane)

A-5: X-22-164 (Shin-Etsu Chemical Co., Ltd., linear dimethylpolysiloxane containing methacrylic group-containing groups at both ends)

· A-6: X-22-164AS (manufactured by Shin-Etsu Chemical Co., Ltd., containing methacrylic group-containing groups at both ends, linear dimethylpolysiloxane)

· A-7: X-22-164A (manufactured by Shin-Etsu Chemical Co., Ltd., containing methacrylic group-containing groups at both ends, linear dimethylpolysiloxane)

· A-8: X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd., containing methacrylic group-containing groups at both ends, linear dimethylpolysiloxane)

· A-9: X-22-164E (manufactured by Shin-Etsu Chemical Co., Ltd., containing methacrylic group-containing groups at both ends, linear dimethylpolysiloxane)

· A-10: A resin synthesized by the following method.

KF-6001 (A-4) (20.78 g), 1,1-(bisacryloyloxymethyl) ethyl isocyanate (Karenzu BEI manufactured by Showa Denko Co., Ltd.) (8.13 g), PGMEA (96 .4 g), 2,2,6,6-tetramethylpiperidine-1-oxyl (manufactured by Koei Chemical Industry Co., Ltd.) (16.3 mg), and bismath tris (2-ethylhexanoate) (Nitto Kasei Co., Ltd. ) Neostan U-600) (16.3 mg) was added, the temperature was raised to 90° C., and the mixture was stirred for 72 hours to obtain a 30% PGMEA solution of siloxane resin XX-1.

Thiomalic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) (2.55 g) and ethanol (41.6 g) were added to the resulting solution, and the mixture was stirred at room temperature. Triethylamine (172 mg) was added dropwise. Stirred for an hour. Then, ethyl acetate (150 g) was added to the above solution, and 0.1N HCl aqueous solution (150 g) and distilled water (150 g) were added to the solution and mixed, then the organic phase in the solution was extracted. Sodium sulfate was added to the resulting organic phase and stirred for 10 minutes, the sodium sulfate was filtered, and the obtained filtrate was distilled off under reduced pressure to obtain XX-2 (28.5 g). The obtained XX-2 was designated as resin A-10.

· A-11 to A-15: Resins synthesized by the following method.

PGMEA (62.9 g) (and, if necessary, chain transfer agent 2-mercaptoethanol (Yg)) was added to a three-necked eggplant flask, and the temperature was raised to 75° C. under a nitrogen atmosphere. In this flask, X-22-2404 (manufactured by Shin-Etsu Chemical Co., Ltd., linear dimethylpolysiloxane containing a methacrylic group-containing group at one end) (60.0 g), HO-MS (manufactured by Kyoeisha Chemical, 2-methacryloyloxyethyl succinic acid) (29.8 g), PGMEA (146.7 g), and initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd., 2,2'-azobis (2-methylpropionic acid ) dimethyl) (Xg) was added dropwise over 2 hours.

After the addition, the flask was stirred at 75° C. for an additional 2 hours before adding V-601 (0.75 g) and PGMEA (23.8 g). Furthermore, the flask was heated to 90° C. and stirred for 3 hours. The resulting solution was replaced with air, and after confirming that the atmospheric oxygen concentration in the flask was 18% by mass or more, GMA (manufactured by Tokyo Chemical Industry Co., Ltd., glycidyl methacrylate) (10.2 g), TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) (0.11 g) and dimethyldodecylamine (4.4 g) were added and stirred at 90° C. for 48 hours to form a polymer containing resin. A solution was obtained.

Resins A-11 to A-15 were synthesized using the amounts X (g) of V-601 and Y (g) of 2-mercaptoethanol as shown in Table 1 below. The obtained resins A-11 to A-15 were used for the preparation of compositions in the form of a PGMEA solution having a solid content of 30% of the resins A-11 to A-15.

The molecular weight (number average molecular weight (Mn), weight average molecular weight (Mw)), acid value, and C=C value of Resins A-1 to A-15 are shown below.

Among the above resins, A-2, A-3, A-5 to A-15 are specific resins. Among them, A-2, A-3, A-5 to A-10 are main chain type specific resins, and A-11 to A-15 are side chain type specific resins.

<Polymerization initiator>

· I-1: the following compound

・ I-2: the following compound

· I-3: the following compounds

· I-4: the following compounds

All of the polymerization initiators I-1 to I-4 are oxime compounds.

Among the above polymerization initiators, when 0.001% by mass of I-1 to I-3 are dissolved in acetonitrile, the absorbance at a wavelength of 340 nm at an optical path length of 10 mm of the resulting solution is 0.45 or more. Met. On the other hand, when tested similarly using I-4, the absorbance of the resulting solution at a wavelength of 340 nm was less than 0.45.

<Polymerizable compound>

・ M-1: NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd., a compound represented by the following structure)

· M-2: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of compounds represented by the following structure)

・M-3: Viscoat #802 (manufactured by Osaka Organic Chemical Industry Co., Ltd., compound represented by the following structure)

<Polymerization inhibitor>

・PI-1: p-methoxyphenol

<Solvent>

・PGMEA: propylene glycol monomethyl ether acetate

The above ingredients were mixed to prepare the compositions shown in Table 3 below.

<Silica particle dispersion>

(Synthesis of silica particles PS-1)

Dispersion of hollow silica particles (“Sururia 4110” manufactured by Nikki Shokubai Kasei Co., Ltd., solid content concentration: 20% by mass, dispersion medium: isopropyl alcohol, average primary particle size: 60 nm) 100 g, KBM-503 (Shin-Etsu Chemical Co., Ltd. 4 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Co., Ltd.), 0.5 g of a 10% formic acid aqueous solution, and 1 g of water were mixed and stirred at 60° C. for 3 hours. After replacing the dispersion medium with 1-methoxy-2-propanol using a rotary evaporator, the solid content concentration is adjusted by adding 1-methoxy-2-propanol to obtain silica particles having a solid content concentration of 20% by mass. A dispersion of PS-1 (surface-treated hollow silica) was obtained.

(Preparation of modified silica dispersion S-1)

In a three-necked flask, a dispersion of silica particles PS-1 (solid content 20% by mass, 30.0 g), a surface modifier MA-1 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X-22-2404", One-end methacrylic-modified silicone oil) (1.8 g) and PGMEA (28.2 g) were added, and the temperature was raised to 80°C in a nitrogen atmosphere. 0.01 g of polymerization initiator V-601 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added to the flask and stirred for 3 hours. Additional V-601 (0.02 g) was added to the flask and stirred for 2 hours before microfiltration of the dispersion. 1-Methoxy-2-propanol was added to the obtained filtrate to obtain a modified silica dispersion S-1 (31.3 g) containing surface-modified silica particles and having a solid content concentration of 20% by mass. Obtained.

(Preparation of modified silica dispersions S-2 to S-14)

Modified silica dispersions S-2 to S-14 were prepared according to the method for preparing modified silica dispersion S-1 described above, except that the silica particles and surface modifiers listed in Table 3 were used.

The silica particles and surface modifiers used in the preparation of each modified silica dispersion are shown below.

-Silica particles-

・ PS-2: Gel of surface-treated solid silica particles ("PGM-AC-4130Y" manufactured by Nissan Chemical Industries, Ltd., solid content concentration: 32% by mass, dispersion medium: 1-methoxy-2-propanol, average Primary particle size: 45 nm)

・ PS-3: Dispersion of hollow silica particles ("Sururia 4320" manufactured by JGC Catalysts and Chemicals Co., Ltd., solid content concentration: 20% by mass, dispersion medium: methyl isobutyl ketone, average primary particle size: 60 nm)

1-Methoxy-2-propanol was added to the silica particles PS-2 to prepare a dispersion having a solid concentration of 20% by mass, and then the dispersion was used to prepare the modified silica dispersion.

-Surface Modifier-

・ MA-2: X-22-174ASX (manufactured by Shin-Etsu Chemical Co., Ltd., one end methacrylic modified silicone oil)

・MA-3: X-22-174BX (manufactured by Shin-Etsu Chemical Co., Ltd., one end methacrylic modified silicone oil)

・ MA-4: iBMA (manufactured by Tokyo Chemical Industry Co., Ltd., isobutyl methacrylate)

・ MA-5: MAC6F13 (manufactured by Tokyo Chemical Industry Co., Ltd., 1H, 1H, 2H, 2H-tridecafluoro-n-octyl methacrylate)

・ MA-6: HEMA (manufactured by Tokyo Chemical Industry Co., Ltd., 2-hydroxyethyl methacrylate)

・MA-7: HO-MS (manufactured by Kyoeisha Chemical Co., Ltd., 2-methacryloyloxyethyl succinic acid)

[evaluation]

〔test〕

The following tests were conducted using each composition described above.

<Evaluation of light shielding>

Each composition was applied onto a glass substrate by spin coating, and then heated on a hot plate at 100° C. for 2 minutes to obtain a composition layer. Next, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon), the resulting composition layer was exposed at 200 mJ/cm ² through a mask having a square pattern of 2 cm square. The exposed composition layer was puddle-developed for 60 seconds with a developer "CD-2060" (manufactured by Fuji Film Electronic Materials Co., Ltd.) and then spin-dried. After that, it was heated on a hot plate at 220° C. for 5 minutes to obtain a light-shielding film (cured film) having a thickness of 1.5 μm. The obtained light-shielding film was evaluated for light-shielding properties using UV-3600 (manufactured by Hitachi, Ltd.: spectrophotometer) according to the following evaluation criteria. A and B were considered acceptable.

"A": the maximum transmittance at a wavelength of 400 to 700 nm is 0.5% or less

"B": the maximum transmittance at a wavelength of 400 to 700 nm is higher than 0.5% and 2% or less

"C": Transmittance at wavelength 400-700 nm is higher than 2%

<Evaluation of reflectance before development (evaluation of low reflectance before development)>

Each composition was applied onto a glass substrate by spin coating, and then heated on a hot plate at 100° C. for 2 minutes to obtain a composition layer. Next, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon), the resulting composition layer was exposed at 200 mJ/cm ² through a mask having a square pattern of 2 cm square. Then, it was heated on a hot plate at 220° C. for 5 minutes to obtain a light-shielding film (cured film) having a thickness of 1.5 μm.

Light of 400 to 700 nm was incident on the obtained substrate with a light-shielding film at an incident angle of 8°, and the reflectance was measured using a spectrometer V7200 (trade name) manufactured by JASCO Corporation. The obtained measured values were classified according to the following evaluation criteria, and the reflectance before development (low reflectance before development) was evaluated. A and B were considered acceptable.

"A": the maximum reflectance at a wavelength of 400 to 700 nm is 2% or less

"B": the maximum reflectance at a wavelength of 400 to 700 nm is higher than 2% and 5% or less

"C": the maximum reflectance at a wavelength of 400 to 700 nm is higher than 5%

<Evaluation of reflectance after development (evaluation of low reflectance after development)>

In the procedure of "evaluation of reflectance before development" described above, after exposing the composition layer, the exposed composition layer is paddled for 60 seconds with developer "CD-2060" (manufactured by Fuji Film Electronic Materials Co., Ltd.). It was developed and then spun dry. Then, it was heated on a hot plate at 220° C. for 5 minutes to obtain a light-shielding film (cured film).

Thereafter, the same method and criteria were used to measure and evaluate the reflectance, and the post-development reflectance (post-development low reflectance) was evaluated.

When both the reflectance before development (low reflectance before development) and the reflectance after development (low reflectance after development) are both A or B, it is judged that the low reflectance of the light shielding film is excellent.

<Evaluation of light resistance>

Using a super xenon phase meter (manufactured by Suga Test Instruments Co., Ltd.) on the substrate with a light-shielding film prepared in the above "Evaluation of reflectance before development", at an illuminance of 50 mW / cm ² , a wavelength of 300 nm or more with a 7.5 kW xenon lamp was irradiated with light at an integrated exposure amount of 50 million Lux·h. After that, the reflectance is measured using a spectrometer V7200 (trade name) manufactured by JASCO Corporation, and the reflectance fluctuation for light of each wavelength is calculated before and after the irradiation treatment, and the light resistance is evaluated according to the following criteria. evaluated.

Reflectance variation is calculated by the following formula.

Reflectance variation (%) = | (reflectance (%) after irradiation treatment - reflectance (%) before irradiation treatment) |

"A": the maximum value of reflectance fluctuation at a wavelength of 400 to 700 nm is 1% or less

"B": the maximum value of reflectance fluctuation at a wavelength of 400 to 700 nm is higher than 1% and 3% or less

"C": the maximum value of reflectance variation is higher than 3% at a wavelength of 400 to 700 nm

〔result〕

The formulations of the compositions tested and the results of tests performed with the corresponding compositions are shown in the table below.

In Table 4, the number written in the box corresponding to each raw material name column indicates the content (parts by mass) of each raw material in each composition.

For example, Composition 1 contains 78.00 parts by mass of Dispersion A.

In addition, in the table, the addition amount (parts by mass) including the mass of components other than the solid content is described for the raw materials used in the preparation of the composition in a form in which the solid content is not 100%.

For example, Composition 34 more specifically contains 3.25 parts by mass of a resin solution containing 30% by mass of Resin A-11.

The column of "colorant" indicates the type of black colorant contained in the composition subjected to the test. "TB" means titanium black (T-1), "CB" means coated carbon black, "IB" means Irgaphor Black S 0100 CF, "RB" means the mixture of Red and Blue pigments. Indicates a mixed pigment.

The "Resin Type" column indicates the type of specific resin contained in the composition tested. A "main chain" means a main chain type specific polymer, and a "side chain" means a side chain type specific polymer.

The column of "Addition amount of resin" shows the content of resin contained in the composition subjected to the test. The content of the resin was shown in mass percentage (% by mass) with respect to the total solid content of the composition. In addition, as resin mentioned here, resin shown in the above-mentioned column of <Resin> is intended. For example, the dispersant contained in the composition is not counted as the resin content for calculating the "resin addition amount".

The column of "initiator absorption characteristics" shows that when the polymerization initiator contained in the composition subjected to the test is dissolved in acetonitrile at a concentration of 0.001% by mass, the absorbance at a wavelength of 340 nm of the resulting solution is It indicates whether or not it is 0.45 or more. When this requirement is satisfied, it is described as A, and when it is not satisfied, it is described as B.

The column of "film thickness of coating layer" indicates the film thickness of the coating layer in the light-shielding film prepared in the light-shielding evaluation. The film thickness of the coating layer was measured by cross-sectional SEM. It should be noted that, for the light-shielding films described as not measurable, the coating layer had a rough surface condition, so the film thickness of the coating layer could not be measured.

As shown in the table, it was confirmed that the problems of the present invention can be solved by using the composition of the present invention.

It was also confirmed that when the black colorant is a metal nitride pigment such as titanium black, the obtained light-shielding film has better low reflectivity (comparison with Examples 6 to 10, etc.).

In Example 6, titanium black was vanadium nitride VN-O (manufactured by Nippon New Metal Co., Ltd.), niobium nitride NbN-O (manufactured by Japan New Metal Co., Ltd.), and Japanese Patent Application Laid-Open No. 2017-222559 (Example 1 ) were changed to zirconium nitride prepared by the method of ) and evaluated in the same manner.

In Example 6, the titanium black was changed to silica-coated zirconium nitride (JP-A-2015-117302) and the same evaluation was performed.

In Example 6, similar effects were obtained even when titanium black was replaced with titanium black: zirconium nitride = 1:9, 3:7, 5:5, 7:3, 9:1 (the ratio is the weight ratio ). Further, the same effect was obtained even when titanium black:silica-coated zirconium nitride=1:9, 3:7, 5:5, 7:3 and 9:1 (ratios are weight ratios).

It was confirmed that when the specific resin is a main chain type specific resin (specific resin represented by the general formula (2)), the obtained light shielding film has more excellent low reflectivity (Examples 1 and 2 and comparison with Examples 6 and 7, etc.).

In Example 6, A-10 was synthesized in the same manner as XX-1 and changed to the following compound (main chain type specific resin, Mn 3000, Mw 5100, acid value 0 mgKOH / g, C = C value 0.67 mmol / g) As a result of evaluation in the same manner, the results were the same as in Example 6.

When the specific resin is a side chain type specific resin, when the content of the side chain type specific resin is 5.0% by mass or more with respect to the total mass of the solid content, low reflection of the obtained light shielding film after development (Comparison between Examples 1 and 21, etc.).

When the specific resin is a side chain type specific resin, when the content of the side chain type specific resin is 10.0% by mass or less with respect to the total mass of the solid content, low reflection of the obtained light shielding film after development (Comparison of Examples 21 and 22, etc.).

When the polymerization initiator contained in the composition is dissolved in acetonitrile at a concentration of 0.001% by mass, the resulting solution has an optical path length of 10 mm and a wavelength of 340 nm. A polymerization initiator that has an absorbance of 0.45 or more. In this case, it was confirmed that the obtained light-shielding film had better low reflectivity after development (results of Example 14, etc.).

In Example 6, the polymerization initiator I-1 was changed to IRGACURE 369 (trade name, manufactured by BASF) and evaluated in the same manner. was equivalent to

In Example 1, the same results as in Example 1 were obtained even when no polymerization inhibitor was added. Moreover, in Example 6, the same results as in Example 6 were obtained even when no polymerization inhibitor was added.

Using the light-shielding film of Example 6, a solid-state imaging device was produced according to the method described in International Publication WO2018/061644, and had good performance.

To composition 6, 13 parts by mass of silica particle dispersion S-1 (solid content: 20% by mass) prepared by the method described above was added, and then PGMEA was added so that the solid content concentration was the same as composition 6. A composition 101 was prepared. The content of the surface-modified silica particles in composition 101 was 8% by mass relative to the solid content in composition 6. As a result of changing Composition 6 to Composition 101 and evaluating in the same manner as in Example 6, the same evaluation as in Example 6 was obtained.

The solid content concentration is the same as composition 6 according to the above-described method except that silica particle dispersion liquids S-2 to S-14 (all of which have a solid content of 20% by mass) are used instead of silica particle dispersion liquid S-1. Compositions 102-114 were prepared, respectively. Compositions 102 to 114 were used instead of Composition 6 and evaluated in the same manner as in Example 6. As a result, evaluations equivalent to those in Example 6 were obtained.

10... Cured film

12... Black layer

14... Coating layer

16 Substrate

100 Solid-state imaging device

101 Solid-state imaging device

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 electrodes

111... lens layer

112 Lens material

113 support

114, 115...Light shielding 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 pixels

205bm: black matrix

206 p-well layer

207 ... Readout gate section

208 Vertical transfer path

209 element isolation region

210 Gate insulating film

211 Vertical transfer electrodes

212 Light shielding film

213, 214... insulating film

215... Planarization film

300... Infrared sensor

310 Solid-state imaging device

311... Infrared absorption filter

312 color filter

313... Infrared transmission filter

314 Resin film

315 Micro lens

316... Planarization film

Claims (9)

A black coloring material, a polymerizable compound, a photopolymerization initiator, and a light-shielding composition containing a resin,
The resin contains a polymerizable group and a group represented by general formula (1) as a main chain ,
The resin has a number average molecular weight of 100 to 15,000,
A light-shielding composition, wherein the content of the resin is 2.0 to 15.0% by mass with respect to the total mass of the solid content of the light-shielding composition.
*-(SiR ¹ R ² -O) _na -* (1)
In general formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
na represents an integer from 2 to 200;
* represents a binding position. A black coloring material, a polymerizable compound, a photopolymerization initiator, and a light-shielding composition containing a resin,
The resin is a compound represented by the general formula (2),
The resin has a number average molecular weight of 100 to 15,000,
A light-shielding composition, wherein the content of the resin is 2.0 to 15.0% by mass with respect to the total mass of the solid content of the light-shielding composition.
R. ³ -(SiR ¹ R. ² -O) _nb -SiR ¹ R. ² -R ³ (2)
In general formula (2), R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
R. ³ represents a group containing an ethylenically unsaturated group.
nb represents an integer from 3 to 200; ^3. The light-shielding composition according to claim 2, wherein at least one of said R3 has an acid group. The light-shielding composition according to claim 2 or ³ , wherein at least one of said R3 has at least one selected from the group consisting of an ether bond, an ester bond, a urethane bond and a thioether bond. 5. The light-shielding composition according to any one of claims 1 to 4, wherein the black colorant is one or more selected from the group consisting of metal nitrides and metal oxynitrides. A cured film obtained using the light-shielding composition according to any one of claims 1 to 5. The cured film contains a black layer and a coating layer disposed on the surface of the black layer,
The coating layer has a thickness of 20 to 200 nm,
The cured film according to claim 6, wherein the coating layer contains a cured product of the resin. 8. The cured film according to claim 6, which is a light shielding film. A solid-state imaging device comprising the cured film according to any one of claims 6 to 8.

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