JP5414590B2 - Black curable composition, light-shielding color filter for solid-state imaging device, method for producing the same, and solid-state imaging device. - Google Patents

Description

  The present invention relates to a black curable composition, a light-shielding color filter for a solid-state image sensor, a manufacturing method thereof, and a solid-state image sensor.

A color filter used in a liquid crystal display device is provided with a light-shielding color filter called a black matrix for the purpose of shielding light between colored pixels and improving contrast. Also in the solid-state imaging device, a light shielding film is provided for the purpose of preventing noise generation and improving image quality.
As a composition for forming a black matrix for a liquid crystal display device or a light-shielding color filter for a solid-state imaging device, a black curable composition containing a black color material such as carbon black or titanium black is known. (For example, refer to Patent Documents 1 to 5.)

The black matrix for liquid crystal display devices is mainly required to have a light shielding property in the visible region, while the light shielding color filter for the solid-state imaging device has a light shielding property in the infrared region in addition to the light shielding property in the visible region. It is necessary to prepare.
In addition, a light-shielding color filter for a next-generation solid-state image sensor is required to improve both light-shielding properties and to reduce the thickness. In order to make these compatible, it is necessary to increase the content of the black color material in the black curable composition.

  However, when the content of the black color material in the conventional black curable composition is increased as a light-shielding color filter for a solid-state imaging device, light necessary for decomposition of the polymerization initiator is shielded, and a curable component is present. In order to reduce, especially hardening of a pattern peripheral part (boundary between an unexposed part and an exposed part) becomes inadequate. Therefore, it has been found that even if a pattern can be formed, a part of the pattern is lost. On the other hand, if the amount of exposure is increased and the curability is improved in order to improve the pattern defect, the curing proceeds to the unexposed part and the pattern size becomes large, so that the desired pattern size cannot be formed. In addition, it was found that a residue was generated in the unexposed area.

  Patent Document 6 and Patent Document 7 describe a photosensitive composition containing a resin having a specific structure having an acid group and an amino group for the purpose of improving dispersibility, reducing the residue in the non-exposed area, and the like. Furthermore, as a curable composition used for forming a light-shielding region in a solid-state imaging device, improvement in pattern formability has been demanded.

Japanese Patent Laid-Open No. 10-246955 JP-A-9-54431 Japanese Patent Laid-Open No. 10-46042 JP 2006-36750 A JP 2007-115921 A JP 2010-6932 A JP 2004-37986 A

In view of the above circumstances, the present invention provides a black curable composition capable of forming a light-shielding color filter for a solid-state imaging device that can form a pattern even at a low exposure amount, even if it contains an inorganic pigment at a high concentration, and suppresses pattern loss. The issue is to provide goods.
Furthermore, it is an object of the present invention to provide a light-shielding color filter for a solid-state imaging device that is excellent in light-shielding performance in a wide wavelength region including an infrared region, a manufacturing method thereof, and a solid-state imaging device.

As a result of intensive studies, the present inventors have found that the above problem can be solved by a black curable composition containing a resin having a specific structure, and have completed the present invention.
Means for solving the above-mentioned problems are as follows.

< 1 > (A) inorganic pigment (excluding carbon black), (B) (b-1) a monomer having at least one group selected from an amino group and a nitrogen-containing heterocyclic group, and (b- 2) a copolymer containing acrylic acid or methacrylic acid and (b-3) a macromonomer having a weight average molecular weight of 1,000 or more and 50,000 or less, (C) a polymerization initiator, (D) a polymerizable compound, And (E) an alkali-soluble resin having an unsaturated double bond, wherein the content of the (E) alkali-soluble resin is 0.3 or more and 2.5 on a mass basis with respect to the (D) polymerizable compound. The black curable composition for solid-state image sensors which is the following.
< 2 > (A) inorganic pigment (excluding carbon black), (B) (b-1) a monomer having at least one group selected from an amino group and a nitrogen-containing heterocyclic group, and (b- 2) a monomer having at least one group selected from the group consisting of a carboxy group, a phosphoric acid group, and a sulfonic acid group; and (b-3) a macromonomer having a weight average molecular weight of 1,000 or more and 50,000 or less. A copolymer containing (C) a polymerization initiator, (D) a polymerizable compound, and (E) an alkali-soluble resin having an unsaturated double bond, and the content of the (E) alkali-soluble resin is It is 0.3 or more and 2.5 or less on a mass basis with respect to the (D) polymerizable compound, and the (b-3) macromonomer is a polyester macromonomer represented by the following general formula (M). For solid-state image sensor Color curable composition.
< 3 > The black curable composition for a solid-state imaging device according to <1> or < 2>, wherein the (A) inorganic pigment is at least one selected from metal pigments containing silver and / or tin, and titanium black. Composition.
< 4 > The black curable composition for a solid-state imaging device according to < 3 >, wherein the (A) inorganic pigment is titanium black.
< 5 > The black curable composition for a solid-state imaging device according to < 3 > or < 4 >, wherein the titanium black has an average primary particle diameter of 30 nm to 65 nm.
< 6 > In any one of <1> to < 5 >, the content of the (B) copolymer is 0.15 or more and 0.35 or less on a mass basis with respect to the (A) inorganic pigment. The black curable composition for solid-state image sensors described.

< 7 > The black curable composition for a solid-state imaging device according to any one of <1> to < 6 >, wherein the (C) polymerization initiator is an oxime ester compound or a hexaarylbiimidazole compound.
< 8 > The black curable composition for a solid-state imaging device according to any one of <1> to < 7 >, further comprising (F) an organic pigment.
< 9 > The process of apply | coating the black curable composition for solid-state image sensors of any one of <1>-< 8 > on a support body, the process of carrying out pattern exposure of the apply | coated black curable composition layer, And the manufacturing method of the light-shielding color filter for solid-state image sensors which has the process of developing the exposed black curable composition layer and forming a light-shielding pattern in this order.
<1 0 > A light-shielding color filter for a solid-state imaging device having a pattern formed using the black curable composition for a solid-state imaging device according to any one of <1> to < 8 >.
<1 1 > A solid-state imaging device comprising the light-shielding color filter for a solid-state imaging device according to <1 0 >.

According to the present invention, there is provided a black curable composition capable of forming a light-shielding color filter for a solid-state imaging device capable of forming a pattern even with a low concentration and containing an inorganic pigment at a high concentration and suppressing pattern loss. can do.
Furthermore, it is possible to provide a light-shielding color filter for a solid-state imaging device that is excellent in light-shielding performance in a wide wavelength region including an infrared region, a manufacturing method thereof, and a solid-state imaging device.

  Hereinafter, embodiments for carrying out the invention will be described in detail. In addition, in the description of a group (atomic group) in this specification, the description which does not describe substitution and non-substitution means that what has a substituent is included with what does not have a substituent. For example, the expression “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

[Black curable composition for solid-state imaging device]
The black curable composition for a solid-state imaging device of the present invention (hereinafter referred to as “the black curable composition of the present invention” as appropriate) comprises (A) an inorganic pigment (however, excluding carbon black), (B) ( b-1) a monomer having at least one group selected from an amino group and a nitrogen-containing heterocyclic group; (b-2) acrylic acid or methacrylic acid ; and (b-3) a weight average molecular weight of 1,000. A copolymer containing a macromonomer having a molecular weight of 50,000 or less, (C) a polymerization initiator, (D) a polymerizable compound, and (E) an alkali-soluble resin having an unsaturated double bond, ) The content of the alkali-soluble resin is 0.00 on a mass basis with respect to the polymerizable compound (D). 3 or more 5 or less.
Further, the black curable composition for a solid-state imaging device of the present invention was selected from (A) inorganic pigment (excluding carbon black), (B) (b-1) an amino group, and a nitrogen-containing heterocyclic group. A monomer having at least one group, (b-2) a monomer having at least one group selected from the group consisting of a carboxy group, a phosphate group, and a sulfonic acid group; and (b-3) a weight average molecular weight. A copolymer containing 1,000 or more and 50,000 or less macromonomer, (C) a polymerization initiator, (D) a polymerizable compound, and (E) an alkali-soluble resin having an unsaturated double bond, The content of the (E) alkali-soluble resin is 0.3 or more and 2.5 or less on a mass basis with respect to the (D) polymerizable compound, and the macromonomer (b-3) is represented by the following general formula (M ) Polyester represented by It is a macro monomer.


(In General Formula (M), R ^1A represents a hydrogen atom or a methyl group. R ^2A represents an alkylene group. R ^3A represents an alkyl group. N represents an integer of 5 to 100.)
By setting the black curable composition of the present invention to the above-described configuration, it was possible to suppress the pattern defect that was a problem when forming the pattern of the light shielding region in the solid-state imaging device.

Although this mechanism of action is not yet clear, it is estimated as follows.
If the developability and curability of the black curable composition are low, the pattern region cannot be completely cured at the boundary between the non-exposed part and the exposed part in irradiation with a low exposure amount, and a part of the pattern is lost. . On the other hand, in the high exposure area, the development area (non-exposed area) close to the exposed area is also cured, so that the pattern dimension becomes large and a light-shielding pattern having a desired pattern size cannot be formed, and a residue remains in the non-exposed area. Occurs. That is, in order to suppress pattern defects, to form a pattern of a desired size, and to suppress a residue in an unexposed portion, both the developability and curability of the black curable composition are improved, and a soluble disc It is necessary to increase the limit.

  Generally, a dispersion resin is a component that deteriorates the developability and curability of a black curable composition because it has a water-repellent steric repulsion group to prevent aggregation between pigments and has no curability. . However, the specific resin of the present invention has at least one acid group selected from a carboxy group, a phosphoric acid group and a sulfonic acid group, and at least one basic group selected from an amino group and / or a nitrogen-containing heterocyclic group. It functions as a dispersion resin and also functions as an alkali-soluble resin during alkali development. In the specific resin of the present invention, when the pattern of the exposed portion is formed in the development process, part of the acid group and the basic group forms a counter salt structure, thereby promoting the permeability of the developer and improving the developability. At the same time, since a network of acid groups and basic groups is formed between the specific resins, the hardness of the exposed pattern is improved. It is considered that this action can suppress pattern defects and improve the developability of the non-exposed area. Furthermore, by adding an alkali-soluble resin having an unsaturated double bond, the developability and curability of the black curable composition can be further improved, which was a problem when producing a light-shielding film for a solid-state imaging device. Both the pattern defect and the improvement in developability of the unexposed area could be solved at the same time.

The black curable composition for a solid-state image sensor of the present invention is used for forming a light-shielding cured film (hereinafter, appropriately referred to as “light-shielding film”) in the solid-state image sensor.
In this specification, “light-shielding property” means the ability to suppress the transmission of light having a wavelength of 400 nm to 800 nm.
Hereafter, each component contained in the black curable composition for solid-state image sensors of this invention is demonstrated one by one.

<(A) Inorganic pigment>
The black curable composition of the present invention contains an inorganic pigment (excluding carbon black) as a component that can function as a light-shielding agent, from the viewpoint of storage stability and safety.

  As the inorganic pigment, an inorganic pigment having absorption in a wavelength region from the ultraviolet region to the infrared region is preferable from the viewpoint of developing a light-shielding property with respect to light in a wide wavelength region from the ultraviolet region to the infrared region. Examples of such inorganic pigments include pigments made of simple metals, pigments made of metal compounds selected from metal oxides, metal complex salts, and the like.

Specific examples of the inorganic pigment include, for example, zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow (zinc yellow 1 type, 2 types of zinc yellow), ultramarine blue, prussian blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, Victoria green, bitumen (unrelated to Prussian blue), vanadium Zirconium blue, chrome tin pink, pottery red, salmon pink and the like. The black inorganic pigment includes a metal oxide containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. And metal nitrogenous substances.
In the present invention, carbon black is treated as an organic pigment.
In particular, it is possible to use not only a single substance but also a mixture of a plurality of kinds of inorganic pigments for the purpose of expressing a light-shielding property against light in a wide wavelength range from the ultraviolet region to the infrared region.

  The inorganic pigment is more preferably a metal pigment containing silver and / or tin and titanium black from the viewpoints of light shielding properties and curability, and a light shielding property with respect to light in a wide wavelength range from the ultraviolet region to the infrared region. Is most preferably titanium black.

  In the present invention, titanium black is black particles having titanium atoms. Titanium black is preferably low-order titanium oxide or titanium oxynitride.

  The surface of titanium black can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. As a modification of the surface of titanium black, for example, a treatment of coating the surface of titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide is possible, and Japanese Patent Application Laid-Open No. 2007-302836. A treatment using a water repellent material as shown in the publication is also possible.

  As examples of commercially available titanium black, titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N (above, manufactured by Mitsubishi Materials Corporation), Tilac D (Ako Kasei) Etc.).

  As a method for producing titanium black, a mixture of titanium dioxide and metal titanium is heated in a reducing atmosphere for reduction (a method described in JP-A-49-5432), and obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing ultrafine titanium dioxide in a reducing atmosphere containing hydrogen (a method described in JP-A-57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (JP-A). 60-65069, the method described in JP-A-61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at high temperature in the presence of ammonia (JP-A-61-201610). However, the method is not limited to these.

The specific surface area of titanium black is not particularly limited, but the value measured by the BET method is usually about 5 to 150 m ² / g, particularly about 20 to 100 m ² / g.

  In addition to titanium black, for the purpose of adjusting dispersibility, colorability, etc., a composite oxide such as Cu, Fe, Mn, V, Ni, black pigments such as cobalt oxide, iron oxide, carbon black, aniline black, etc. You may use it in combination of seed | species or 2 or more types. In this case, it is preferable that titanium black occupies 50% by mass or more of the inorganic pigment.

As for the particle size of the inorganic pigment in the present invention, the average primary particle size is preferably 5 nm to 0.01 mm, and from the viewpoints of dispersibility, light shielding properties, and sedimentation with time, the average primary particle size is 10 nm to More preferably, it is 1 μm.
The average primary particle size of titanium black suitably used as an inorganic pigment is not particularly limited, but from the viewpoint of dispersibility and colorability, the average primary particle size is preferably 3 nm to 2000 nm, and 10 nm to 100 nm. Further preferred. In particular, in the solid-state imaging device application of the present invention, pattern defects are suppressed by using titanium black having an average primary particle size of 30 nm to 65 nm. This is presumed that when a pattern is formed from fine titanium black, the smoothness of the pattern is improved and the unevenness is reduced, so that the external force load on the fine pattern during development and rinsing is reduced.

  In the black curable composition of the present invention, only one inorganic pigment may be used, or two or more inorganic pigments may be used in combination. As will be described later, organic pigments and dyes may be used in combination as desired for the purpose of adjusting the light shielding property.

  The content of the inorganic pigment in the black curable composition is preferably 5 to 70% by mass and more preferably 10 to 60% by mass with respect to the solid content of the composition.

  When the inorganic pigment is contained in the black curable composition, the inorganic pigment is previously dispersed using a specific resin to prepare a pigment dispersion, and the pigment dispersion is used for the preparation of the black curable composition. From the viewpoint of the uniformity of the resulting black curable composition.

<(B) (b-1) a monomer having at least one group selected from an amino group and a nitrogen-containing heterocyclic group; and (b-2) a group consisting of a carboxy group, a phosphate group, and a sulfonic acid group A copolymer comprising a monomer having at least one group selected from (b-3) and a macromonomer having a weight average molecular weight of 1,000 or more and 50,000 or less: a specific resin>
The black curable composition of the present invention comprises (B) (b-1) a monomer having at least one group selected from an amino group and a nitrogen-containing heterocyclic group, and (b-2) a carboxy group and phosphoric acid. A copolymer having a group and a monomer having at least one group selected from the group consisting of sulfonic acid groups, and (b-3) a macromonomer having a weight average molecular weight of 1,000 to 50,000. Hereinafter, it is appropriately referred to as “specific resin”).

The specific resin functions as a dispersant for (A) an inorganic pigment.
In the present invention, an inorganic pigment is dispersed in advance with a specific resin to prepare a pigment dispersion. This is preferable because the inorganic pigment is finely dispersed and exhibits excellent dispersion stability. Thereby, the pattern formation property of a black curable composition can be improved.

  The specific resin includes, as a raw material, (b-1) a monomer having at least one group selected from an amino group and a nitrogen-containing heterocyclic group, and (b-2) a carboxy group, a phosphate group, and a sulfonic acid. A monomer having at least one group selected from the group consisting of groups, (b-3) a macromonomer having a weight average molecular weight of 1,000 or more and 50,000 or less, and any other structure as necessary. It is produced by copolymerizing with a monomer.

  Hereinafter, (b-1) a monomer having at least one group selected from an amino group and a nitrogen-containing heterocyclic group, which is a raw material for obtaining a specific resin, (b-2) a carboxy group, a phosphate group, And a monomer having at least one group selected from the group consisting of sulfonic acid groups, (b-3) a macromonomer having a weight average molecular weight of 1,000 to 50,000, and a monomer having another structure, respectively. .

<(B-1) Monomer having at least one group selected from amino group and nitrogen-containing heterocyclic group>
(B-1) A monomer having at least one group selected from an amino group and a nitrogen-containing heterocyclic group (hereinafter referred to as “monomer (b-1)” as appropriate) is an amino group and / or a nitrogen-containing group. A monomer having a heterocyclic group and a molecular weight of 50 or more and 1,000 or less.

Examples of the amino group that the monomer (b-1) has include primary, secondary, and tertiary amino groups, and from the viewpoint of dispersion stability, a secondary or tertiary amino group is preferable. More preferably, it is a tertiary amino group. The amino group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an amino group having an aryl group having 6 to 15 carbon atoms. Most preferred are amino groups having -5 linear or branched alkyl groups. Specific examples of the amino group, -NHMe, -NHEt, -NHPr, -NHiPr , -NHBu, -NH (tert-Bu), - NMe 2, -NEt 2, -NPr 2, -NPh 2, morpholino Etc. (Here, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.)

  The nitrogen-containing heterocyclic group contained in the monomer (b-1) is a cyclic substituent having at least one nitrogen atom in the ring structure, and the ring structure is an unsaturated ring even if it is a saturated ring. It may be a single ring or a condensed ring, and may be unsubstituted or may have a substituent. Further, the nitrogen-containing heterocyclic group derived from the monomer (b-1) may be contained in the side chain structure or the main chain structure in the specific resin. From the viewpoint of dispersion stability, it is more preferably contained in the side chain structure.

  Specific examples of the ring structure of the nitrogen-containing heterocyclic group include, for example, pyrrolidine, pyrroline, tetrahydropyridine, piperazine, homopiperazine, piperidine, triazine, morpholine, hexamethylenetetramine, diazabicycloundecene, decahydroquinoline, dia Zabicyclooctane, pyrrolidinone, δ-valerolactam, succinimide, glutarimide, imidazolidone, tetrahydropyrimidone, urazole, dihydrouracil, barbituric acid, indole, carbazole, julolidine, phenoxazine, phenothiazine, oxindole, phenanthridinone, Isatin, phthalimide, diiminoisoindoline, iminoisoindolinone, diiminobenzisoindoline, naphthalimide, quinazolinedione, pyrrole, porph Phosphorus, porphyrin metal complex, phthalocyanine, phthalocyanine metal complex, naphthalocyanine, naphthalocyanine metal complex, pyrazole, imidazole, triazole, tetrazole, isoxazole, oxazole, isothiazole, thiazole, thiadiazole, thiatriazole, iminostilbene, azaindole, indazole, Benzimidazole, benzotriazole, azabenzimidazole, anthranil, benzisoxazole, benzoxazole, benzothiazole, benzofurazan, benzothiadiazole, triazolepyrimidine, triazolepyridine, purine, xanthine, pyridine, pyridazine, pyrimidine, pyrimidone, uracil, pyrazine, Quinoline, acridine, cinnoline, benzocinnoline, Examples thereof include nitrogen-containing heterocyclic groups such as quinoxaline, quinazoline, quinoxaline, phenazine, phenanthroline, perimidine, and acridone, and these may be unsubstituted or have a substituent.

  More preferred examples of the ring structure of the nitrogen-containing heterocyclic group include indole, carbazole, phenoxazine, phenothiazine, oxindole, phenanthridinone, isatin, phthalimide, diiminoisoindoline, iminoisoindolinone, diiminobenz. Isoindoline, naphthalimide, quinazolinedione, pyrrole, pyrazole, imidazole, triazole, tetrazole, isoxazole, oxazole, isothiazole, thiazole, thiadiazole, thiatriazole, iminostilbene, azaindole, indazole, benzimidazole, benzotriazole, azabenzimidazole , Anthranil, benzisoxazole, benzoxazole, benzothiazole, benzofurazan, benzothiadiazole, tria Lumpur pyrimidine, triazole, pyridine, purine, xanthine, pyridine, pyridazine, pyrimidine, pyrimidone, uracil, pyrazine, quinoline, acridine, cinnoline, Benzoshin'norin, quinoxaline, quinazoline, quinoxaline, phenazine, phenanthroline, include acridone.

  As the substituent that the nitrogen-containing heterocyclic group contained in the monomer (b-1) may have, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic ring Group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group ( Alkylamino group, anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group Group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, A phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a silyl group, etc. are mentioned.

The substituents that the nitrogen-containing heterocyclic group may have will be described in more detail below.
Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), an alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl having 1 to 30 carbon atoms). Groups such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl groups (preferably substituted with 3 to 30 carbon atoms) Or an unsubstituted cycloalkyl group such as cyclohexyl and cyclopentyl, and a polycyclic cycloalkyl group such as a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, For example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3- Le) and groups of polycyclic structures such as tricycloalkyl groups. Preferably monocyclic cycloalkyl group, a bicycloalkyl group, a monocyclic cycloalkyl group is particularly preferred.)

An alkenyl group (a linear or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably A substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, and a polycyclic cycloalkenyl group such as a bicycloalkenyl group (Preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] octo- 2-en-4-yl) and tricycloalkenyl groups, and monocyclic cycloalkenyl groups are particularly preferred.), Alkynyl groups (preferably Is properly, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, e.g., ethynyl, propargyl, trimethylsilylethynyl group),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 to 5 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably the ring-constituting atom is selected from carbon atom, nitrogen atom and sulfur atom And a heterocyclic group having at least one heteroatom of any one of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. For example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy , Nitro group, a carboxy group,

An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably Is a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 2,4-di-t-amylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having a carbon number of 2 30 substituted or unsubstituted heterocyclic oxy groups, wherein the heterocyclic moiety is Preferably heterocyclic portion described in cyclic group, for example, 1-phenyl-5-oxy, 2-tetrahydropyranyloxy),

An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably having 2 to 30 carbon atoms) Or an unsubstituted alkoxycarbonyloxy group such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted group having 7 to 30 carbon atoms). Substituted aryloxycarbonyloxy groups such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 0 to 30 carbon atoms); For example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino), acylamino group (preferably formylamino group, carbon number A substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3, 4,5-tri-n-octyloxyphenylcarbonylamino), amino A rubonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl- Methoxycarbonylamino),

Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) A sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino A sulfonylamino), alkyl or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methyl Sulfonylami , Butyl sulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenyl sulfonylamino, p- methylphenyl sulfonylamino), a mercapto group,

An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms). , For example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, and the heterocyclic portion is the aforementioned heterocyclic group The heterocyclic moiety described in the above is preferable, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamo Le, N, N- dimethylsulfamoyl, N- acetyl sulfamoyl, N- benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), a sulfo group,

An alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl , Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms) Group, example For example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, For example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl),

  An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably having a carbon number) 1-30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl or hetero A ring azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocycle portion is the heterocycle described in the above heterocyclic group); Ring portion is preferred), for example, phenylazo, p Chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms such as N-succinimide and N-phthalimide) A phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably substituted having 2 to 30 carbon atoms) Or an unsubstituted phosphinyl group such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),

A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino group ( Preferably, it is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably substituted with 3 to 30 carbon atoms) Or an unsubstituted silyl group, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).

  Among the above functional groups, those having a hydrogen atom may have the hydrogen atom substituted with any of the above groups. Examples of such functional groups include alkylcarbonylaminosulfonyl group, arylcarbonylaminosulfonyl group, alkylsulfonylaminocarbonyl group, arylsulfonylaminocarbonyl group, specifically methylsulfonylaminocarbonyl, p-methyl. Examples include phenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

  The monomer (b-1) is a monomer having an amino group, pyridinyl group, imidazolyl group, phthalimide group, naphthalimide group, benzimidazole group, or acridone group from the viewpoints of dispersion stability, developability, and light resistance. A monomer having an amino group or a naphthalimide group is more preferable.

  As the monomer (b-1), a known monomer having an amino group and / or a nitrogen-containing heterocyclic group and having a molecular weight of 50 or more and 1,000 or less can be used. The monomer is preferably an acrylic monomer or a styrene monomer from the viewpoint of polymerizability, and is represented by an acrylic ester monomer represented by the following general formula (K) or the following general formula (L). Most preferred is a styrene monomer. By having such a monomer-derived structural unit, the specific resin has an amino group or a nitrogen-containing heterocyclic group that can strongly interact with the inorganic pigment in the side chain portion, so that the dispersion stability of the black curable composition Will improve.

In General Formula (K), R ^A represents a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group, a fluorine atom, or a chlorine atom. B represents an oxygen atom, —N (R ^B ) —. R ^B represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. L represents a divalent linking group. A represents an amino group or a nitrogen-containing heterocyclic group.

As R ^A in formula (K), a hydrogen atom and a methyl group are particularly preferable.
Examples of the divalent linking group represented by L include alkylene groups having 2 to 20 carbon atoms, alkyleneaminocarbonyl groups having 2 to 20 carbon atoms, cycloalkylene groups having 5 to 10 carbon atoms, and 6 to 10 carbon atoms. An arylene group is preferable, and an alkylene group having 2 to 10 carbon atoms and an alkyleneaminocarbonyl group having 2 to 10 carbon atoms are most preferable.
Examples of the alkyl group represented by R ^B, include an alkyl group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 1 to 5 carbon atoms. The amino group or nitrogen-containing heterocyclic group represented by A has the same meaning as described above as the amino group or heterocyclic group that the monomer (b-1) has, and the preferred range is also the same.

  In general formula (L), A represents an amino group or a nitrogen-containing heterocyclic group. The amino group or heterocyclic group represented by A has the same meaning as described above as the amino group or heterocyclic group of the monomer (b-1), and the preferred range is also the same.

  Monomer (b-1) may use only 1 type and may use 2 or more types together.

Hereinafter, although the specific example of a monomer (b-1) is shown, this invention is not limited to these. In specific examples (M-1) to (M-23) and (M-31) to (M-50), ^RA represents a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group, or a fluorine atom. Or a chlorine atom.

Among the specific examples (M-1) to (M-23) and (M-31) to (M-50), the specific examples (M-1) to (M-) in which R ^A is a hydrogen atom or a methyl group. 6), (M-9) to (M-16), (M-21) to (M-23), (M-37), (M-40), (M-47), (M-48) And (M-49) are preferred, and in particular, R ^A is a hydrogen atom or a methyl group (M-1), (M-2), (M-11), (M-12), (M- 37), (M-47), and (M-48) are particularly preferable from the viewpoints of the dispersion stability of the pigment dispersion and the developability and suppression of pattern defects exhibited by the black curable composition using the pigment dispersion. preferable.

<(B-2) Monomer having at least one group selected from the group consisting of carboxy group, phosphoric acid group, and sulfonic acid group: monomer (b-2)>
(B-2) A monomer having at least one group selected from the group consisting of a carboxy group, a phosphoric acid group, and a sulfonic acid group (hereinafter, appropriately referred to as “monomer (b-2)”) is at least. It is a monomer having at least one group selected from one carboxy group, phosphoric acid group, and sulfonic acid group and having a molecular weight of 50 or more and 500 or less. From the viewpoint of polymerizability, an acrylic monomer or styrene Preferably, it is a monomer, and (meth) acrylic ester monomers and (meth) acrylic amide monomers are most preferred.

Among the carboxy group, phosphoric acid group, or sulfonic acid group that the monomer (b-2) has, a carboxy group and a phosphoric acid group are preferable, and a carboxy group is most preferable.
The monomer (b-2) may have two or more carboxy groups, phosphoric acid groups, and sulfonic acid groups, and is preferably a carboxy group and a phosphoric acid group, or a carboxy group and a sulfonic acid group. .
Moreover, a monomer (b-2) may use only 1 type and may use 2 or more types together.

Hereinafter, although the specific example of a monomer (b-2) is shown, this invention is not limited to these. In specific examples (M-51) to (M-68), R ^A represents a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group, a fluorine atom, or a chlorine atom.

Of the specific examples (M-51) to (M-68), R ^A is a hydrogen atom or a methyl group (M-62), that is, acrylic acid or methacrylic acid is most preferable. In the repeating unit consisting of (M-62), the carboxy group is close to the polymer main chain, the penetration of the developer into the interface between the substrate and the black curable composition layer is suppressed, and the substrate adhesion is improved.

<(B-3) Macromonomer having a weight average molecular weight of 1,000 or more and 50,000 or less: Macromonomer (b-3)>
(B-3) A macromonomer having a weight average molecular weight of 1,000 or more and 50,000 or less (hereinafter appropriately referred to as “macromonomer (b-3)”) has the weight average molecular weight and has a terminal. It is an oligomer or polymer having a polymerizable group.

  The weight average molecular weight of the macromonomer (b-3) is 1,000 or more and 50,000 or less, preferably 1,000 or more and 20,000 or less, and more preferably 2,000 or more and 10,000 or less. More preferably, it is 2,000 or more and 5,000 or less. When the weight average molecular weight of the macromonomer (b-3) is within this range, the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the black curable composition using the pigment dispersion are improved.

  In addition, the weight average molecular weight in this specification is a polystyrene conversion value measured by GPC (gel permeation chromatography) method.

A known macromonomer can be used as the macromonomer (b-3).
Examples of the macromonomer (b-3) include macromonomer AA-6 (polymethyl methacrylate whose terminal group is a methacryloyl group) and AS-6 (polystyrene whose terminal group is a methacryloyl group) manufactured by Toa Gosei Co., Ltd. ), AN-6S (a copolymer of styrene and acrylonitrile whose terminal group is a methacryloyl group), AB-6 (polybutyl acrylate whose terminal group is a methacryloyl group), Placel Cell FM5 manufactured by Daicel Chemical Industries, Ltd. Ε-caprolactone 5 molar equivalent addition product of 2-hydroxyethyl methacrylate), FA10L (10 molar equivalent addition product of ε-caprolactone of 2-hydroxyethyl acrylate), and polyester-based macro described in JP-A-2-272009 Monomer. Among these, a polyester-based macromonomer that is particularly flexible and excellent in solvophilicity has dispersibility and dispersion stability of the pigment dispersion, and developability and light resistance of the black curable composition using the pigment dispersion. The polyester macromonomer represented by the following general formula (M) is most preferable from the viewpoint.

In General Formula (M), R ^1A represents a hydrogen atom or a methyl group. R ^2A represents an alkylene group. R ^3A represents an alkyl group. n represents an integer of 5 to 100.

R ^2A is particularly preferably a linear or branched alkylene group having 5 to 20 carbon atoms, and most preferably — (CH ₂ ) ₅ —. R ^3A is preferably a linear or branched alkyl group having 5 to 20 carbon atoms. As n, the integer of 5-30 is preferable and the integer of 10-20 is the most preferable.

  Only 1 type may be used for a macromonomer (b-3), and 2 or more types may be used together.

  The specific resin preferably contains 10 to 50% by mass, more preferably 15 to 45% by mass, of repeating units derived from the monomer (b-1), based on the total mass of the specific resin. It is most preferable to contain -40 mass%. When the content of the repeating unit derived from the monomer (b-1) is within this range, the dispersibility and dispersion stability of the pigment dispersion and the developability exhibited by the black curable composition using the pigment dispersion Is further improved.

The repeating unit derived from the monomer (b-1) possessed by the specific resin preferably contains an amino group from the viewpoint of dispersibility and dispersion stability of the pigment dispersion.
The repeating unit derived from the monomer (b-1) possessed by the specific resin preferably contains both an amino group and a nitrogen-containing heterocyclic group from the viewpoint of further improving dispersibility and dispersion stability. More preferably, the nitrogen-containing heterocyclic group is contained in the side chain structure of the specific resin.
The content ratio (amino group: nitrogen-containing heterocyclic group, mass ratio) of the amino group and the nitrogen-containing heterocyclic group in the repeating unit derived from the monomer (b-1) of the specific resin is 100: 0 to 5: 95 is preferable, 100: 0 to 10:90 is more preferable, and 100: 0 to 15:85 is most preferable.

  The acid value of the specific resin is preferably 10 mgKOH / g to 200 mgKOH / g, more preferably 20 mgKOH / g to 150 mgKOH / g, and most preferably 40 mgKOH / g to 100 mgKOH / g. When the acid value of the specific resin is within this range, the dispersibility and dispersion stability of the pigment dispersion and the developability exhibited by the black curable composition using the pigment dispersion are improved. The acid value of the specific resin can be measured by titration with a base.

  The content of the repeating unit derived from the monomer (b-2) in the specific resin is preferably included in the specific resin so that the acid value of the specific resin falls within the above range.

  The specific resin preferably contains 15 to 90% by mass, more preferably 25 to 80% by mass of the repeating unit derived from the macromonomer (b-3), based on the total mass of the specific resin. It is most preferable to contain 35-60 mass%. When the content of the repeating unit derived from the macromonomer (b-3) is within this range, the dispersibility and dispersion stability of the pigment dispersion and the developability exhibited by the black curable composition using the pigment dispersion And further improve.

  Specific examples of the specific resin include, but are not limited to, resins (J-1) to (J-18) shown in the examples described later together with synthesis examples.

  The specific resin preferably has a weight average molecular weight of 5,000 or more and 70,000 or less, more preferably 7,000 or more and 25,000 or less, and more preferably 10,000 or more and 20 or less, in terms of polystyrene by GPC method. Most preferably, it is 1,000 or less. When the weight average molecular weight of the specific resin is within this range, the dispersibility and dispersion stability of the pigment dispersion and the developability exhibited by the black curable composition using the pigment dispersion are further improved.

  Content ratio of repeating unit derived from monomer (b-1), repeating unit derived from monomer (b-2), and repeating unit derived from macromonomer (b-3) in the specific resin (b-1: b- 2: b-3, mass ratio) is preferably 10-50: 2-30: 30-80, more preferably 15-45: 5-20: 40-70, and more preferably 20-40: 8-20: 40. ~ 60 is more preferred.

  The specific resin is preferably composed of (meth) acrylic and styrene-based repeating units. By comprising these repeating units, the specific resin has a relatively low thermal mobility, and as a result, the light shielding film becomes hard. For this reason, the permeability of the developer to the interface between the substrate and the light shielding film is suppressed, and the adhesion to the substrate is improved.

The specific resin itself may be curable.
In order to impart curability to the specific resin, a polymerizable group may be introduced into the specific resin. As a method for introducing a polymerizable group, for example, a method of reacting a carboxy group of a specific resin with a (meth) acrylate containing an epoxy group (for example, glycidyl methacrylate), a hydroxy group of a specific resin, and an isocyanate A known method such as a method of reacting a (meth) acrylate containing a group or a cyclic acid anhydride containing a polymerizable group can be used.

  When specific resin has a polymeric group, it is preferable that the repeating unit which has a polymeric group is contained 5-50 mass% with respect to the total mass of specific resin, and it is more contained 10-40 mass%. preferable.

  The specific resin may contain a repeating unit having a structural unit other than those described above in order to improve solubility in a solvent and coatability. Examples of such repeating units include alkyl (meth) acrylate, cycloalkyl (meth) acrylate, aralkyl (meth) acrylate, (meth) acrylate amide, 2-hydroxyethyl (meth) acrylate, styrene And repeating units derived from the above.

  The specific resin is produced by radical polymerization using a monomer (b-1), a monomer (b-2), a macromonomer (b-3), and a monomer having any other structure as necessary as a raw material. It is preferable. The polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing a specific resin by the radical polymerization method are the same as in the conventional method.

As content in the black curable composition of (B) specific resin of this invention, it is preferable to add 15 to 35 mass% with respect to (A) inorganic pigment, and is 20 to 30 mass%. It is most preferable to add the following. By being in this range, suppression of pattern defects obtained by curing the black curable composition and applicability of the black curable composition are improved.
Moreover, only 1 type may be used for specific resin and it may use 2 or more types together.

The black curable composition of the present invention preferably contains the following dispersant in addition to the (B) specific resin. By containing the dispersing resin and the dispersing agent, the dispersibility of the pigment can be improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.

  Specifically, many kinds of compounds can be used, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether Nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; W004, W005, W017 (manufactured by Yusho Co., Ltd.) Anionic surfactants such as EFKA 46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15. Disperse aid 9100 (all manufactured by San Nopco) and other polymer dispersants; Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L12 P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162 , 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (manufactured by Big Chemie Co., Ltd.). In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer.

  1-100 mass% is preferable with respect to the total mass of a pigment, and, as for the total content of (B) specific resin and the above-mentioned other dispersing agent in a black curable composition, 3-70 mass% is more preferable. .

<(C) Polymerization initiator>
The black curable composition of the present invention contains (C) a polymerization initiator.
The polymerization initiator in the black curable composition of the present invention is a compound that is decomposed by light or heat and starts and accelerates polymerization of a polymerizable compound described later, and has an absorption in a wavelength region of 300 to 500 nm. It is preferable.

Specific examples of the polymerization initiator include, for example, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, organic boric acid. Examples include compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, acylphosphine (oxide) compounds, and hexaarylbiimidazole compounds.
As the polymerization initiator, an oxime ester compound and a hexaarylbiimidazole compound are particularly preferable from the viewpoints of residue reduction and adhesion between the light shielding film and a surface on which the light shielding film is formed (substrate or the like).

  As a suitable oxime ester compound, a known compound known as a photopolymerization initiator of a photosensitive composition for use in electronic parts can be used. For example, JP-A-57-116047, JP-A-61-24558, JP-A-62-2201859, JP-A-62-286961, JP-A-7-278214, JP-A-2000-80068, JP-A-2001-233842, Special Tables. 2004-534797, JP 2002-538241, JP 2004-359639, JP 2005-97141, JP 2005-220097, WO 2005-080337A1, JP 2002-518732, JP 2001-235858, JP 2005-227525, It can be used by selecting from the compounds described in JP-A-2006-78749.

In general, the oxime ester compound has low sensitivity in the near ultraviolet region such as 365 nm and 405 nm, and thus has low sensitivity. However, it is known that the sensitizer increases the sensitivity in the near ultraviolet region and increases the sensitivity. Yes. Further, it is known that the combined use with cosensitizers such as amines and thiols increases the amount of effective radicals generated, but practically higher sensitivity has been required.
In the present invention, even an oxime ester compound having a small absorption in the near ultraviolet region such as 365 nm or 405 nm can be remarkably increased in sensitivity by using in combination with a sensitizer and reach a practical sensitivity.

  As the oxime ester compound, a compound having a small absorption in the range of 380 nm to 480 nm and a high decomposition efficiency, or a compound having a small absorption in the region by photolysis even if the absorption in the range of 380 nm to 480 nm is large (by-product) The compound whose absorption of a thing is a short wavelength) is preferable.

In the present invention, among oxime ester compounds, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- (O-acetyloxime) -1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is preferred.
Further, as the oxime photopolymerization initiator, a compound represented by the following formula (1) (hereinafter also referred to as “specific oxime compound”) is preferable. The specific oxime compound is a mixture of the (E) isomer and the (Z) isomer, regardless of whether the oxime N—O bond is an (E) oxime compound or a (Z) oxime compound. It may be.

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

The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Phosphinoyl group, heterocyclic group, alkylthiocarbonyl group, arylthiocarbonyl group, dialkylaminocarbonyl group, dialkylaminothiocarbonyl group and the like. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryloxy groups such as phenoxy group and p-tolyloxy group. , Methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group or aryloxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, Acyl groups such as methacryloyl group and methoxalyl group, alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group, Group, alkylamino group such as cyclohexylamino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, arylamino group such as phenylamino group, p-tolylamino group, methyl group, ethyl group, In addition to alkyl groups such as tert-butyl group and dodecyl group, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, etc., hydroxy groups, carboxy groups, formyl groups , Mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphono group, trimethylammonium group, dimethylsulfonium group, triphenyl Phenacylphosphonium group And the like.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and , 3 Nitorofenashiru group can be exemplified.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, Xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, ASEAN Trirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, ter Nthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

  The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and specific examples include a vinyl group, an allyl group, and a styryl group.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and specific examples include an ethynyl group, a propynyl group, and a propargyl group.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, and specifically includes a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, and a butylsulfinyl group. Group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, and methoxymethylsulfinyl group. .

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, and specifically includes a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2- Chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitro Phenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenol Rusurufiniru group, and a 4-dimethylaminophenyl sulfinyl group can be exemplified.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specifically includes a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group. Group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, and perfluoro An alkylsulfonyl group can be illustrated.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specifically includes a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, 2- Chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitro Phenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, and 4-dimethyl Aminophenyl sulfonyl group can be exemplified.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and And 4-methoxybenzoyl group.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanyl. Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl , 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, specifically, a dimethylphosphinoyl group, a diethylphosphinoyl group, a dipropylphosphinoyl group, or diphenyl. Examples include phosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, and bis (2,4,6-trimethylphenyl) phosphinoyl group.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl Group Midinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group Examples include a group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxanthryl group.

  Specific examples of the alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group. Examples thereof include a group and a trifluoromethylthiocarbonyl group.

  Specific examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, and a 4-phenylsulfanylphenylthiocarbonyl group. 4-dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3 -Chlorophenylthiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenyl Two thiocarbonyl group, and a and a 4-methoxyphenylthiocarbonyl group.

  Specific examples of the dialkylaminocarbonyl group include a dimethylaminocarbonyl group, a dimethylaminocarbonyl group, a dipropylaminocarbonyl group, and a dibutylaminocarbonyl group.

  Examples of the dialkylaminothiocarbonyl group which may have a substituent include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group, and a dibutylaminothiocarbonyl group.

  Among these, from the viewpoint of increasing sensitivity, as R, an acyl group is more preferable, and specifically, an acetyl group, a propanoyl group, a benzoyl group, and a toluoyl group are more preferable.

The monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, the structure shown below is particularly preferable.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (2) described later, and preferred examples are also the same.

Examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent. Examples of the substituent include the above-described substituents.
Specifically, phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group , Quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracene Nyl group, anthraquinolyl group, phenanthryl group Triphenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentaphenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubienyl group, coronenyl group, trinaphthylenyl group , A heptaphenyl group, a heptacenyl group, a pyrantrenyl group, and an oberenyl group.
Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the formula (1), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure. Me represents a methyl group, and Et represents an ethyl group.

  The specific oxime compound in the present invention is preferably a compound represented by the following formula (2).

  (In formula (2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0-5. (It is an integer.)

  R, A, and Ar in formula (2) have the same meanings as R, A, and Ar in formula (1), and preferred examples are also the same.

  Examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, and an arylsulfinyl group. Group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, amino group, phosphinoyl group, heterocyclic group and halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

  The alkyl group, aryl group, alkenyl group, alkynyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, phosphinoyl group, and heterocyclic ring in X The group is an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group of R in the formula (1). , Phosphinoyl group and heterocyclic group, and the preferred range is also the same.

  The alkoxy group is preferably an alkoxy group having 1 to 30 carbon atoms, specifically, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, or a tert-butoxy group. Pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, decyloxy, dodecyloxy, octadecyloxy, ethoxycarbonylmethyl, 2-ethylhexyloxycarbonylmethyl Oxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarbonylmethyloxy group Group, N- methyl -N- benzylaminocarbonyl methyl group, a benzyl group, and a cyano methyl group can be exemplified.

  The aryloxy group is preferably an aryloxy group having 6 to 30 carbon atoms, and specifically includes a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, and 2-methylphenyloxy. Group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, 4-fluorophenyloxy Group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, and 4-phenylsulfanylphenyloxy group.

  As the acyloxy group, an acyloxy group having 2 to 20 carbon atoms is preferable. Specifically, an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, a trifluoromethylcarbonyloxy group, a benzoyloxy group , 1-naphthylcarbonyloxy group, and 2-naphthylcarbonyloxy group.

  As the alkylsulfanyl group, an alkylsulfanyl group having 1 to 20 carbon atoms is preferable, and specifically, a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a cyclohexylsulfanyl group. Octylsulfanyl group, 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, and methoxymethylsulfanyl group.

  The arylsulfanyl group is preferably an arylsulfanyl group having 6 to 30 carbon atoms, and specifically includes a phenylsulfanyl group, a 1-naphthylsulfanyl group, a 2-naphthylsulfanyl group, a 2-chlorophenylsulfanyl group, and 2-methylphenylsulfanyl. Group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 4-fluorophenylsulfanyl group A group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfanyl group, and 4-dimethylamino-phenylsulfanyl group can be exemplified.

  The carbamoyl group is preferably a carbamoyl group having 1 to 30 carbon atoms, specifically, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, an N-butylcarbamoyl group, or an N-hexylcarbamoyl group. Group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2-chlorophenylcarbamoyl group, N 2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenylcarbamoyl group, N- 4-metoki Phenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N-dimethylcarbamoyl group N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group.

  As the sulfamoyl group, a sulfamoyl group having 0 to 30 carbon atoms is preferable, and specifically, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, an N, N-dialkylsulfamoyl group. , N, N-diarylsulfamoyl group and N-alkyl-N-arylsulfamoyl group. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Preferred examples include a group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, and N, N-diphenylsulfamoyl group.

The amino group is preferably an amino group having 0 to 50 carbon atoms, and specifically includes an amino group (—NH ₂ ), an N-alkylamino group, an N-arylamino group, an N-acylamino group, and an N-sulfonyl group. Examples include an amino group, an N, N-dialkylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, and an N, N-disulfonylamino group. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenyla Group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino Group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenyl Amino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) An amino group, an N, N- (dibutylsulfonyl) amino group, an N, N- (diphenylsulfonyl) amino group, a morpholino group, and 3,5-dimethyl-morpholino group, a carbazole group can be preferably exemplified.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Among these, X is an alkyl group, an aryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkylsulfanyl group, an arylsulfanyl group, from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region, An amino group is preferred.
Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

  Examples of the divalent organic group represented by Y include the structures shown below. In the groups shown below, “*” represents a bonding position between Y and an adjacent carbon atom in the formula (2).

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

  The specific oxime compound in the present invention is preferably a compound represented by the following formula (3).

  (In formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5.)

  R, X, A, Ar, and n in Formula (3) have the same meanings as R, X, A, Ar, and n in Formula (2), respectively, and preferred examples are also the same.

  Specific examples (K-1) to (K-88) of the specific oxime compound in the present invention are shown below, but the present invention is not limited thereto.

  The specific oxime compound in the present invention has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and has high absorbance at 365 nm and 455 nm. Is particularly preferred. In particular, since the specific oxime compound has an absorption in a long wavelength region as compared with a conventional oxime compound, it exhibits excellent sensitivity when exposed to a light source of 365 nm or 405 nm.

The specific oxime compound in the present invention preferably has a molar extinction coefficient at 365 nm or 405 nm of 10,000 to 300,000, more preferably 15,000 to 300,000, from the viewpoint of sensitivity. 000 to 200,000 is particularly preferable.
In the present invention, a known method can be used for the molar extinction coefficient of the compound. Specifically, for example, in an ultraviolet-visible spectrophotometer (Vary Inc., Carry-5 spectrophotometer), an ethyl acetate solvent is used. Is preferably measured at a concentration of 0.01 g / L.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5 5'-tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  The content of the (C) polymerization initiator in the black curable composition of the present invention is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass in the total solid content of the black curable composition. 2-20 mass% is especially preferable. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

  Depending on the polymerization initiator used, it is preferable to add a chain transfer agent to the black curable composition of the present invention. Examples of chain transfer agents include N, N-dialkylaminobenzoic acid alkyl esters and thiol compounds. As the thiol-based compound, for example, 2-mercaptobenzothiazole, 2-mercapto-1-phenylbenzimidazole, 3-mercaptopropionic acid, or the like can be used alone or in combination. In particular, it is preferable to use a combination of a hexaarylbiimidazole compound and a thiol compound from the viewpoint of residue and adhesion.

<(D) Polymerizable compound>
The black curable composition of the present invention contains (D) a polymerizable compound.
As the polymerizable compound, a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure is preferable.

Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Monofunctional acrylates and methacrylates such as phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) Ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and the addition of ethylene oxide and propylene oxide followed by (meth) acrylate conversion, poly (pentaerythritol or dipentaerythritol poly ( (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B-52-30490 and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid can be mentioned.
Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, those introduced as photocurable monomers and oligomers can also be used.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used as a polymerizable compound.

  Among these, as the polymerizable compound, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these (meth) acryloyl groups are interposed via ethylene glycol and propylene glycol residues are preferable. These oligomer types can also be used.

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, Also suitable are urethane compounds having an ethylene oxide-based skeleton described in 58-49860, JP-B 56-17654, JP-B 62-39417, and JP-B 62-39418. Further, as polymerizable compounds, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are exemplified. By using it, it is possible to obtain a curable composition having an extremely excellent photosensitive speed.
Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
Further, as the polymerizable compound, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxy group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and carboxy. And TO-1382 which is a group-containing pentafunctional acrylate.
The polymerizable compound used in the present invention is more preferably a tetrafunctional or higher acrylate compound.

A polymeric compound may be used individually by 1 type, and may be used in combination of 2 or more type.
As content in the black curable composition of a polymeric compound, 3-55 parts are preferable with respect to 100 parts of total solids in mass conversion, More preferably, it is 10-50 parts. (D) When the content of the polymerizable compound is within the above range, a sufficient curing reaction proceeds.

<(E) Alkali-soluble resin having unsaturated double bond: specific alkali-soluble resin>
The black curable composition of the present invention contains an alkali-soluble resin having an unsaturated double bond (hereinafter appropriately referred to as “specific alkali-soluble resin”). The alkali-soluble resin here is different from the specific resin (B), and (b-3) has substantially no repeating unit composed of a macromonomer having a weight average molecular weight of 1,000 or more and 50,000 or less. Resin is shown.
The specific alkali-soluble resin is preferably a polymer compound having a group represented by the following general formula (I) to general formula (III) as an unsaturated double bond in the side chain.

In the general formula ^{(I) ~ (III),} R l ~R ll each independently represent a hydrogen atom, or a monovalent organic group. L ¹ and L ² represent an oxygen atom, a sulfur atom, or —N—R ¹² , and Z represents an oxygen atom, a sulfur atom, —N—R ^12, or a phenylene group. R ¹² represents a hydrogen atom or a monovalent organic group.

In the general formula (I), R ^{1 to} R ³ each independently represents a hydrogen atom or a monovalent organic group. As R ¹ , a hydrogen atom or an alkyl group which may have a substituent, alkoxy Group, alkoxycarbonyl group, and the like. Among them, a hydrogen atom, a methyl group, a methylalkoxy group, and a methyl ester group are preferable. R ² and R ³ may each independently have a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxy group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or a substituent. Alkyl group, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituted An arylamino group which may have a group, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like, among them, a hydrogen atom, a carboxyl group, alkoxycarbonyl A group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable.
Here, examples of the substituent that can be introduced include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.
L ¹ represents an oxygen atom, a sulfur atom, or —N—R ¹² , where R ¹² includes a hydrogen atom, an alkyl group that may have a substituent, and the like.
In R < ¹ > -R < ³ > of general formula (I), as an alkyl group, a linear or cyclic C1-C30 alkyl group is mentioned, A C1-C20 alkyl group is preferable, C1-C1 Ten alkyl groups are particularly preferred.
In R < ¹ > -R < ³ > of general formula (I), C6-C30 is mentioned as an aryl group, C6-C20 is preferable and C6-C10 is especially preferable.

In the general formula (II), R ^{4 to} R ⁸ each independently represents a hydrogen atom or a monovalent organic group, and R ^{4 to} R ⁸ are, for example, a hydrogen atom, a halogen atom, an amino group, or a dialkylamino. Group, carboxy group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent An aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, a substituent An arylsulfonyl group which may have a group, and the like are mentioned. Among them, a hydrogen atom, a carboxy group, an alkoxycarbonyl group, an alkyl group which may have a substituent, an aryl which may have a substituent It is preferred. Examples of the substituent that can be introduced include those listed in the general formula (I). L ² represents an oxygen atom, a sulfur atom, or —N—R ¹² . Examples of R ¹² include the same as those in general formula (I). In R ^{4 to} R ⁸ of the general formula (II), examples of the alkyl group and aryl group include the same as those in the general formula (I), and preferred examples are also the same.

In Formula (III), R ⁹ ~R ^ll is each independently represent a hydrogen atom or a monovalent organic group, examples of the organic group, specifically, for example, a halogen atom, an amino group, a dialkylamino Group, carboxy group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent An aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, a substituent An arylsulfonyl group which may have a group, and the like. Among them, a hydrogen atom, a carboxy group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent. Lumpur group.
Here, examples of the substituent that can be introduced include those exemplified in the general formula (I).
Z represents an oxygen atom, a sulfur atom, —N—R ¹² or a phenylene group. Examples of R ¹² include the same as those in general formula (I).
The alkyl group and aryl group in R ⁹ to R ^ll of formula (III), the like can be mentioned for the formula (I), and preferred examples are also the same.

As the unsaturated double bond, among general formulas (I) to (III), general formula (I) is preferable from the viewpoint of curability, R ¹ is a methyl group or a hydrogen atom, R ² is a hydrogen atom, R Most preferably, ³ is a hydrogen atom.

  The specific alkali-soluble resin in the present invention can be produced by at least one of the following synthesis methods (a) to (e).

(A) Method of synthesizing by reacting a polymer having an acid group with a compound having both an epoxy group and an unsaturated double bond in the molecule (b) At least two or more unsaturated groups in the molecule and the monomer having an acid group Method of synthesizing by polymerizing monomer having double bond (c) Synthesis by reaction of polymer having acid group and hydroxy group in side chain with compound having both isocyanate group and unsaturated double bond in molecule (D) A method of synthesizing by reacting a polymer having an acid group and an epoxy group in the side chain with a compound having both an acid group and an unsaturated double bond in the molecule. (E) The acid group and the isocyanate group are on the side. A method of synthesizing by reacting a polymer having a chain with a compound having both a hydroxyl group and an unsaturated double bond in the molecule is described in detail below.

<(A) Method of synthesizing by reacting a polymer having an acid group with a compound having both an epoxy group and an unsaturated double bond in the molecule>
The polymer having an acid group is an organic polymer having an acid group in the main chain or side chain, and is particularly preferably a copolymer of an acid group-containing monomer and another copolymerizable monomer. . Examples of acid group-containing monomers include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, α-trifluoromethylacrylic acid, α-hydroxymethylacrylic acid, α-chloromethylacrylic acid, cinnamic acid, Styrene carboxylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2 -(Meth) acryloyloxyethyl], 1,2-cyclohexanedicarboxylic acid mono [2- (meth) acryloyloxyethyl], carboxy group-containing monomers such as ω-carboxypolycaprolactone mono (meth) acrylate, acid phosphooxyethyl ( (Meth) acrylate, acid phosphooxypolyoxy Phosphoric acid group-containing monomers such as ethylene glycol mono (meth) acrylate, acid phosphooxypolyoxypropylene glycol mono (meth) acrylate, 3-chloro-2-acid phosphooxypropyl (meth) acrylate, vinylphosphonic acid, 2-acrylamide Examples thereof include sulfonic acid group-containing monomers such as 2-methylsulfonic acid, vinyl sulfonic acid, and vinyl styrene sulfonic acid, and carboxyl group-containing monomers are particularly preferable. (Meth) acrylic acid, styrene carboxylic acid, succinic acid mono [2 -(Meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], 1,2-cyclohexanedicarboxylic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (me ) Acrylate, and most preferably (meth) acrylic acid.

  Only 1 type may be used for an acid group containing monomer, and 2 or more types may be used together.

Examples of other copolymerizable monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, Phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, phenetic (Meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol Cole (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl ( (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol Aliphatic or aromatic (meth) acrylate such as relate, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) ) Epoxy group-containing (meth) acrylate such as acrylate glycidyl ether, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Hydroxyl group-containing (meth) acrylates such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, isocyanate ethyl (meth) acrylate, 2- (2-isocyanatoethoxy) ethyl (meth) Isocyanate group-containing (meth) acrylates such as acrylate, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, Ether dimer type (meth) acrylates such as dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (meth) (Meth) acrylic acid amides such as acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid isopropylamide, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc. Carboxylic acid vinyl ester, vinyl methyl ether, vinyl ethyl ether And ethers, unsaturated ethers such as allyl glycidyl ether, vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) Unsaturated amides such as acrylamide and N-vinylpyrrolidone, aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylphenol, m-vinylphenol, p-vinylphenol, p-hydroxy-α-methylstyrene, o-vinylbenzylmethyl ether , M-bi Aromatic vinyl compounds such as n-benzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, N-phenylmaleimide, N-cyclohexylmaleimide, N -Monomaleimide compounds such as laurylmaleimide and N- (4-hydroxyphenyl) maleimide.

As other copolymerizable monomers, (meth) acrylic acid monomers and aromatic vinyl compounds are particularly preferred, and alkyl (meth) acrylate, benzyl (meth) acrylate and styrene having an alkyl group having 1 to 10 carbon atoms. Is most preferred.
Other copolymerizable monomers may be used alone or in combination of two or more.

  The polymer having an acid group can be produced by a known radical polymerization method. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing by the radical polymerization method can be easily set by those skilled in the art and can be set. .

The specific alkali-soluble resin can be synthesized by reacting the above-described polymer having an acid group with a compound having both an epoxy group and an unsaturated double bond in the molecule.
As the compound having both an epoxy group and an unsaturated double bond in the molecule, known compounds can be used. For example, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4- Epoxycyclohexyl) methyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether and the like can be mentioned, and glycidyl (meth) acrylate is particularly preferable.

  In the reaction between the polymer having an acid group and the compound having both an epoxy group and an unsaturated double bond in the molecule, it is preferable to add a catalyst to accelerate the reaction. As the catalyst, a known catalyst can be used. For example, a tertiary amino group or triphenylphosphine is preferable. The catalyst is preferably added in an amount of 0.1 to 2% by mass based on the solid content of the specific alkali-soluble resin to be synthesized. Although reaction temperature can be set suitably, it can carry out normally at 80-120 degreeC.

  Further, a cyclic acid anhydride may be added to a hydroxyl group produced by a reaction between a polymer having an acid group and a compound having both an epoxy group and an unsaturated double bond in the molecule. Examples of cyclic acid anhydrides include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, anhydrous Examples thereof include anhydrides of three or more bases such as pyromellitic acid, benzophenone tetracarboxylic acid anhydride, and biphenyl tetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferable. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

By adding such a component, alkali solubility can be imparted to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%. If the addition ratio is too large, the remaining film ratio during development may decrease, and if it is too small, the solubility may be insufficient. In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.

  Furthermore, in order to improve sensitivity, after adding the above-mentioned polybasic acid anhydride, a glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. Also good.

<(B) Method of synthesizing by polymerizing a monomer having an acid group and a monomer having at least two unsaturated double bonds in the molecule>
A specific alkali resin can be synthesized by copolymerizing the acid group-containing monomer mentioned in (a) above and a monomer having at least two unsaturated double bonds in the molecule. A (meth) acrylic monomer having an aliphatic alkenyl group such as an allyl group or a homoallyl group, or an aliphatic cycloalkenyl group such as cyclohexenyl or cyclododecenyl group is preferred, and allyl (meth) acrylate is preferred.

  As other copolymerization components other than the monomer having an acid group and the monomer having at least two or more unsaturated double bonds in the molecule, <other copolymerizable monomers> mentioned in the above (a) can be mentioned. The preferred examples are also the same.

<(C) Method of synthesizing by reacting a polymer having an acid group and a hydroxyl group in the side chain with a compound having both an isocyanate group and an unsaturated double bond in the molecule>
As a polymer having an acid group and a hydroxyl group in the side chain, the acid group-containing monomer and the hydroxyl group-containing (meth) acrylate mentioned in the above (a) can be synthesized by copolymerization by a known method. Compounds having both an isocyanate group and an unsaturated double bond in the molecule include isocyanate ethyl (meth) acrylate, 2- (2-isocyanatoethoxy) ethyl (meth) acrylate, 1,1- [bis (meta ) Acryloyloxymethyl] ethyl isocyanate. The reaction method of these isocyanate compounds and a polymer having an acid group and a hydroxyl group in the side chain can be carried out using a known urethanization reaction.

<(D) Method of synthesizing by reacting a polymer having an acid group and an epoxy group in the side chain with a compound having both an acid group and an unsaturated double bond in the molecule>
(D) The polymer having an acid group and an epoxy group in the side chain can be synthesized by copolymerizing the acid group-containing monomer and the epoxy group-containing (meth) acrylate mentioned in (a) by a known method. Examples of the compound having both an acid group and an unsaturated double bond in the molecule include the acid group-containing monomers mentioned in the above (a), and particularly preferred are carboxy group-containing monomers, (meth) acrylic acid, Styrene carboxylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], 1,2-cyclohexanedicarboxylic acid mono [2- (meth) acryloyloxyethyl] Ω-carboxypolycaprolactone mono (meth) acrylate is more preferred, and (meth) acrylic acid is most preferred. A known method (for example, JP 2009-53652 A) is used for the reaction between a compound having both an acid group and an unsaturated double bond in the molecule and a polymer having an acid group and an epoxy group in the side chain. be able to.

<(E) Method of synthesizing by reacting a polymer having an acid group and an isocyanate group in the side chain with a compound having both a hydroxyl group and an unsaturated double bond in the molecule>
The polymer having an acid group and an isocyanate group in the side chain can be synthesized by copolymerizing the acid group-containing monomer and the isocyanate group-containing (meth) acrylate mentioned in (a) by a known method. Examples of the compound having both a hydroxyl group and an unsaturated double bond in the molecule include the hydroxyl group-containing (meth) acrylates mentioned in (a) above. The reaction method between the polymer having an acid group and an isocyanate group in the side chain and the compound having both a hydroxyl group and an unsaturated double bond in the molecule can be performed using a known urethanization reaction.

  In addition to the synthesis methods (a) to (e) described above, a monomer having an unsaturated double bond and a divalent hydroxy group and a monomer having two cyclic acid anhydride groups described in JP-A No. 2001-354735 A resin obtained by the reaction with can also be used.

  The acid value of the specific alkali-soluble resin of the present invention is particularly preferably 10 to 100 mgKOH / g, more preferably 20 to 80 mgKOH / g, and most preferably 30 to 60 mgKOH / g. By being in this range, the adhesion of the fine pattern of the solid-state imaging device and the developability of the non-exposed part are compatible.

  400-3,000 are preferable and, as for the unsaturated equivalent (mass of resin per 1 mol of unsaturated double bonds) of specific alkali-soluble resin, 500-2,000 are the most preferable. By being in this range, the sclerosis | hardenability of a black curable composition increases and the adhesiveness of the fine pattern of a solid-state image sensor improves.

  The weight average molecular weight of the specific alkali-soluble resin is preferably 5,000 to 50,000, and more preferably 7,000 to 20,000. By being in this range, the adhesion of the fine pattern of the solid-state imaging device and the developability of the non-exposed part are compatible, and the coating property is further improved.

  The preferable acid value, unsaturated equivalent and molecular weight of the specific alkali-soluble resin described above can be controlled by the component ratio of the repeating units and the polymerization conditions (temperature, polymerization concentration, initiator addition amount, etc.). The specific alkali-soluble resin of the present invention is particularly preferably produced by the production methods (a), (b) and (c) from the viewpoint of reaction control, and the method (a) is most preferred.

  Although the specific example of specific alkali-soluble resin is shown below, this invention is not limited to these.

  The addition amount when the specific alkali-soluble resin is added to the black curable composition of the present invention is preferably 5 to 50% by mass, more preferably 10%, based on the solid content of the black curable composition. It is -35 mass%. If the specific alkali-soluble resin is in this range, the cured black curable composition has a suitable film strength, and it is preferable to control the solubility during development. Moreover, it is preferable also in the point which becomes easy to obtain the coating film of desired thickness. In particular, a uniform coating film can be formed for spin coating on a large-area substrate, and the yield is high, and a good coating film can also be obtained by the slit coating method. The specific alkali-soluble resin in the present invention may be added when the inorganic pigment is dispersed or may be added after the dispersion.

In black curable composition of the present invention, the content of (E) the specific alkali-soluble resin, on a mass basis relative to (D) polymerizable compound, Ri 0.3 2.5 der less, 0. It is more preferably 4 or more and 2.3 or less, and most preferably 0.5 or more and 2.0 or less. By being in this range, it is excellent in suppressing pattern defects.
In the black curable composition of the present invention, in particular, the mass ratio of (B) specific resin to (E) specific alkali-soluble resin is (B) specific resin: (E) specific alkali-soluble resin = 20: 80. -50: 50 is preferable, and 25: 75-40: 60 is most preferable. By being in this range, it is excellent in pattern formation property and applicability | paintability.

<Other ingredients>
The black curable composition of the present invention may contain other components as described below as necessary. Details are described below.

(solvent)
When preparing the black curable composition of this invention, a solvent can generally be contained. The solvent used is not particularly limited as long as the solubility of each component of the black curable composition and the applicability of the black curable composition are satisfied, but in particular, dissolution of specific resins, specific alkali-soluble resins, etc. Is preferably selected in consideration of the properties, applicability, and safety.
Also, it is preferable to use a solvent in the preparation of the pigment dispersion.
Examples of the solvent include a solvent described in paragraph 0272 of JP-A-2008-292970. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol Acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable.
It is also preferable to mix two or more of these organic solvents from the viewpoint of the solubility of the component to be added and the coating property of the black curable composition. The content of the solvent in the dispersion composition is preferably such that the total solid concentration in the dispersion composition is 5% by mass to 30% by mass, and more preferably 10% by mass to 20% by mass.

(Coloring agent)
In the black curable composition of the present invention, (A) a colorant other than an inorganic pigment such as an organic pigment or a dye can be used in combination with (A) the inorganic pigment in order to develop a desired light-shielding property.
Examples of the colorant that can be used in combination include organic pigments such as pigments described in paragraph numbers [0030] to [0044] of JP-A-2008-224982, and C.I. I. Pigment Green 58, C.I. I. Pigment Blue 79 in which the Cl substituent is changed to OH. Among these, examples of the organic pigment that can be preferably used include the following. However, the organic pigment that can be used in the present invention is not limited thereto.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment Orange 36,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255,
C. I. Pigment Violet 19, 23, 29, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37, 58
C. I. Pigment Black 1, 7
In the present invention, PB7 (carbon black) is treated as an organic pigment.

  There is no restriction | limiting in particular as dye which can be used as a coloring agent, A well-known dye can be selected suitably and can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 Examples thereof include dyes described in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

  Examples of the dye include pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene. Dyes having chemical structures such as phthalocyanine, phthalocyanine, benzopyran, and indigo can be suitably used.

  In the present invention, in the combination of (A) inorganic pigment and (F) organic pigment, titanium black, which is a preferred embodiment of the inorganic pigment, and organic having absorption at 400 to 600 nm as a combination that achieves both curability and light shielding properties. It is preferable to combine with a pigment, and it is preferable to combine at least one organic pigment selected from the group consisting of an orange pigment, a red pigment, and a violet pigment with titanium black, and most preferably a combination of a red pigment and titanium black. It is a combination.

  The organic pigment (F) may be prepared by dispersing with an inorganic pigment, or may be prepared by dispersing with a dispersant and adding a dispersion. As the dispersant used in preparing the dispersion, the specific resin (B) of the present invention may be used, and the above-described known pigment dispersants and surfactants may be used. The mass ratio of the pigment dispersant to the (F) organic pigment is preferably 20 to 80 mass%, more preferably 25 to 70 mass%, and most preferably 30 to 60 mass%.

(G: sensitizer)
The black curable composition of the present invention may contain (G) a sensitizer for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the photosensitive wavelength.
As the sensitizer that can be used in the present invention, a sensitizer that is sensitized by an electron transfer mechanism or an energy transfer mechanism to the polymerization initiator used in combination is preferable.
Preferable examples of the sensitizer include compounds described in paragraph numbers [0085] to [0098] of JP-A-2008-214395.
The content of the sensitizer in the black curable composition is preferably in the range of 0.1 to 30% by mass with respect to the mass of the total solid content of the black curable composition, from the viewpoint of sensitivity and storage stability. The range of -20 mass% is more preferable, and the range of 2-15 mass% is still more preferable.

(H: polymerization inhibitor)
A small amount of (H) polymerization inhibitor is added to the black curable composition of the present invention in order to prevent unnecessary thermal polymerization of the polymerizable compound (D) during the production or storage of the composition. Is desirable.
As the polymerization inhibitor, known thermal polymerization inhibitors can be used. Specifically, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 , 4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
The addition amount of the thermal polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the black curable composition.
Further, if necessary, in order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added, and the coating film is applied in the drying process after coating the higher fatty acid derivative. The surface may be unevenly distributed. The addition amount of the higher fatty acid derivative or the like is preferably about 0.5 to about 10% by mass of the total composition.

(I: adhesion improver)
In order to improve the adhesion between the light shielding film and the surface on which the light shielding film is formed, (I) an adhesion improver can be added to the black curable composition of the present invention. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.
Silane coupling agents include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, and γ-mercaptopropyltrimethoxy. Silane, γ-aminopropyltriethoxysilane, and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane is preferable.
0.5-30 mass% is preferable in the total solid of a black curable composition, and, as for the addition amount of an adhesion improving agent, 0.7-20 mass% is more preferable.
In particular, when a solid-state imaging device is produced on a substrate with the black curable composition of the present invention, it is preferable to add an adhesion improver from the viewpoint of improving sensitivity.

(J: surfactant)
Various (J) surfactants may be added to the black photosensitive composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

In particular, since the black photosensitive composition of the present invention contains a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the coating thickness is uniform. And the liquid-saving property can be further improved.
That is, when a film is formed using a coating liquid to which a black photosensitive composition containing a fluorosurfactant is applied, by reducing the interfacial tension between the coated surface and the coating liquid, The wettability is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

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

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F479, F482, F780, F781 (above, DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (manufactured by Asahi Glass Co., Ltd.), and the like.

  Specific examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol dilaurate. Stearate, sorbitan fatty acid ester (pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, manufactured by BASF, Tetronic 304, 701, 704, 901, 904, 150R1, etc. are mentioned.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).

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

Examples of the silicone-based surfactant include “Tore Silicone DC3PA”, “Tore Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, and “Tore Silicone SH29PA” manufactured by Torre Silicone Co., Ltd. , “Tole Silicone SH30PA”, “Tole Silicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-444 (4) (5)” manufactured by Momentive Performance Materials 6) (7) 6 ”,“ TSF-4460 ”,“ TSF-4442 ”,“ KP341 ”manufactured by Shin-Etsu Silicone Co., Ltd.,“ BYK323 ”,“ BYK330 ”manufactured by Big Chemie.
Only one type of surfactant may be used, or two or more types may be combined.

(K) Other additives Furthermore, the black curable composition has a purpose of further improving the sensitivity of the sensitizing dye and the initiator to active radiation, or to suppress inhibition of polymerization of the photopolymerizable compound by oxygen. For the purpose, a co-sensitizer may be contained. Moreover, you may add well-known additives, such as a diluent and a plasticizer for improving the physical property of a cured film as needed.

  The black curable composition of the present invention comprises the above-mentioned (A) inorganic pigment (preferably as a pigment dispersion composition containing a pigment dispersant), (B) a specific resin, (C) a polymerization initiator, (D) A polymerizable compound, (E) a specific alkali-soluble resin, and various additives that are used in combination together with a solvent can be contained together with a solvent, and an additive such as a surfactant can be mixed and prepared as necessary. .

  The black curable composition suitable for the light-shielding film for a solid-state imaging device of the present invention has a high-sensitivity, highly light-shielding and high-definition light-shielding film (light-shielding pattern) by adopting the above-described configuration. Can be formed. Moreover, since a black curable composition is excellent in developability, the residue of the residue derived from a black curable composition is reduced outside the formation area of a light shielding film.

[Light-shielding color filter for solid-state imaging device and manufacturing method thereof]
The light-shielding color filter for a solid-state imaging device of the present invention is characterized by having a pattern formed using the black curable composition of the present invention.

  The method for producing a light-shielding color filter for a solid-state imaging device of the present invention comprises a step of applying the black curable composition of the present invention on a support (hereinafter referred to as “black curable composition layer forming step” as appropriate), A step of exposing the applied black curable composition layer through a mask (hereinafter referred to as “exposure step” as appropriate), and a step of developing the exposed black curable composition layer to form a pattern (hereinafter referred to as appropriate). "Development process") in this order.

More specifically, the black curable composition of the present invention is applied on a support (substrate) directly or via another layer to form a black curable composition layer (black curable composition). Layer formation process), exposing through a predetermined mask pattern, curing only the light-irradiated coating film part (exposure process), and developing with a developer (development process) to form a pattern of black pixels A light-shielding color filter for a solid-state imaging device of the present invention can be produced by forming a film.
Hereinafter, each process in the manufacturing method of the light-shielding color filter for solid-state image sensors of this invention is demonstrated.

[Black curable composition layer forming step]
In the black curable composition layer forming step, the black curable composition layer of the present invention is applied on the support to form a black curable composition layer.

Examples of the support that can be used in this step include a photoelectric conversion element substrate (for example, a silicon substrate for CCD or CMOS), soda glass, alkali-free glass, Pyrex (registered trademark) glass, quartz used in a solid-state imaging device or the like. Examples thereof include glass and those obtained by attaching a transparent conductive film to these.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

As a coating method of the black curable composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied. .
The coating thickness of the black curable composition is preferably 0.35 μm to 1.5 μm, more preferably 0.40 μm to 1.0 μm, in terms of resolution and developability from the viewpoint of resolution and developability.

  The black curable composition coated on the support is usually dried at 70 ° C. to 110 ° C. for about 2 minutes to 4 minutes to form a black curable composition layer.

[Exposure process]
In the exposure step, the black curable composition layer formed in the black curable composition layer forming step is subjected to pattern exposure, and only the coating film portion irradiated with light is cured. The pattern exposure may be either a method of exposing through a mask or a scanning exposure, but a method of exposing through a mask is preferable.
Exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are particularly preferably used. Among these, i-line is preferable, and an exposure machine is used. I-line steppers are preferred. The irradiation intensity is more preferably ^5mJ / cm ^{2 ~1500mJ} / cm 2 is preferably ^{10mJ / cm 2 ~1000mJ / cm 2} , 10mJ / cm 2 ~800mJ / cm 2 being most preferred.

[Development process]
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part remains.
As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

Examples of the organic alkali used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4, An alkaline aqueous solution obtained by diluting an organic alkaline compound such as 0] -7-undecene with pure water to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.
In addition, an inorganic alkali may be used for the developer, and as the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metaoxalate and the like are preferable.

  In addition, in the manufacturing method of the light-shielding color filter for solid-state image sensors in this invention, after performing the black curable composition layer formation process, the exposure process, and the image development process which were mentioned above, the pattern formed as needed is carried out. A curing step for curing by heating and / or exposure may be included.

The light-shielding color filter for a solid-state imaging device according to the present invention can be produced through the black curable composition layer forming step, the exposure step, and the developing step (and further the curing step as necessary) described above.
Furthermore, in the black curable composition layer forming step, the chromatic color curable composition is obtained by replacing the inorganic pigment (A) in the black curable composition with a colorant having a desired hue (for example, a chromatic pigment or dye). Can be used to form a chromatic curable composition layer corresponding to RGB (hereinafter also referred to as “chromatic curable composition layer forming step”).

  Therefore, for example, the chromatic color curable composition layer forming step, the exposure step, and the developing step (and, if necessary, the curing step) are further added to the light-shielding color filter for a solid-state imaging device obtained as described above. By repeating the number of hues, a color filter having a chromatic pattern having a desired hue is produced.

  Even when the black curable composition of the present invention adheres to, for example, a nozzle of a coating apparatus discharge section, a piping section of a coating apparatus, or the inside of a coating apparatus, it can be easily washed and removed using a known cleaning liquid. In this case, in order to perform more efficient cleaning and removal, it is preferable to use the above-described solvent as the cleaning liquid as the solvent contained in the black curable composition of the present invention.

JP-A-7-128867, JP-A-7-146562, JP-A-8-278737, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, The cleaning liquids described in JP-A 2007-2101, JP-A 2007-2102, JP-A 2007-281523 and the like are also preferably used as cleaning liquids for cleaning and removing the black curable composition of the present invention. it can.
As the cleaning liquid, it is preferable to use alkylene glycol monoalkyl ether carboxylate or alkylene glycol monoalkyl ether.
These solvents that can be used as the cleaning liquid may be used alone or in combination of two or more.
When mixing 2 or more types of solvent, the mixed solvent formed by mixing the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group is preferable. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 80/20. The mixed solvent is a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), and the ratio is particularly preferably 60/40.
In addition, in order to improve the permeability of the cleaning liquid with respect to the black curable composition, the surfactant described above may be added to the cleaning liquid as a surfactant that can be contained in the black photosensitive composition.

[Solid-state image sensor]
The solid-state image sensor according to the present invention includes the light-shielding color filter for the solid-state image sensor according to the present invention. Since the light-shielding color filter for a solid-state imaging device in the present invention uses the black curable composition of the present invention, the formed pattern exhibits high adhesion to the support substrate and is cured. Since the product is excellent in development resistance, the exposure sensitivity is excellent, the adhesion between the exposed portion and the substrate is good, and a high-resolution pattern giving a desired cross-sectional shape can be formed. Therefore, it is suitable for a high-resolution CCD element, CMOS, or the like exceeding 1 million pixels.
The light-shielding color filter for a solid-state image sensor according to the present invention is used, for example, as a light-shielding color filter for a solid-state image sensor disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light. Can do.

  Moreover, the black curable composition for a solid-state imaging device can transmit transmitted light from the other surface of the silicon substrate having a solid-state imaging device portion on one surface, in addition to the formation of the light-shielding color filter for the solid-state imaging device described above. It can also be suitably used to form a light-shielding film for a solid-state imaging device for shielding light or a light-shielding film used for other purposes.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

[Synthesis Example 1]
(Synthesis of Resin (J-1))
Resin (J-1) which is a specific resin was synthesized as follows.
Macromonomer (the following structure, N-1) 55 g (weight average molecular weight (polystyrene conversion value) 3,500 in GPC method), monomer ( ^RA in the exemplified compound M-1 described above is a methyl group, B- 1) 35 g, 10 g of methacrylic acid, and 6 g of dodecanethiol were added to 233 g of propylene glycol monomethyl ether, and the mixture was stirred at 75 ° C. for 1 hour in a nitrogen atmosphere. To this, 0.5 g of dimethyl 2,2′-bisisobutyrate (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated for 2 hours. Further, 0.5 g of 2,2′-azobis (methyl isobutyrate) was added and heated for 2 hours. Then, after heating at 90 degreeC for 2 hours, it stood to cool and obtained the 30 wt% solution of resin (J-1).
A synthesis scheme is shown below. The composition ratio of (J-1) is a mass ratio.

  The macromonomer (N-1), monomer (B-1), and methacrylic acid used in Synthesis Example 1 are the macromonomer (b-3), monomer (b-1), and It corresponds to the monomer (b-2).

[Synthesis Examples 2 to 13]
Synthesis of Resins (J-2) to (J-18) Macromonomer (N-1), monomer (B-1), and methacrylic acid used in Synthesis Example 1 are classified into the types of macromonomers shown in Table 1 below, and Except having changed into the kind and quantity of each monomer, operation similar to the synthesis example 1 was performed, and resin (J-2)-(J-18) which is specific resin was obtained.
The weight average molecular weight, amine value, and acid value of the obtained specific resins (J-1) to (J-18) are shown together in Table 2.

The macromonomer (N-2) shown in Table 1 is “AA-6” manufactured by Toa Gosei Co., Ltd. (weight average molecular weight (polystyrene equivalent) in the GPC method 6,500), and (N-3) is Daicel Chemical. "PLAXEL FA10L" manufactured by Kogyo Co., Ltd. (weight average molecular weight (polystyrene equivalent value) 3,000 in GPC method), (N-4) and (N-5) are macromonomers ((N-4 ): Weight average molecular weight (polystyrene conversion value) 13,000, (N-5): weight average molecular weight (polystyrene conversion value) 21,000).
Monomers (M-7), (M-17), (M-37), (M-40), (M-47) and (M-48) shown in Table 1 are the same as those of monomer (b-1). It is the monomer illustrated as a specific example. The monomer (M-66) is a monomer exemplified as a specific example of the monomer (b-2).

  The amine value of the specific resin was measured using 0.1 N perchloric acid (acetic acid solvent) as a titrant, and the acid value was measured using a 0.1 N aqueous sodium hydroxide solution as a titrant.

<Example 1 to Example 10, Reference Example 11, and Example 12 to Example 40>
(Dispersion adjustment)
The components shown below (Composition I) were subjected to a high viscosity dispersion treatment with a two-roll, to obtain a dispersion. The kneader was kneaded for 30 minutes before the high viscosity dispersion treatment.

(Composition I)
-Titanium black A or titanium black B (described in Table 3) 45 parts-30% by mass propylene glycol methyl ether acetate (hereinafter referred to as "PGMEA") solution of each resin (J-1) to (J-18) 5 parts (solid content 1.5 parts)

  Titanium black A is titanium black 12S (average primary particle diameter 60 nm) manufactured by Mitsubishi Materials Corporation, and titanium black B is titanium black 13MT (average primary particle diameter 90 nm) manufactured by Mitsubishi Materials Corporation.

  Resins (J-1) to (J-18) and 150 parts of PGMEA shown in Table 3 were added to the obtained dispersion, and the mixture was stirred for 3 hours using a homogenizer at 3,000 rpm. The obtained mixed liquid was subjected to fine dispersion treatment for 4 hours with a disperser (trade name: manufactured by Dispermat GETZMANN) using zirconia beads having a diameter of 0.3 mm to obtain a titanium black dispersion. In addition, the number in the parenthesis shown in Table 3 is the solid content value of the added resin.

(Preparation of black curable composition)
The composition of the following (Composition II) is added to the above titanium black dispersion and mixed with a stirrer to cure each black color of Examples 1 to 10, Reference Example 11, and Examples 12 to 40 A sex composition was prepared.
(Composition II)
Alkali-soluble resin: Resin D-1 to Resin D-4 described in Tables 3 and 4 (structures are shown below), all 30% by mass PGMEA solution Amounts and polymerizable compounds described in Tables 3 and 4 : Compounds described in Tables 3 and 4 (structures are shown below) Amounts and polymerization initiators described in Tables 3 and 4: Compounds described in Tables 3 and 4 (structures are shown below) 10 .0 part. Solvent: PGMEA 50 parts. .Gamma.-methacryloxypropyltrimethoxysilane 0.1 part. Megafac F171 0.05 part

<Example 41>
(Preparation of black curable composition using silver tin composition)
In 200 ml of pure water kept at 60 ° C., 15 g of tin colloid (average primary particle size: 20 nm, solid content: 20%, manufactured by Sumitomo Osaka Cement Co., Ltd.) and silver colloid (average primary particle size: 7 nm, solid content: 20) %, Manufactured by Sumitomo Osaka Cement Co., Ltd.) and a solution obtained by dissolving 0.75 g of polyvinylpyrrolidone in 100 ml of water were added to obtain a colloidal solution.
Next, this colloidal solution was stirred for 60 minutes while being kept at 60 ° C., and then irradiated with ultrasonic waves for 5 minutes. Next, this colloidal solution was concentrated by centrifugation to obtain a liquid A having a solid content of 25%. The liquid A was dried by a freeze drying method to obtain a powder sample.

  In Example 5, a black curable composition was obtained in the same manner as in the preparation of the black curable composition of Example 5 except that the silver tin powder obtained above was used instead of titanium black A.

<Examples 42 and 43>
(Preparation of black curable composition using titanium black and organic pigment)
In Example 5, instead of titanium black A, titanium black A and C.I. I. Pigment Red254 (mass ratio Titanium Black A / Pigment Red254 = 80/20), or Titanium Black and C.I. I. The black curable compositions of Examples 42 and 43 were the same as the preparation of the black curable composition of Example 5 except that a mixture of Pigment Orange 36 (mass ratio Titanium Black A / Pigment Orange 36 = 80/20) was used. I got a thing.

<Comparative Examples 1-3>
(Preparation of black curable composition)
Comparison was made in the same manner as in the preparation of the black curable composition of Example 1, except that the titanium black A in Example 1 was changed to titanium black B and the specific resin and the specific alkali-soluble resin were changed to the resins shown in Table 3, respectively. The black curable composition of Examples 1-3 was obtained.
DISPERBYK-112 and DISPERBYK-180 are dispersion resins manufactured by Big Chemie.

<Comparative Example 4>
(Preparation of black curable composition using carbon black)
Titanium black A in Example 1 was changed to carbon black (Toka Black # 7400, average primary particle diameter 28 nm, manufactured by Tokai Carbon Co., Ltd.), and other than that, comparison was made in the same manner as the preparation of the black curable composition of Example 1. The black curable composition of Example 4 was prepared.

Specific resins used for the black curable compositions of Examples 1 to 10, Reference Example 11, Examples 12 to 43, and Comparative Examples 1 to 4, or comparative resins, alkali-soluble resins, and polymerization initiators Tables 3 and 4 show. The polymerization initiators used are the compounds (C-1) to (C-6) shown below, the polymerizable compound (Q-1) is dipentaerythritol hexaacrylate (product name DPHA, manufactured by Nippon Kayaku), and polymerizable. Compound (Q-2) is dipentaerythritol pentaacrylate succinic acid monoester (trade name TO-1382 manufactured by Toa Gosei Co., Ltd.).

[Production and evaluation of light-shielding color filter for solid-state image sensor]
(Formation of black curable composition layer)
Components of the following composition were mixed and dissolved to prepare an undercoat layer resist solution.
<Composition of resist solution>
Solvent: PGMEA 19.20 parts Solvent: ethyl lactate 36.67 parts Alkali-soluble resin: benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/22/18, weight) 30.51 parts of 40% PGMEA solution having an average molecular weight of 15,000 and a number average molecular weight of 9,000) Polymerizable compound: 12.20 parts of dipentaerythritol hexaacrylate Polymerization inhibitor: 0.0061 part of p-methoxyphenol Fluorosurfactant: F-475, manufactured by DIC Corporation 0.83 parts, polymerization initiator: trihalomethyltriazine-based photopolymerization initiator 0.586 parts (TAZ-107, manufactured by Midori Chemical Co., Ltd.)

  A 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the undercoat layer resist solution is applied onto the silicon wafer so as to have a dry film thickness of 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. An attached silicon wafer substrate was obtained.

  Examples 1 to 44 and Comparative Examples 1 to 44 were formed on a silicon wafer (substrate) with an undercoat layer by adjusting the spin coating speed so that the film thickness after coating and heat treatment was 2.0 μm. Each black curable composition of No. 3 was uniformly applied and heat-treated for 120 seconds with a hot plate having a surface temperature of 120 ° C. In this way, a black curable composition layer having a thickness of 2.0 μm was obtained.

(exposure)
Next, using an i-line stepper, FPA-3000iS + (manufactured by Canon Inc.), an exposure dose in the range of 100 to 5000 mJ / cm ² is set to 50 mJ through a 10.0 μm line and space pattern photomask. Irradiation (exposure) was performed by changing in steps of / cm ² .

(developing)
After irradiation (exposure), paddle development is performed at 23 ° C. for 60 seconds using a tetramethylammonium hydroxide (TMAH) 0.3% aqueous solution, and then rinsed with pure water for 20 seconds in a spin shower. And further washed with pure water.

Thereafter, the adhered water droplets were removed with air, the substrate was dried, and further heated at 200 ° C. for 1 minute to obtain a black image pattern (10.0 μm line-and-space pattern).
Thus, the light-shielding color filter for solid-state image sensors was obtained.

[Evaluation]
The following evaluation was performed about each black curable composition obtained as mentioned above and each light-shielding color filter for solid-state image sensors. The evaluation results are summarized in Table 5.

(Sensitivity evaluation)
In SEM observation, the minimum exposure amount at which the pattern size reached 10.0 μm was evaluated as sensitivity. It shows that board | substrate adhesiveness is so high that the value of a sensitivity is small.

(Pattern defect evaluation)
At the minimum exposure amount at which the pattern size reached 10.0 μm, an area of 100 μm was observed along the line of the line portion using SEM, and the number of defects in the pattern was counted. This was performed at five line parts, and the average number of pattern defects (the number of observed pattern defects / 5) was calculated. It shows that pattern formation is so favorable that a value is small.

(Light shielding evaluation)
Using the obtained light-shielding color filter, the maximum transmittance in a wavelength region of 400 nm to 800 nm was measured with a spectrophotometer (Shimadzu Corporation UV23600). The smaller the number, the better. When the maximum transmittance is less than 1%, the light shielding property is good.

From Table 5, it can be seen that pattern defects can be suppressed by using the black curable composition of the present invention.
Further, the black curable compositions of Examples 1 to 40 containing only titanium black as an inorganic pigment are particularly sensitive in comparison with the black curable composition of Example 41 containing an inorganic pigment other than titanium black. It turns out that it is excellent. Moreover, it turns out that light-shielding property improves further by using together titanium black and a red organic pigment like the black curable composition of Example 42 and Example 43. FIG.

<Example 44>
(Production of solid-state image sensor)
-Preparation of chromatic color curable composition-
Example except that in the black curable composition (B-4) prepared in Example 4, the black pigment Titanium Black 12S [manufactured by Mitsubishi Materials Corporation] was changed to the chromatic pigments described below. In the same manner as the adjustment of the black curable composition of No. 4, a chromatic curable composition for red, a chromatic curable composition for green, and a chromatic curable composition for blue were prepared.

Chromatic pigment and red pigment for forming chromatic pixels for each color of RGB I. Pigment Red 254
Green pigment C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 139 70/30 [mass ratio] mixture and blue pigment C.I. I. Pigment Blue 15: 6 and C.I. I. 70/30 [mass ratio] mixture with pigment violet 23

-Fabrication of full-color color filters for solid-state image sensors-
The black curable composition used in Example 4 was spin-coated on a silicon wafer so that the film thickness after drying was 0.8 μm, and the resulting silicon wafer having the black curable composition layer was 100 μm. It exposed at 400 mJ / cm < ² > with the i line | wire stepper used in Example 1 through the mask which has a lattice pattern (a frame width is 10 micrometers). Development, rinsing, drying and curing were performed in the same manner as in Example 1 to produce a light-shielding color filter.
In the obtained light-shielding color filter, red pixels are formed in an island pattern of 1.0 × 1.0 μm using the chromatic curable composition for red, and then 2/4 of the remaining lattice. A green pixel is formed in a 1.0 × 1.0 μm Bayer pattern using the chromatic curable composition for green, and the chromatic curable composition for blue is used in the remaining lattice. A blue pixel was formed on the 1.0 × 1.0 μm island pattern to produce a color filter for the light-shielding portion solid-state imaging device.

-Evaluation-
When the obtained full-color color filter for a solid-state image sensor is incorporated in the solid-state image sensor, the solid-state image sensor has a high light-shielding property, a high resolution, and a good color separation property. It was confirmed.

Claims (11)

  (A) inorganic pigment (excluding carbon black), (B) (b-1) a monomer having at least one group selected from an amino group and a nitrogen-containing heterocyclic group, and (b-2) acrylic A copolymer containing acid or methacrylic acid and (b-3) a macromonomer having a weight average molecular weight of 1,000 or more and 50,000 or less, (C) a polymerization initiator, (D) a polymerizable compound, and (E ) An alkali-soluble resin having an unsaturated double bond is contained, and the content of the (E) alkali-soluble resin is 0.3 to 2.5 on a mass basis with respect to the (D) polymerizable compound. Black curable composition for solid-state image sensor. (A) inorganic pigment (excluding carbon black), (B) (b-1) a monomer having at least one group selected from an amino group and a nitrogen-containing heterocyclic group, and (b-2) carboxy A monomer having at least one group selected from the group consisting of a group, a phosphoric acid group, and a sulfonic acid group; and (b-3) a macromonomer having a weight average molecular weight of 1,000 to 50,000. A polymer, (C) a polymerization initiator, (D) a polymerizable compound, and (E) an alkali-soluble resin having an unsaturated double bond, wherein the content of the (E) alkali-soluble resin is (D ) For a solid-state imaging device, which is 0.3 to 2.5 on a mass basis with respect to the polymerizable compound, and (b-3) the macromonomer is a polyester macromonomer represented by the following general formula (M) Black curability Narubutsu.


(In General Formula (M), R ^1A represents a hydrogen atom or a methyl group. R ^2A represents an alkylene group. R ^3A represents an alkyl group. N represents an integer of 5 to 100.) (A) the inorganic pigment, silver and / or metal pigments containing tin, as well as claim 1 or a solid-state imaging device for black curable composition according to claim 2 is at least one selected from titanium black. The black curable composition for a solid-state imaging device according to claim 3 , wherein the (A) inorganic pigment is titanium black. The average primary particle diameter of the titanium black, claim 3 or a solid-state imaging device for black curable composition according to claim 4 is 30nm or more 65nm or less. The solid content according to any one of claims 1 to 5 , wherein a content of the (B) copolymer is 0.15 or more and 0.35 or less on a mass basis with respect to the (A) inorganic pigment. Black curable composition for image sensor. The black curable composition for a solid-state imaging device according to any one of claims 1 to 6 , wherein the polymerization initiator (C) is an oxime ester compound or a hexaarylbiimidazole compound. Further, (F) a solid-state imaging device for black curable composition according to any one of claims 1 to 7 containing an organic pigment. The process of apply | coating the black curable composition for solid-state image sensors of any one of Claims 1-8 on a support body, the process of carrying out pattern exposure of the apply | coated black curable composition layer, and exposure The manufacturing method of the light-shielding color filter for solid-state image sensors which has the process of developing the formed black curable composition layer and forming a light-shielding pattern in this order. The light-shielding color filter for solid-state image sensors which has a light-shielding pattern which uses the black curable composition for solid-state image sensors of any one of Claims 1-8 . A solid-state imaging device including a solid-state imaging device for light-shielding color filter according to claim 1 0.