JP2011202023A - Black curable composition for wafer level lens, wafer level lens and camera module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a black curable composition for wafer level lens capable of forming a cured film having excellent light shieldability and excellent in co-formability of both a large pattern and a fine pattern.SOLUTION: The black curable composition for a wafer level lens contains (A) an inorganic pigment, (B) a copolymer containing (b-1) a monomer having at least one group selected from an amino group and a nitrogen-containing heterocyclic group, (b-2) a monomer having at least one group selected from among a carboxyl group, a phosphoric acid group and a sulfonic acid group and (b-3) a macromonomer having a weight-average molecular weight of ≥1,000 and ≤50,000, (C) a polymerization initiator, (D) a polymerizable compound and (E) an alkali-soluble resin having an unsaturated double bond.

Description

  The present invention relates to a black curable composition for a wafer level lens useful for forming a light-shielding film for a wafer level lens, and a wafer level lens and a camera module obtained using the same.

  In recent years, portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin imaging units. Such an imaging unit generally includes a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor or a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, and a lens that forms a subject image on the solid-state imaging device. I have.

  With the downsizing / thinning of portable terminals and the widespread use of portable terminals, further reduction in size / thinning is required for imaging units mounted on the portable terminals, and productivity is required. In response to such a request, a lens substrate on which a plurality of lenses are formed and a sensor substrate on which a plurality of solid-state image sensors are formed are combined in an integrated manner, and then each lens substrate includes a lens and a solid-state image sensor. In addition, a method of mass-producing an imaging unit by cutting a sensor substrate is known. In addition, as another method of manufacturing the imaging unit, a method in which only a lens is manufactured on a glass wafer or the like, cut into an appropriate size for combining with an individual sensor, and combined with an image sensor that has been separated into pieces in advance, A method of forming a plurality of lenses with a mold using only resin and combining and cutting them on a sensor substrate, cutting a lens into a size for combining with individual sensors, and combining with a pre-divided imaging device You can take methods.

  Conventionally, as a wafer level lens array composed of a lens substrate and a lens group formed on the lens substrate, a curable resin material is dropped on the surface of a parallel plate substrate formed of a light transmissive material such as glass, This resin material is cured in a state of being shaped into a predetermined shape with a mold, and a plurality of lenses are formed (for example, see Patent Documents 1 and 2). In order to adjust the amount of light, a light-shielding region made of a black film or a metal film may be formed in a region other than the lens portion of the wafer level lens or a part of the lens. Further, depending on the intended use, a fine pattern of 50 μm or less may be formed on the same substrate. The light-shielding region is generally formed by applying a curable light-shielding composition or depositing a metal using a photolithography method.

  As a method of forming a light-shielding region using a photolithography method, a light-shielding composition is applied on a lens or a substrate such as a glass substrate, and a portion to be the light-shielding region is exposed and cured, and then alkali development is performed. The method of forming the light-shielding area | region comprised with the light shielding film by removing the light-shielding composition of an unexposed part with a liquid is mentioned. However, when forming a light-shielding film using a conventional curable composition, there is a problem that adhesion of a fine pattern on the same substrate is low. On the other hand, in the case where the light shielding film is formed in a high exposure amount region necessary for forming a fine pattern, there is a problem that curing proceeds to a developing portion which is a non-exposed portion and a residue remains. That is, it is difficult to form both the light shielding film (large pattern) and the fine pattern on the same substrate.

  Patent Document 4 and Patent Document 5 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 and reducing a residue in a non-exposed portion. Furthermore, as a curable composition used for forming a light-shielding region in a wafer level lens having a large pattern and a fine pattern on the same substrate, improvement in pattern formability has been demanded.

Japanese Patent No. 3926380 International Publication No. 2008/102648 Pamphlet US Pat. No. 6,426,829 JP 2010-6932 A JP 2004-37986 A

This invention is made | formed in view of the said conventional condition, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a black curable composition for a wafer level lens, which can form a cured film excellent in light-shielding properties and is excellent in the simultaneous formation of both a large pattern and a fine pattern.
Furthermore, a further object of the present invention is to provide a wafer level lens in which the amount of light is appropriately adjusted by including a light-shielding film formed from the black curable composition for a wafer level lens of the present invention, and which can be easily manufactured. It is to provide a camera module.

As a result of intensive studies, the present inventor has found that the above problem can be solved by a black curable composition containing a specific resin, and has completed the present invention.
Means for solving the above-mentioned problems are as follows.
<1> (A) inorganic pigment, (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 a phosphate 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, (C A black curable composition for a wafer level lens, comprising: a) a polymerization initiator, (D) a polymerizable compound, and (E) an alkali-soluble resin having an unsaturated double bond.

<2> (A) The black curable composition for wafer level lenses according to <1>, wherein the inorganic pigment is titanium black.
<3> The wafer level lens according to <1> or <2>, wherein 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. Black curable composition.
<4> 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 any one of <1> to <3> The black curable composition for wafer level lenses described in 1.

<5> The black curable composition for a solid-state imaging device according to any one of <1> to <4>, wherein one type of the (b-2) monomer is at least acrylic acid or methacrylic acid.
<6> The black curable composition for a wafer level lens according to any one of <1> to <5>, wherein the polymerization initiator (C) is an oxime ester compound or a hexaarylbiimidazole compound.

<7> The black curable composition for wafer level lenses according to any one of <2> to <6>, wherein the titanium black has an average primary particle size of 30 nm to 65 nm.
<8> The black curable composition for a wafer level lens according to any one of <1> to <7>, further comprising (F) an organic pigment.
<9> Wafer level having a light-shielding film obtained using the black curable composition for a wafer level lens according to any one of <1> to <8> at a peripheral portion of a lens present on the substrate. lens.
<10> A camera module comprising the wafer level lens according to <9>.

ADVANTAGE OF THE INVENTION According to this invention, the cured film excellent in light-shielding property can be formed, and the black curable composition for wafer level lenses excellent in the simultaneous formation of both a large pattern and a fine pattern can be provided.
In addition, by providing the light-shielding film formed of the black curable composition for a wafer level lens of the present invention, it is possible to provide a wafer level lens and a camera module in which the amount of light is appropriately adjusted and can be easily manufactured. .

It is a top view which shows an example of a wafer level lens array. It is the sectional view on the AA line shown in FIG. It is a figure which shows the state which is supplying the molding material used as a lens to a board | substrate. 4A to 4C are diagrams showing a procedure for forming a lens on a substrate with a mold. 5A to 5C are schematic views illustrating a process of forming a patterned light-shielding film on a substrate on which a lens is molded. It is sectional drawing which shows an example of a wafer level lens array. 7A to 7C are schematic views showing other modes of the light shielding film forming step. FIG. 8A to FIG. 8C are schematic views showing a process of forming a lens on a substrate having a patterned light shielding film. It is drawing of the pattern in the exposure used for the Example.

  Hereinafter, a black curable composition for a wafer level lens of the present invention and a wafer level lens provided with a light-shielding film obtained using the black curable composition 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).

  Here, in this specification, the “wafer level lens” is a lens provided in the solid-state imaging device, and includes individual lenses existing on the substrate and a light-shielding film provided on the periphery of the lens. Means things. A group consisting of the wafer level lenses is referred to as a “wafer level lens array”.

[Black curable composition for wafer level]
The black curable composition for wafer level of the present invention (hereinafter also referred to as “the black curable composition of the present invention” as appropriate) comprises (A) an inorganic pigment, (B) (b-1) an amino group and / or A monomer having a nitrogen-containing heterocyclic group, (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) weight A copolymer containing a macromonomer having an average molecular weight of 1,000 or more and 50,000 or less (hereinafter referred to as “specific resin” as appropriate), (C) a polymerization initiator, (D) a polymerizable compound, and (E ) It contains an alkali-soluble resin having an unsaturated double bond.

  The black curable composition of the present invention improved the simultaneous formation of a large pattern and a fine pattern, which was a problem when forming a light-shielding region of a wafer level lens by a photolithography method. The “large pattern” in the present invention is a projection pattern having a short side of a size of about 500 μm to 5000 μm, and the fine pattern is a projection pattern having a short side of a size of about 5 μm to 50 μm.

Although this mechanism of action is not yet clear, it is estimated as follows.
When the developability and curability of the black curable composition are low, the fine pattern cannot be completely cured in the low exposure range where a large pattern can be formed, and the adhesion to the substrate is deteriorated. On the other hand, in the high exposure amount region where the substrate adhesion of the fine pattern can be ensured, since the curing proceeds even to the developing portion (outside the light shielding film forming region) which is a non-exposed portion, a residue is generated. That is, in order to form a large pattern and a fine pattern at the same time, it is necessary to improve both the developability and curability of the black curable composition and the solubility discrimination.

  Generally, a dispersion resin is a component that has a water-repellent steric repulsion group to prevent aggregation between pigments and does not have curability, and thus deteriorates the developability and curability of the black curable composition. . On the other hand, 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 a basic group which is an amino group and / or a nitrogen-containing heterocyclic group. It is a dispersion resin having a specific structure. In the specific resin of the present invention, when a pattern is formed, a part of the acid group and the basic group becomes a counter salt, so that the permeability of the developer is improved and the developability is improved. Since the network of acid and base is formed, the hardness of the exposed film is improved. This action is considered to have improved the pattern forming properties of both large and fine patterns at the same time. 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, and a light-shielding film (large pattern) that has been a problem at the time of wafer level lens creation And the problem of forming a fine pattern simultaneously can be solved.

The black curable composition for a wafer level lens of the present invention is used for forming a light-shielding cured film (hereinafter also referred to as “light-shielding film” as appropriate) in a wafer level lens.
Here, “light shielding” in this specification means the ability to suppress transmission of light having a wavelength of 400 nm to 800 nm.

  Hereafter, each component contained in the black curable composition for wafer level lenses of this invention is demonstrated one by one.

<(A) Inorganic pigment>
The black curable composition of the present invention contains an inorganic pigment 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 particle size of titanium black suitably used as the 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, preferably 10 nm to 100 nm. is there. In particular, in the wafer level lens application of the present invention, the pattern forming property is improved by using titanium black having an average primary particle diameter 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.

  It is preferable that content of the inorganic pigment in a black curable composition is 5-70 mass% with respect to solid content of a black curable composition, and it is more preferable that it is 10-60 mass%.

  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 phosphoric acid 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 comprising a monomer having at least one group selected from the group consisting of a group and a sulfonic acid group, 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 formability of both the large pattern and the fine pattern 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 the dispersion stability of the pigment dispersion, the developability exhibited by the black curable composition using the pigment dispersion, and the patterns of large and fine patterns. Particularly preferred from the viewpoint of formability.

<(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.

The mass ratio of (B) specific resin to (A) inorganic pigment of the present invention is preferably 0.15 or more and 0.35 or less, and most preferably 0.20 or more and 0.30 or less. By being in this range, adhesion to both large and fine pattern substrates 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.

<(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, heptalenyl 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 carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and carboxyl. 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 a preferred example of the combination, it is preferable to combine two types of monomers having different polymerizable groups, and combining a monomer having a polymerizable group of 4 or less and a monomer having a functionality of 5 or more can improve developability and adhesion. More preferable from the viewpoint.
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) 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 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%. When the addition ratio is too large, the remaining film ratio at the time of development may decrease, and when 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 the black curable composition of the present invention, the content of the (E) specific alkali-soluble resin is preferably 0.3 or more and 2.5 or less on a mass basis with respect to the (D) polymerizable compound. It is more preferably 0.4 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 in the preparation of the pigment dispersion, it is preferable to use a solvent.
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 viewpoints of solubility, applicability of the colored curable composition, and the like. 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. By setting this range, the solubility can be kept good.

(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.

  The dyes 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 black curable composition of the present invention is preferably made into a pigment dispersion using a specific resin in advance. At this time, by adding a dispersant or a pigment derivative in addition to the specific resin, further dispersibility and dispersion stability are obtained. 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, L121, -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.

  As content in the pigment dispersion of a dispersing agent, 1-100 mass% is preferable with respect to the total amount of an inorganic pigment and the organic pigment which is an arbitrary component, and 3-70 mass% is more preferable.

  Further, a pigment derivative is added to the pigment dispersion as necessary. Part of the pigment that has an affinity for the dispersant or a pigment derivative with a polar group is adsorbed on the pigment surface, and this is used as the adsorption point for the dispersant to disperse the pigment as fine particles and prevent reaggregation. And a pigment dispersion excellent in dispersion stability and a black curable composition can be obtained.

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included. Examples of the dye derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. And JP-A-2005-234478, JP-A-2003-240938, and JP-A-2001-356210 can be used.

  As content in the pigment dispersion of the pigment derivative based on this invention, 1-30 mass% is preferable with respect to the mass of a pigment, and 3-20 mass% is more preferable. When the content is within the above range, the dispersion can be favorably performed while the viscosity is kept low, and the dispersion stability after dispersion can be improved.

(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 An adhesion improver can be added to the black curable composition of the present invention in order to improve the adhesion between the light shielding film and the surface on which the light shielding film is formed. 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 wafer level lens is produced on a glass 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, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by 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.), W001 (manufactured by Yusho Co., Ltd.), and the like.

  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 for a wafer level lens of the present invention can be cured with high sensitivity, excellent in light shielding properties, and can form a light shielding film (light shielding pattern) with high definition by adopting the above-described configuration. . Moreover, since the black curable composition for wafer level lenses is excellent in developability, the residue of the residue derived from the black curable composition is reduced outside the formation region of the light shielding film.

<Wafer level lens>
The wafer level lens of the present invention is characterized by having a light-shielding film obtained by using the black curable composition of the present invention at the periphery of the lens present on the substrate.
The wafer level lens of the present invention will be described below with reference to the drawings.

FIG. 1 is a plan view showing an example of the configuration of a wafer level lens array having a plurality of wafer level lenses.
As shown in FIG. 1, the wafer level lens array includes a substrate 10 and lenses 12 arranged on the substrate 10. Here, in FIG. 1, the plurality of lenses 12 are two-dimensionally arranged with respect to the substrate 10, but may be arranged one-dimensionally.
2 is a cross-sectional view taken along line AA shown in FIG.
As shown in FIG. 2, in the wafer level lens array, a light shielding film 14 that prevents light from being transmitted from places other than the lens 12 is provided between the plurality of lenses 12 arranged on the substrate 10.
The wafer level lens of the present invention is composed of one lens 12 existing on the substrate 10 and a light shielding film 14 provided on the peripheral edge thereof. The black curable composition of the present invention is used for forming the light shielding film 14.

  Hereinafter, a configuration of a wafer level lens array in which a plurality of lenses 12 are two-dimensionally arranged with respect to the substrate 10 as shown in FIG. 1 will be described as an example.

  The lens 12 is generally made of the same material as the substrate 10 and is molded integrally on the substrate 10 or formed as a separate structure and fixed on the substrate. is there. Although an example is given here, the wafer level lens of the present invention is not limited to this mode, and can take various modes such as a multi-layer structure and a lens module separated by dicing.

  Examples of the material for forming the lens 12 include glass. There are many types of glass, and a glass having a high refractive index can be selected. Therefore, the glass is suitable for a lens material that requires a large power. Further, glass has excellent heat resistance, and has an advantage of withstanding reflow mounting on an imaging unit or the like.

  Resin is mentioned as another material which forms the lens 12. FIG. Resin is excellent in processability and is suitable for forming a lens surface easily and inexpensively with a mold or the like.

In forming the wafer level lens, it is preferable to use an energy curable resin. The energy curable resin may be either a resin curable by heat or a resin curable by irradiation with active energy rays (for example, heat, ultraviolet rays, or electron beam irradiation).
In consideration of reflow mounting of the imaging unit, a resin having a relatively high softening point such as 200 ° C. or higher is preferable, and a resin having a softening point of 250 ° C. or higher is more preferable.
Hereinafter, a resin suitable as a lens material will be described.

Examples of the ultraviolet curable resin include an ultraviolet curable silicon resin, an ultraviolet curable epoxy resin, and an acrylic resin. As the epoxy resin, those having a linear expansion coefficient of 40 to 80 [10 ⁻⁶ / K] and a refractive index of 1.50 to 1.70, preferably 1.50 to 1.65 can be used.

Examples of the thermosetting resin include a thermosetting silicone resin, a thermosetting epoxy resin, a thermosetting phenol resin, and a thermosetting acrylic resin. For example, a silicon resin having a linear expansion coefficient of 30 to 160 [10 ⁻⁶ / K] and a refractive index of 1.40 to 1.55 can be used. As the epoxy resin, those having a linear expansion coefficient of 40 to 80 [10 ⁻⁶ / K] and a refractive index of 1.50 to 1.70, preferably 1.50 to 1.65 can be used. As the phenol resin, one having a linear expansion coefficient of 30 to 70 [10 ⁻⁶ / K] and a refractive index of 1.50 to 1.70 can be used. As the acrylic resin, those having a linear expansion coefficient of 20 to 60 [10 ⁻⁶ / K] and a refractive index of 1.40 to 1.60, preferably 1.50 to 1.60 can be used.

  As these thermosetting resins, commercially available products can be used. Specifically, for example, SMX-7852, SMX-7877, manufactured by Fuji Polymer Industries Co., Ltd., IVSM-4500 manufactured by Toshiba Corporation, Toray Dow Examples thereof include SR-7010 manufactured by Corning.

Examples of the thermoplastic resin include polycarbonate resin, polysulfone resin, polyether sulfone resin, and the like. As the polycarbonate, one having a linear expansion coefficient of 60 to 70 [10 ⁻⁶ / K] and a refractive index of 1.40 to 1.70, preferably 1.50 to 1.65 can be used. As the polysulfone resin, one having a linear expansion coefficient of 15 to 60 [10 ⁻⁶ / K] and a refractive index of 1.63 can be used. As the polyethersulfone resin, one having a linear expansion coefficient of 20 to 60 [10 ⁻⁶ / K] and a refractive index of 1.65 can be used.

In general, the linear expansion coefficient of optical glass is 4.9 to 14.3 [10 ⁻⁶ / K] at 20 ° C., and the refractive index is 1.4 to 2.1 at a wavelength of 589.3 nm. Further, the linear expansion coefficient of quartz glass is 0.1 to 0.5 [10 ⁻⁶ / K], and the refractive index is about 1.45.

  The curable resin composition that can be applied to the formation of the lens preferably has an appropriate fluidity before curing from the viewpoint of moldability such as mold shape transfer suitability. Specifically, it is liquid at room temperature and has a viscosity of about 1000 mPa · s to 50000 mPa · s.

  On the other hand, it is preferable that the curable resin composition that can be applied to the formation of the lens has a heat resistance that does not cause thermal deformation even after the reflow process after curing. From this viewpoint, the glass transition temperature of the cured product is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, and particularly preferably 300 ° C. or higher. In order to impart such high heat resistance to the resin composition, it is necessary to constrain the mobility at the molecular level, and as effective means, (1) means for increasing the crosslinking density per unit volume, (2) Means utilizing a resin having a rigid ring structure (for example, alicyclic structures such as cyclohexane, norbornane, tetracyclododecane, aromatic ring structures such as benzene and naphthalene, and cardo structures such as 9,9′-biphenylfluorene And resins having a spiro structure such as spirobiindane, specifically, for example, JP-A-9-137043, JP-A-10-67970, JP-A-2003-55316, JP-A-2007-334018, JP-A-2007-238883. (3) means for uniformly dispersing a substance having a high Tg such as inorganic fine particles (for example, Japanese Patent Laid-Open No. Hei 5- 09027, JP-described), and the like in the 10-298265 Patent Publication. A plurality of these means may be used in combination, and it is preferable to make adjustments within a range that does not impair other characteristics such as fluidity, shrinkage rate, and refractive index characteristics.

  From the viewpoint of shape transfer accuracy, it is preferable to use a curable resin composition having a small volume shrinkage due to the curing reaction. The curing shrinkage rate of the resin composition is preferably 10% or less, more preferably 5% or less, and particularly preferably 3% or less.

  Examples of the resin composition having a low curing shrinkage rate include (1) resin compositions containing a high molecular weight curing agent (such as a prepolymer) (for example, JP-A Nos. 2001-19740 and 2004-302293, The number average molecular weight of the high molecular weight curing agent is preferably in the range of 200 to 100,000, more preferably in the range of 500 to 50,000, and particularly preferably 1,000. The value calculated by the number average molecular weight of the curing agent / the number of curing reactive groups is preferably in the range of 50 to 10,000, and is preferably 100 to 5,000. More preferably in the range of 200 to 3,000), and (2) containing non-reactive substances (organic / inorganic fine particles, non-reactive resins, etc.). Resin compositions (for example, described in JP-A-6-298883, JP-A-2001-247793, JP-A-2006-225434, etc.), (3) Resin compositions containing low-shrinkage crosslinking reactive groups (for example, A ring-polymerizable group; for example, an epoxy group (for example, described in JP-A-2004-210932), an oxetanyl group (for example, described in JP-A-8-134405), an episulfide group (for example, JP-A-2002-2002) 105110, etc.), cyclic carbonate groups (for example, described in JP-A-7-62065, etc.), ene / thiol curing groups (for example, described in JP-A 2003-20334, etc.), hydrosilylation Curing group (for example, described in JP-A-2005-15666) and the like, and (4) rigid skeleton resin (fluorene, adamantane, isophor A resin composition (for example, described in JP-A-9-137043), and (5) an interpenetrating network structure (so-called IPN structure) including two types of monomers having different polymerizable groups. Resin composition (for example, described in JP-A-2006-131868), (6) Resin composition containing an expandable substance (for example, JP-A-2004-2719, JP-A-2008-238417, etc.) And the like can be suitably used in the present invention. In addition, it is preferable from the viewpoint of optimizing physical properties to use a plurality of curing shrinkage reducing means in combination (for example, a resin composition containing a prepolymer containing a ring-opening polymerizable group and fine particles).

For forming the wafer level lens of the present invention, it is desirable to use two or more types of resin compositions having different Abbe numbers.
The resin on the high Abbe number side preferably has an Abbe number (νd) of 50 or more, more preferably 55 or more, and particularly preferably 60 or more. The refractive index (nd) is preferably 1.52 or more, more preferably 1.55 or more, and particularly preferably 1.57 or more.
As the resin contained in such a resin composition, an aliphatic resin is preferable, and in particular, a resin having an alicyclic structure (for example, a cyclic structure such as cyclohexane, norbornane, adamantane, tricyclodecane, tetracyclododecane, etc.). Specifically, for example, JP-A-10-152551, JP-A-2002-212500, JP-A-2003-20334, JP-A-2004-210932, JP-2006-199790, and 2007-2144. No. 2007, No. 2007-284650, No. 2008-105999, etc.) are preferable.

  The resin on the low Abbe number side preferably has an Abbe number (νd) of 30 or less, more preferably 25 or less, and particularly preferably 20 or less. The refractive index (nd) is preferably 1.60 or more, more preferably 1.63 or more, and particularly preferably 1.65 or more. Such a resin is preferably a resin having an aromatic structure. For example, a resin having a structure such as 9,9′-diarylfluorene, naphthalene, benzothiazole, benzotriazole (specifically, for example, JP-A-60- No. 38411, JP-A-10-67977, JP-A-2002-47335, 2003-23884, 2004-83855, 2005-325331, 2007-238883, International Publication. 2006/095610, the resin described in Japanese Patent No. 2537540, and the like) are preferable.

The resin composition used for forming the wafer level lens uses an organic-inorganic composite material in which inorganic fine particles are dispersed in a matrix for the purpose of increasing the refractive index or adjusting the Abbe number. This is also a preferred embodiment.
Examples of the inorganic fine particles in the organic-inorganic composite material include oxide fine particles, sulfide fine particles, selenide fine particles, and telluride fine particles. More specifically, for example, fine particles of zirconium oxide, titanium oxide, zinc oxide, tin oxide, niobium oxide, cerium oxide, aluminum oxide, lanthanum oxide, yttrium oxide, zinc sulfide, and the like can be given.

The inorganic fine particles may be used alone or in combination of two or more. Moreover, the composite by several components may be sufficient.
In addition, for various purposes such as reducing photocatalytic activity and water absorption, inorganic fine particles can be doped with different metals, or the surface can be coated with different metal oxides such as silica and alumina, silane coupling agents, titanate cups, etc. The surface may be modified with a ring agent, an organic acid (carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid, etc.), or a dispersant having an organic acid group.
The number average primary particle size of the inorganic fine particles may be usually about 1 nm to 1000 nm. However, if it is too small, the properties of the substance may change. If it is too large, the effect of Rayleigh scattering becomes significant. 15 nm is preferable, 2 nm-10 nm are still more preferable, and 3 nm-7 nm are especially preferable. Further, it is desirable that the particle size distribution of the inorganic fine particles is narrow. There are various ways of defining such monodisperse particles. For example, a numerical value range as described in JP 2006-160992 A applies to a preferable particle size distribution range.
Here, the above-mentioned number average primary particle size can be measured by, for example, an X-ray diffraction (XRD) apparatus or a transmission electron microscope (TEM).

  The refractive index of the inorganic fine particles is preferably 1.90 to 3.00, more preferably 1.90 to 2.70 at 22 ° C. and a wavelength of 589.3 nm, and more preferably 2.00 to 2 .70 is particularly preferred.

  In the organic-inorganic composite material, the content of the resin, which is a matrix of inorganic fine particles, is preferably 5% by mass or more, more preferably 10% by mass to 70% by mass from the viewpoint of transparency and high refractive index. 30 mass%-60 mass% is especially preferable.

The matrix resin used in the organic-inorganic composite material includes the UV curable resin, the thermosetting resin, the thermoplastic resin, the high Abbe number resin, and the low Abbe number resin described above as the material of the wafer level lens. Either can be used. Further, a resin having a refractive index higher than 1.60 described in JP-A-2007-93893, a block copolymer composed of a hydrophobic segment and a hydrophilic segment described in JP-A-2007-211114, and JP-A-2007 238929, Japanese Patent Application Nos. 2008-12645, 2008-208427, 2008-229629, and 2008-219952 can form arbitrary chemical bonds with inorganic fine particles at the polymer ends or side chains. Examples thereof include resins having functional groups and thermoplastic resins described in Japanese Patent Application Nos. 2008-197054 and 2008-198878.
In addition, additives, such as a plasticizer and a dispersing agent, can be added to the organic-inorganic composite material as necessary.

Here, preferred combinations of the matrix resin and the inorganic fine particles include the following.
That is, when a high Abbe number resin as described above is used as a matrix, it is preferable to disperse fine particles such as lanthanum oxide, aluminum oxide, and zirconium oxide as inorganic fine particles, and when a low Abbe number resin is used as a matrix. It is preferable to disperse fine particles such as titanium oxide, tin oxide, and zirconium oxide as inorganic fine particles.

  In order to uniformly disperse the inorganic fine particles, for example, a dispersant containing a functional group having reactivity with a resin monomer forming a matrix (for example, described in Examples of JP-A-2007-238884) , A block copolymer composed of a hydrophobic segment and a hydrophilic segment (for example, described in JP-A-2007-2111164), or a function capable of forming an arbitrary chemical bond with inorganic fine particles at the polymer terminal or side chain It is desirable to appropriately use a resin having a group (for example, described in JP2007-238929A, JP2007-238930A).

  In addition, in the resin composition used for forming the wafer level lens, known release agents such as silicon-based, fluorine-based, and long-chain alkyl group-containing compounds and additives such as antioxidants such as hindered phenols are appropriately used. It may be blended.

  Furthermore, a curing catalyst or an initiator can be blended in the resin composition used for forming the wafer level lens, if necessary. Specifically, for example, compounds that promote the curing reaction (radical polymerization or ionic polymerization) by the action of heat or active energy rays described in paragraph numbers [0065] to [0066] of JP-A-2005-92099 are listed. be able to. The amount of these curing reaction accelerators to be added varies depending on the type of catalyst and initiator, or the difference in the curing reactive site, and cannot be specified unconditionally, but in general, the total solid content of the resin composition About 0.1% by mass to 15% by mass is preferable, and about 0.5% by mass to 5% by mass is more preferable.

  The resin composition used for producing the wafer level lens of the present invention can be produced by appropriately blending the above components. At this time, if other components can be dissolved in a liquid low molecular weight monomer (reactive diluent), etc., it is not necessary to add a separate solvent, but if this is not the case, use a solvent. Thus, the resin composition can be produced by dissolving the constituent components. The solvent that can be used in the resin composition is not particularly limited and may be appropriately selected as long as the composition can be uniformly dissolved or dispersed without precipitation. Specifically, for example, ketones (Eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (eg, ethyl acetate, butyl acetate, etc.), ethers (eg, tetrahydrofuran, 1,4-dioxane, etc.) alcohols (eg, methanol, ethanol, isopropyl, etc.) Alcohol, butanol, ethylene glycol, etc.), aromatic hydrocarbons (eg, toluene, xylene, etc.), water and the like. When the resin composition contains a solvent, it is preferable to perform a mold shape transfer operation after casting the composition on a substrate and / or a mold and drying the solvent.

  The same material as the molding material of the lens 12 can be used for the substrate 10. Moreover, as long as the board | substrate 10 consists of materials, such as glass transparent with respect to visible light, you may form with the material different from the molding material of the lens 12. FIG. In this case, the material forming the substrate 10 is preferably a material having the same or very close linear expansion coefficient as the material forming the lens 12. When the linear expansion coefficients of the material forming the lens 12 and the material forming the substrate 10 are the same or close to each other, when reflow mounting of the wafer level lens on the image pickup unit, heating caused by different linear expansion coefficients The distortion and cracking of the lens 12 can be suppressed.

  Although not shown in FIGS. 1 and 2, an infrared filter (IR filter) may be formed on the surface of the substrate 10 on the light incident side.

  Hereinafter, with reference to FIGS. 3 to 8, the form and production of the wafer level lens will be described in detail by taking an example of a production method of the wafer level lens array.

[Wafer Level Lens Form and Fabrication (1)]
-Lens formation-
First, a method for forming the lens 12 on the substrate 10 will be described with reference to FIGS. 3 and 4A to 4C.
Here, FIG. 3 is a diagram showing a state in which a molding material (described as M in FIG. 3), which is a resin composition for lens formation, is supplied to the substrate 10.
4A to 4C are diagrams showing a procedure for forming the lens 12 on the substrate 10 with the mold 60. FIG.

  As shown in FIG. 3, the molding material M is dropped onto the portion of the substrate 10 where the lens 12 is molded using the dispenser 50. Here, an amount of the molding material M corresponding to one lens 12 is supplied to one part to be supplied.

After the molding material M is supplied to the substrate 10, a mold 60 for molding the lens 12 is disposed on the surface side of the substrate 10 to which the molding material M is supplied, as shown in FIG.
Here, the mold 60 is provided with recesses 62 for transferring the shape of the lens 12 in accordance with the desired number of lenses 12.

  As shown in FIG. 4B, the mold 60 is pressed against the molding material M on the substrate 10, and the molding material M is deformed following the shape of the recess 62. When the mold 60 is pressed against the molding material M and the molding material M is a thermosetting resin or an ultraviolet curable resin, the molding material M is cured by irradiating heat or ultraviolet rays from the outside of the mold 60. Let

  After the molding material M is cured, the substrate 10 and the lens 12 are released from the mold 60 as shown in FIG.

-Formation of light shielding film-
Next, with reference to FIGS. 5A to 5C, a method for forming the light shielding film 14 on the periphery of the lens 12 will be described.
Here, FIGS. 5A to 5C are schematic cross-sectional views showing a process of providing the light shielding film 14 on the substrate 10 on which the lens 12 is molded.

  The light-shielding film 14 is formed by a light-shielding coating layer forming step (see FIG. 5A) in which the black curable composition of the present invention is applied to the substrate 10 to form the light-shielding coating layer 14A. The light-shielding coating layer 14A is subjected to pattern exposure through a mask 70 (see FIG. 5B), and the exposed light-shielding coating layer 14A is developed to remove uncured portions, thereby forming a pattern. Development step (see FIG. 5C) for forming the light shielding film 14.

The light shielding film 14 can be formed arbitrarily before or after the lens 12 is manufactured. Here, a method after the lens 12 is manufactured will be described in detail.
Hereinafter, each process in the formation method of the light shielding film 14 is demonstrated.

<Light-shielding coating layer forming step>
In the light-shielding coating layer forming step, as shown in FIG. 5A, a black curable composition is coated on the substrate 10 to form a light-shielding coating layer 14A having a low light reflectance made of the black curable composition. Form. At this time, the light-shielding coating layer 14 </ b> A is formed so as to cover the surface of the substrate 10 and the surfaces of the lens surface 12 a and the lens edge portion 12 b of the lens 12.

There is no restriction | limiting in particular as the board | substrate 10 which can be used for this process. Examples include soda glass, alkali-free glass, Pyrex (registered trademark) glass, quartz glass, and transparent resin.
In addition, the board | substrate 10 said here says the form containing both the lens 12 and the board | substrate 10 in the aspect which forms the lens 12 and the board | substrate 10 integrally.
In addition, an undercoat layer may be provided on these substrates 10 as necessary in order to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the surface of the substrate 10.

As a method of applying the black curable composition on the substrate 10 and the lens 12, various coating methods such as slit coating, spray coating, ink jet method, spin coating, cast coating, roll coating, and screen printing are applied. can do.
The film thickness immediately after application of the black curable composition is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 5 μm, from the viewpoint of film thickness uniformity of the coating film and ease of drying of the coating solvent. 0.2 μm to 3 μm is more preferable.

  The light-shielding coating layer 14A applied on the substrate 10 can be dried (pre-baked) at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, oven, or the like.

  The coating film thickness after drying of the black curable composition (hereinafter referred to as “dry film thickness” as appropriate) can be arbitrarily selected from the desired performance such as light-shielding properties, and is generally from 0.1 μm to less than 50 μm. Range.

<Exposure process>
In the exposure step, the light-shielding coating layer 14A formed in the light-shielding coating layer forming step is exposed in a pattern. The pattern exposure may be scanning exposure, but as shown in FIG. 5B, a mode in which exposure is performed through a mask 70 having a predetermined mask pattern is preferable.

  In the exposure in this step, pattern exposure of the light-shielding coating layer 14A is performed through a predetermined mask pattern, and only the portion irradiated with light in the light-shielding coating layer 14A is cured by this exposure. Here, a mask pattern for irradiating light onto the surface of the lens edge 12b and the surface of the substrate 10 between the lenses 12 is used. By doing so, only the light-shielding coating layer 14 </ b> A in the region excluding the lens surface 12 a is cured by light irradiation, and this light-cured region forms the light-shielding film 14.

  As radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are particularly preferably used. This radiation may be a light source having a single wavelength, or a light source including all wavelengths such as a high-pressure mercury lamp may be used.

<Development process>
Next, by performing an alkali development process (development process), the light non-irradiated part in exposure, that is, the uncured region of the light-shielding coating layer 14A is eluted in the alkaline aqueous solution, and only the region cured by light irradiation is left.
Specifically, the light-shielding coating layer 14A exposed as shown in FIG. 5B is developed to form a light-shielding coating formed on the lens surface 12a as shown in FIG. 5C. Only the layer 14A is removed, and the cured light shielding film 14 is formed in the other region.

As the alkali agent contained in the developer (alkaline aqueous solution) used in the development step, any of organic or inorganic alkali agents and combinations thereof can be used. In the formation of the light-shielding film in the present invention, it is desirable to use an organic alkali agent from the viewpoint of hardly damaging surrounding circuits.
Examples of the alkaline agent used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0] -7-undecene and other organic alkaline compounds (organic alkaline agents), and inorganic compounds (inorganic alkaline agents) such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like. An alkaline aqueous solution diluted with pure water so that the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass, is preferably used as the developer.

  The development temperature is usually 20 ° C. to 30 ° C., and the development time is in the range of 20 seconds to 90 seconds.

  When a developer composed of such an alkaline aqueous solution is used, the unexposed portion of the coating film is generally removed with a developer and then washed (rinsed) with pure water. That is, after the development process, the excess developer is sufficiently washed and removed with pure water and further subjected to a drying step.

  In addition, after performing the light-shielding coating layer forming step, the exposure step, and the development step described above, the formed light-shielding film (light-shielding pattern) is cured by heating (post-baking) and / or exposure as necessary. A curing step may be included.

Post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 250 ° C. is performed. Conditions such as post-baking temperature and time can be appropriately set depending on the material of the substrate 10 or the lens 12. For example, when the substrate 12 is made of glass, 180 ° C. to 240 ° C. is preferably used within the above temperature range.
In this post-bake treatment, the light-shielding film 14 formed after development is continuously or batchwise heated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. This can be done with the formula

  In the above procedure, the case where the shape of the lens 12 is concave has been described as an example, but the shape is not particularly limited, and may be a convex shape or an aspherical shape. In the above procedure, a wafer level lens in which a plurality of lenses 12 are molded on one surface of the substrate 10 has been described as an example. However, a configuration in which a plurality of lenses 12 are molded on both surfaces of the substrate 10 may be used. In that case, a patterned light shielding film 14 is formed on both surfaces in a region excluding the lens surface.

[Wafer Level Lens Form and Fabrication (2)]
FIG. 6 is a diagram showing another configuration example of the wafer level lens array.
The wafer level lens shown in FIG. 6 has a configuration (monolithic type) in which the substrate 10 and the lens 12 are simultaneously molded using the same molding material.
When producing such a wafer level lens, the same molding material as described above can be used. In this example, a plurality of concave lenses 12 are formed on one surface (upper surface in the drawing) of the substrate 10, and a convex shape is formed on the other surface (lower surface in the drawing). A plurality of lenses 20 are formed. A patterned light shielding film 14 is formed on the substrate 10 except for the lens surface 12a, that is, on the surface of the substrate 10 and the surface of the lens edge 12b. As a patterning method for forming the light shielding film 14, the above-described procedure can be applied.

[Wafer Level Lens Form and Fabrication (3)]
Next, with reference to FIGS. 7A to 7C and FIGS. 8A to 8C, still another configuration example of the wafer level lens array and a procedure for manufacturing the same will be described.
Here, FIGS. 7A to 7C are schematic views showing other processes for forming the patterned light-shielding film 14.
FIGS. 8A to 8C are schematic views showing a process of forming the lens 12 after forming the patterned light-shielding film 14 first.

  In the example of the wafer level lens array shown in FIGS. 3 to 6, the patterned light shielding film 14 is formed on the substrate 10 on which the lens 12 is provided. However, in the procedure described below, first, the substrate 10 is formed. This is a procedure for forming the lens 12 on the substrate 10 after forming the patterned light shielding film 14 on the substrate 10.

-Formation of light shielding film-
First, as shown in FIG. 7A, a light-shielding coating layer forming step of forming a light-shielding coating layer 14A by applying a black curable composition on the substrate 10 is performed.

  Thereafter, the light-shielding coating layer 14A applied on the substrate 10 is dried at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds using a hot plate, oven, or the like. The dry film thickness of a black curable composition can be arbitrarily selected from performances, such as desired light-shielding property, and is the range of about 0.1 micrometer or more and less than 50 micrometers.

Next, as illustrated in FIG. 7B, an exposure process is performed in which the light-shielding coating layer 14 </ b> A formed in the light-shielding coating layer forming process is exposed in a pattern through a mask 70. The mask 70 has a predetermined mask pattern.
In the exposure in this step, the light-shielding coating layer 14 is subjected to pattern exposure to cure only the light-irradiated portion of the light-shielding coating layer 14A. Here, a mask pattern that irradiates light only to the light-shielding coating layer 14 </ b> A in a region excluding a portion that becomes the lens opening 14 a of the lens 12 when the lens 12 is molded in a subsequent process is used. By this method, only the light-shielding coating layer 14A in the region excluding the portion that becomes the lens opening 14a of the lens 12 is cured by light irradiation. As radiation that can be used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferably used, as in the procedure described above.

Next, by performing an alkali development process (development process), only the light-shielding coating layer 14A in the region corresponding to the lens opening 14a of the lens 12 which is an uncured region of the light-shielding coating layer 14A in the pattern exposure is converted into an alkaline aqueous solution. Is eluted. At this time, as shown in FIG. 7C, the light-cured light-shielding coating layer 14A in the region excluding the region of the lens opening 14a of the lens 12 remains on the substrate 10 to form the light-shielding film 14.
Here, as the alkaline agent in the alkaline aqueous solution as the developer, the same procedure as described above can be used.
After the development process, the excess developer is then washed away and dried.

  Also in this embodiment, after performing the light-shielding coating layer forming step, the exposure step, and the development step, the curing step of curing the formed light-shielding film by the above-described post-baking and / or exposure as necessary. You may give it.

  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 to the black curable composition, the surfactant described above as a surfactant that can be contained in the black curable composition may be added to the cleaning liquid.

-Lens formation-
Next, a process of forming the lens 12 after forming the light shielding film 14 will be described.
As shown in FIG. 8A, the molding material M constituting the lens 12 is dropped by the dispenser 50 on the substrate 10 on which the patterned light shielding film 14 is formed. The molding material M is supplied so as to partially include an end portion of the light shielding film 14 adjacent to the opening so as to cover a region corresponding to the lens opening 14 a of the lens 12.

  After the molding material M is supplied to the substrate 10, as shown in FIG. 8B, a mold 80 for molding a lens is disposed on the surface side of the substrate 10 to which the molding material M is supplied. The mold 80 is provided with concave portions 82 for transferring the shape of the lens 12 in accordance with the desired number of lenses 12.

  The mold 80 is pressed against the molding material M on the substrate 10, and the molding material M is deformed following the shape of the recess. When the mold 80 is pressed against the molding material M and the molding material M is a thermosetting resin or an ultraviolet curable resin, the molding material M is cured by irradiating heat or ultraviolet rays from the outside of the mold. .

  After the molding material M is cured, the substrate 10 and the lens 12 are released from the mold 80 to obtain a wafer level lens having a patterned light shielding film 14 on the substrate 10 as shown in FIG. 8C.

  As described above, the patterned light shielding film 14 provided in the wafer level lens is not only provided in the region excluding the lens surface 12a of the lens 12 as shown in FIG. 5, but also as shown in FIG. In addition, the light shielding film 14 may be provided in a region excluding the lens opening 14 a of the lens 12.

  The wafer level lens has a light shielding film 14 formed on a pattern on at least one surface of the substrate 10 and having a low light reflectance, while sufficiently shielding light in a region other than the lens surface 12a or the lens opening 14a of the lens 12. Generation of reflected light can be suppressed. For this reason, when applied to an imaging module having a solid-state imaging device, it is possible to prevent the occurrence of problems such as ghosts and flares associated with reflected light during imaging.

  Further, since the light shielding film 14 is provided on the surface of the substrate, it is not necessary to attach another light shielding member or the like to the wafer level lens, and an increase in manufacturing cost can be suppressed.

  Note that, in the case of a structure in which a surface having an uneven surface is provided around the lens as in the structure shown in the above-mentioned Patent Document 2, light incident on the structure is reflected or diverged, thereby causing a ghost or the like. There is a concern that these problems are likely to occur. Therefore, as shown in FIG. 5, if the patterned light shielding film 14 is provided in a region excluding the lens surface 12a of the lens 12, light can be shielded except the lens surface 12a, and optical performance can be improved. .

  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).
The scheme is shown below.

  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 38>
(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.
Each of the resins (J-1) to (J-18) was previously dissolved in propylene glycol methyl ether acetate (hereinafter referred to as “PGMEA”) to 30 mass%.

(Composition I)
-Titanium black A or titanium black B (described in Tables 3 and 4) 45 parts-30 parts by mass PGMEA solution of each resin (J-1) to (J-18) (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 Tables 3 and 4 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. The numbers in parentheses shown in Tables 3 and 4 are solid content values of the added resin.

(Preparation of black curable composition)
The composition of the following (Composition II) was added to the above titanium black dispersion and mixed with a stirrer to prepare each black curable composition of Examples 1 to 38.
(Composition II)
Alkali-soluble resin: Resin D-1 to Resin D-4 described in Tables 3 and 4 (structures are shown below), 30% by mass PGMEA solution (amounts described in Tables 3 and 4)
Polymerizable compound: 15.0 parts of dipentaerythritol hexaacrylate Polymerizable compound: 5.0 parts of pentaerythritol triacrylate Polymerization initiator: Compounds described in Tables 3 and 4 (structures are shown below) 20 0.0 part, solvent: PGMEA 50 parts, γ-methacryloxypropyltrimethoxysilane 0.1 part, fluorine-based surfactant (manufactured by DIC, MegaFuck F171) 0.05 part

<Example 39>
(Preparation of black curable composition using 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% by mass, manufactured by Sumitomo Osaka Cement Co., Ltd.) and silver colloid (average primary particle size: 7 nm, solid content: 20 g (20% by mass, manufactured by Sumitomo Osaka Cement Co., Ltd.) and a solution of 0.75 g of polyvinylpyrrolidone dissolved 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 40 and 41>
(Preparation of black curable composition using titanium black and organic pigment)
(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 composition of Examples 40 and 41 was 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 PO36 = 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 4, 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 in the preparation of the black curable composition of Example 1. The black curable composition of Example 4 was prepared.

  Tables 3 and 4 show specific resins used for the black curable compositions of Examples 1 to 41 and Comparative Examples 1 to 4, or comparative resins, alkali-soluble resins, and polymerization initiators. The polymerization initiators used are the compounds (C-1) to (C-6) shown below.

[Production and evaluation of light shielding film for wafer level lens on glass substrate]
(Coating process)
Examples 1-41 were applied to a 5 cm × 5 cm glass substrate (thickness: 1 mm, manufactured by Schott, BK7) by adjusting the spin coating coating rotation speed so that the film thickness after the heat treatment was 2.0 μm. And the black curable composition of Comparative Examples 1-4 was apply | coated uniformly, and it heat-processed for 120 second with the hotplate with a surface temperature of 120 degreeC. In this way, a black curable composition layer having a thickness of 2.0 μm was obtained.

(Exposure process)
Then, a black curable composition layer obtained, using a high-pressure mercury lamp, a 50 mJ / cm ² by exposure from the exposure amount 100 mJ / cm ² to 1000 mJ / cm ² through a photomask having a pattern shown in FIG. 9 Changed and exposed. In FIG. 9, a large portion of a 0.2 × 0.2 mm rectangular pattern having a circular hole portion having a diameter of 0.1 mm at the center portion in FIG. 9 and a lattice-shaped fine pattern having a line and space of 10 μm in the three portion. It is a pattern.

(Development process)
The black curable composition layer after the exposure was subjected to paddle development at 23 ° C. for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide. Thereafter, rinsing was performed with a spin shower, and further washing with pure water was performed to obtain a patterned light-shielding film.

<Evaluation of developability (residue) on glass substrate>
At the minimum exposure amount (adhesion sensitivity B) at which the fine pattern cannot be removed during development, the development part on the glass for 50 patterns was observed with a transmission electron microscope (SEM), and the number of residues per pattern The average value was obtained. The smaller the number of residues, the better the developability. The evaluation results are summarized in Table 5.

<Evaluation of adhesion on glass substrate>
Each black curable composition layer was formed on a glass substrate, and the following evaluation was performed using the substrate with a light-shielding film obtained by exposure, development, and rinsing.
The minimum exposure amounts at which the large pattern and the fine pattern were not peeled off during development were defined as adhesion sensitivity A and adhesion sensitivity B, respectively. The lower the adhesion sensitivity, the higher the adhesion, and the smaller the difference in adhesion sensitivity between the large pattern and the fine pattern, the better the pattern formability.

<Evaluation of film thickness uniformity on glass substrate>
The thickness from the central part of the substrate having the black curable composition layer having a thickness of 2.0 μm prepared in the coating process from the edge to the part within 10 mm in the diagonal direction is measured with a stylus-type film thickness meter DECTAC-3 (ULVAC ). The thickness unevenness was expressed by the following formula and expressed in “%”.
Unevenness of thickness = (thickness of the central part−thickness inside the edge 30 mm) / thickness of the central part

<Evaluation of light shielding properties on the substrate>
The maximum transmittance in the wavelength region of 400 nm to 800 nm was measured with a spectrophotometer (UV-3600, manufactured by Shimadzu Corporation) using the substrate in which the black curable composition layer prepared above was formed on a glass wafer. The smaller the value, the better. When the maximum transmittance is less than 1%, the light shielding property is good.
The evaluation results are summarized in Table 5.

From Table 5, it can be seen that by using the black curable composition of the present invention, the adhesion sensitivity of the large pattern and the fine pattern can be improved and the residue of the unexposed portion can be suppressed.
Moreover, the black curable composition using titanium black can provide the black curable composition suitable for producing the light shielding film for wafer level lenses.
Furthermore, as Table 4 shows, the black curable composition of Examples 1-37 containing titanium black as an inorganic pigment is the same as the black curable composition of Example 39 containing an inorganic pigment other than titanium black. In contrast, it can be seen that the adhesion sensitivity is particularly 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 40 and Example 41. FIG.

Example 42
In the same manner as in Example 4, a curable composition for lenses ((alicyclic epoxy resin (EHPE-3150 manufactured by Daicel Chemical Industries)) and arylsulfonium salt derivative (ADEKA manufactured by ADEKA) were formed on a substrate on which a patterned light-shielding film was formed. 1% by mass of SP-172) is used to form a curable resin layer, the shape is transferred with a quartz mold having a lens shape, and the exposure amount is 400 mJ / cm ² by a high-pressure mercury lamp. By curing, a wafer level lens array having a plurality of wafer level lenses was produced.

  The produced wafer level lens array was cut and a lens module was produced thereon, and then an imaging device and a sensor substrate were attached to produce an imaging unit.

  The wafer level lens obtained in Example 42 had no residue at the lens opening, had good transparency, had high uniformity of the coated surface of the light shielding layer, and had high light shielding properties. .

10 substrate 12 lens 14 light shielding film

Claims (10)

  (A) inorganic pigment, (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, a phosphate group, and a sulfone A copolymer comprising a monomer having at least one group selected from the group consisting of acid groups, and (b-3) a macromonomer having a weight average molecular weight of 1,000 to 50,000, (C) polymerization initiation A black curable composition for a wafer level lens comprising an agent, (D) a polymerizable compound, and (E) an alkali-soluble resin having an unsaturated double bond.   (A) The black curable composition for wafer level lenses according to claim 1, wherein the inorganic pigment is titanium black.   The black curing for a wafer level lens according to claim 1 or 2, 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. Sex composition.   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. Black curable composition for wafer level lens.   The black curable composition for wafer level lenses according to any one of claims 1 to 4, wherein at least one of the (b-2) monomers is at least acrylic acid or methacrylic acid.   The black curable composition for a wafer level lens according to any one of claims 1 to 5, wherein the (C) polymerization initiator is an oxime ester compound or a hexaarylbiimidazole compound.   The black curable composition for a wafer level lens according to any one of claims 2 to 6, wherein the titanium black has an average primary particle size of 30 nm or more and 65 nm or less.   Furthermore, (F) The black curable composition for wafer level lenses of any one of Claims 1-7 containing an organic pigment.   The wafer level lens which has the light shielding film obtained using the black curable composition for wafer level lenses of any one of Claims 1-8 in the peripheral part of the lens which exists on a board | substrate.   A camera module comprising the wafer level lens according to claim 9.