JP5518656B2 - Black polymerizable composition and method for producing black layer - Google Patents

Description

  The present invention relates to a black polymerizable composition using a specific alkali-soluble binder, in particular, a black polymerizable composition useful for forming a light-shielding region of a wafer level lens array in which a plurality of lenses are arranged on a substrate, and the black polymerization The present invention relates to a method for manufacturing a black layer using a sexual composition.

  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. ing.

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 for manufacturing an imaging unit, for example, only a lens is previously produced on a solid surface such as a glass wafer, cut into a size to be combined with an individual sensor, and combined with an imaging element that has been separated into pieces in advance. A method of manufacturing an imaging unit, a method of forming a plurality of lenses using only a resin using a mold, combining these on a sensor substrate, and then cutting the lens, cutting the lens into a size that can be combined with each sensor, A method of manufacturing an image pickup unit by combining with an individualized image pickup element is also included.
Hereinafter, each lens of the plurality of lenses formed on the lens substrate is referred to as a wafer level lens, and the lens group formed on the lens substrate is referred to as a wafer level lens array including the lens substrate.

  As a conventional wafer level lens array, a curable resin material is dropped on the surface of a parallel plate substrate made of a light transmissive material such as glass, and the resin material is shaped into a predetermined shape with a mold. And a plurality of lenses are known (see, for example, Patent Documents 1 and 2). In order to adjust the amount of light, other than the lens portion of the wafer level lens or a part of the lens may be coated and vapor-deposited with a black film or a metal film.

  In addition, as another wafer level lens array, a plurality of through holes are formed in a silicon substrate, a spherical lens material formed separately is disposed in each through hole, and the lens material is bonded to the substrate by soldering, and then the lens material is attached. Also known is a plurality of lenses formed by polishing (see Patent Document 3). In order to adjust the amount of light, these may be coated and vapor-deposited with a black film or a metal film.

In the case of vapor-depositing a metal, there are problems such as complicated processes and warping of the lens after vapor deposition, and improvements are required in terms of productivity and performance.
On the other hand, a method of applying a black polymerizable composition by a coating method is also used to form a light shielding region. However, when the light shielding property for light in the visible wavelength range is secured when used for a lens, the composition of the composition is polymerized. In this case, the exposure light source used for curing is not sufficiently exposed to at least one selected from g-line, h-line, and i-line, and curing does not proceed sufficiently. In the case of using a composition that requires an alkali development step for removing the part, there is a problem that the exposed part is peeled off.
In the black polymerizable composition, the use of a dispersion resin having a specific side chain structure in which the dispersibility of the black pigment is good has been proposed for the purpose of improving the light shielding property (see, for example, Patent Document 4). In addition, various black polymerizable compositions having good light-shielding properties and image-forming properties using a binder polymer having an acid group, which are used for a black matrix of a color filter, have been proposed (see, for example, Patent Documents 5 to 7). .)

Japanese Patent No. 3926380 International Publication No. 2008/102648 Pamphlet US Pat. No. 6,426,829 JP 2010-106268 A JP 2002-244294 A Japanese Patent Laid-Open No. 06-230215 JP 2006-251283 A

  An object of the present invention is to provide a black polymerizable composition useful for forming a light-shielding region for a wafer level lens, which can form a black cured film having excellent alkali developer resistance and light-shielding properties. An object of the present invention is to provide a method for producing a black layer that is useful as a light shielding region of a wafer level lens using the composition.

Usually, in a curable composition, a resin containing a carboxylic acid is used as an alkali-soluble group. However, when development is strengthened to remove a residue in an unexposed area, there is a problem that an image area is peeled off. Had.
The black polymerizable composition is usually used for forming a black matrix of a color filter and various light-shielding films. When this is used for a lens aperture, etc., the light-shielding composition covers a wide range of light from visible to infrared. Sex is required.
When forming a light-shielding film using a black polymerizable composition, it is generally imagewise exposed with a light source of 250 nm to 500 nm and then developed with an alkali developer, but black that shields light in the wavelength region of 250 nm to 500 nm. Since the material is contained, the light transmittance of the exposure light source may be insufficient, and the deep part of the formed film may not be sufficiently cured. When development was strengthened to prevent the reduction of the remaining film, strong acid carboxylic acid caused the penetration of the developing solution into the image area, and there was a concern that the black film might peel off due to a decrease in the strength of the image area. .

As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, a high pKa acid acid group is included in the acid group in order to suppress the penetration of the developer into the image area, that is, the uncured portion below the exposed area. It was found that by using a resin using a group, it was possible to achieve both good developability and suppression of peeling, and the present invention was completed.
That is, the configuration of the present invention is as follows.
The black polymerizable composition of the present invention comprises (A) a black material, (B) a polymerization initiator that is an oxime compound , (C) a polymerizable compound, and (D) a (meth) acrylic polymer having a main chain structure. , Styrene resin, and phenol resin, phenolic hydroxyl group, 2-methoxyphenol group, 2-chlorophenol group, methyl 2-hydroxybenzoate, 4-methylphenol group, 1,3-benzenediol group, 1 -Naphthol group, 1,2-benzenediol group, benzenesulfonamide group, N-acetylphenylbenzenesulfonamide group, 4-aminobenzenesulfonamide group, N-phenyl-4-aminobenzenesulfonamide group, and N- ( pKa selected from 4-acetylphenyl) -4-aminobenzene sulfonamide group has a greater than 5 functional groups Containing alkali-soluble binder polymer.
The black polymerizable composition of the present invention has (A) a black material, (B) a polymerization initiator that is an oxime compound, (C) a polymerizable compound, and (D) a functional group having a pKa greater than 5. It contains an alkali-soluble binder polymer selected from acrylic resins having a benzenesulfonamide group, polyhydroxystyrene, novolac resin, and resol resin.
As said (A) black material, titanium black is preferable from a light-shielding viewpoint.
In addition, it is preferable that the functional group having a pKa greater than 5 (D) the alkali-soluble binder polymer is a phenolic hydroxyl group or a sulfonamide group. A resin selected from the group consisting of hydroxystyrene, particularly a polymer containing the following structural unit, that is, a p-vinylphenol-containing structural unit in the molecule is preferable.
Also,

The black polymerizable composition of the present invention can further contain an organic solvent.
In addition, as its application, it is preferably used for forming a light shielding region of a wafer level lens.
When the light-shielding region of the wafer level lens is formed by the black polymerizable composition of the present invention, spray coating is preferable, so that it is a composition that can be applied by spraying and suppresses dripping or the like when applied to a situation. From the viewpoint of, it is preferable that the total content of the solid content excluding the solvent contained in the black polymerizable composition is in the range of 20% by mass to 35% by mass.

 The method for producing a black layer of the present invention includes a step of applying the black polymerizable composition of the present invention to a solid surface by spray coating to form a black polymerizable composition layer, and the formed black polymerizable composition layer And applying energy to the resin to cure. Here, it is preferable that the solid surface is a surface of a light shielding film forming region at a peripheral portion of the wafer level lens and the black layer is a light shielding region formed at a peripheral portion of the wafer level lens.

  According to the present invention, a black polymerizable composition useful for forming a light-shielding region for a wafer level lens, which is capable of forming a black cured film having excellent alkali developer resistance and light-shielding properties, and further, the black polymerizable property. A method for producing a black layer that is useful as a light-shielding region of a wafer level lens using the composition can be provided.

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.

Hereinafter, the black polymerizable composition of the present invention (hereinafter sometimes simply referred to as a polymerizable composition) will be described in detail.
(D) Alkali-soluble binder polymer having a functional group having a pKa greater than 5 First, the binder polymer which is a characteristic component of the polymerizable composition of the present invention will be described. Hereinafter, the alkali-soluble binder polymer having a specific (D) pKa having a functional group greater than 5 as defined in the present invention may be referred to as (D) a specific binder polymer.
The binder polymer usable in the present invention are those having a pKa having greater than 5 functional groups, the main chain structure, (meth) acrylic polymer, scan styrene resins, novolac resins, phenolic resins such as resole resins Etc. are used. In particular, (meth) acrylic polymers, styrene resins, and phenol resins are preferably used.

In the present invention, “(meth) acrylic polymer” means (meth) acrylic acid, (meth) acrylic acid ester (alkyl ester, aryl ester, allyl ester, etc.), (meth) acrylamide, and (meth). A copolymer having a (meth) acrylic acid derivative such as an acrylamide derivative as a polymerization component.
In this specification, when referring to either or both of "acryl" and "methacryl", Ru Kotogaa be referred to as "(meth) acrylic".

The “styrene resin” in the present invention is an aromatic compound such as benzene, naphthalene, anthracene, or heterocyclic ring in which an alkenyl group such as a vinyl group is directly linked, and / or an aromatic compound is a hydroxyl group, a carboxyl group, or a halogen atom. , Alkyl group, alkenyl group, alkynyl group, amino group, carbonyl group, ether group, alkoxycarbonyl group, oxycarbonyl group, cyano group, aryl group, alkoxy group, sulfide group, mercapto group and the like.
Polymerization can be performed by radical polymerization, cationic polymerization, or anionic polymerization. After polymerization, a desired styrene resin can be obtained by performing an alkali treatment, an acid treatment, or the like as necessary.

The binder polymer in the present invention preferably has an acid group having a high acid dissociation constant (pKa) relative to the carboxylic acid, and requires that the pKa has a functional group greater than 5, and the contained pKa has a functionality greater than 5. The group preferably has a pKa of 7 or more and less than 14, more preferably 8 or more and 11 or less.
In the present invention, the acid dissociation constant of the functional groups contained in the alkali-soluble polymer (pKa) will be described 5.5 to 11 functional groups. pKa is preferably in the range of 7-11, more preferably in the range of 8-11.
Specific examples of such functional groups include a phenol group (pKa = 9.99), a 2-methoxyphenol group (pKa = 9.99), a 2-chlorophenol group (pKa = 8.55), 2-hydroxybenzoic acid methyl group (pKa = 9.87), 4-methylphenol group (pKa = 10.28), 1,3-benzenediol group (pKa = 9.20), 1-naphthol group (pKa = 9.30), 1,2-benzenediol group (pKa = 9.45), benzenesulfonamide group (pKa = 10.00), N-acetylphenylbenzenesulfonamide group (pKa = 6.94), 4- Aminobenzenesulfonamide group (pKa = 10.58), N-phenyl-4-aminobenzenesulfonamide group (pKa = 6.30), N- (4-acetylphenoxy) ) -4-aminobenzene sulfonamide group (pKa = 7.61), and the like acetyl ethyl acetate group (pKa = 10.68) is.
Among these, a phenol group which may have a substituent on the aromatic group and a benzenesulfonamide group which may have a substituent on the aromatic group are preferable, and a phenol group (pKa 9-10) is preferable. Most preferably, it is particularly preferred that the phenol group be introduced in the form of p-vinylphenol.

The acid dissociation constant (pKa) described in the above specific examples is E.E. P. SERJEANT et al., “IONISATION CONSTRANTS OF ORGANIC ACIDS IN AQUEOUS SOLUTION” and JOHN A. It is a numerical value described by DEAN, “LANGE'S HAN DBOOK OF CHEMISTRY”.
As the alkali-soluble binder polymer having a functional group having a pKa larger than 5 as used in the present invention, specifically, an acrylic resin having a benzenesulfonamide group, polyhydroxystyrene, novolac resin, or resole resin is preferable. , most preferably a polyhydroxystyrene.

Hereinafter, the novolak resin and polyhydroxystyrene which are preferred (D) specific binder polymers in the present invention will be described in detail.
As a preferred form of the novolak resin suitably used in the present invention, for example, a resin containing a repeating unit represented by the following general formula (A) and having a polystyrene equivalent weight average molecular weight of 1,000 to 10,000 is suitable. It is mentioned as a thing.

In the general formula (A), m represents an integer of 0 to 3.
Examples of the novolak resin used as the binder in the present invention include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p- , M- / p- may be used) Alkali-soluble novolak resins such as mixed formaldehyde resins.

Specific examples of the polyhydroxystyrene that is a suitable binder polymer used in the present invention include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, 2- (o-hydroxyphenyl) propene, 2- Polymerize one or more hydroxystyrenes such as (m-hydroxyphenyl) propene and 2- (p-hydroxyphenyl) propene in the presence of a radical polymerization initiator, an anionic polymerization initiator, or a cationic polymerization initiator. Resin.
Further, for the purpose of adjusting developability, sensitivity, and the like, a resin modified by protecting a part of the phenol group with an ester, acetalizing or etherifying may be used as necessary.

(D) The specific binder polymer preferably has a mass average molecular weight of 1500 or more, more preferably 2000 or more and 100,000 or less, and most preferably 2000 or more and 20,000 or less. Moreover, it is preferable that a number average molecular weight is 1000 or more, and it is more preferable that it is 1500-100,000. The polydispersity (mass average molecular weight / number average molecular weight) is preferably 1.1 to 10.
In addition, the value measured by styrene conversion by GPC method is used for the weight average molecular weight.
(D) The specific binder polymer may be used alone or in combination of two or more.
The content of the binder polymer in the black polymerizable composition of the present invention is preferably from 5 to 75% by mass, preferably from 10 to 70% by mass, based on the total solid content, from the viewpoint of good image area strength and image formability. Is more preferable, and it is still more preferable that it is 10-60 mass%.
Here, the “total solid content” indicates the total amount of all components excluding the solvent in the polymerizable composition.

(A) Black material Examples of the black material used in the present invention include black pigments and black dyes. Further, as a black material, a red pigment, a blue pigment, a green pigment, a yellow pigment, an orange pigment, a violet pigment, a cyan pigment, a magenta pigment, and a gray pigment may be used as a black material by appropriately combining a plurality of types, or , Red dyes, blue dyes, green dyes, yellow dyes, orange dyes, violet dyes, cyan dyes, magenta dyes, and gray dyes may be used in combination as appropriate as a black material, but storage stability and safety A black pigment is selected from the viewpoint of the properties.
Examples of the black pigment include carbon black, which is an inorganic pigment, and black metal-containing inorganic pigments described below.
As the black metal-containing inorganic pigment, a metal oxide or metal containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag Nitrogen can be mentioned. These may be used alone or as a mixture of two or more.
Moreover, you may prepare so that it may have desired light-shielding property by using in combination with the inorganic pigment of another hue further to a black pigment.
Examples of specific inorganic pigments that can be used in combination 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 (1 type of zinc yellow, 2 types of zinc yellow), ultramarine blue, prussian blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, victoria green, bitumen blue (Prussian blue) ), Vanadium zirconium blue, chrome tin pink, pottery red, salmon pink and the like.
In particular, these black pigments and other inorganic pigments having other hues are used not only independently but also in combination with a plurality of types of pigments for the purpose of expressing light-shielding properties in a wide wavelength range from ultraviolet to infrared. Is possible.

From the viewpoint of light shielding and curability, the black material is preferably a silver and / or tin metal pigment, Tyran black, and titanium black is the most preferable from the viewpoint of light shielding in a wide wavelength range from ultraviolet to infrared. preferable.
In the present invention, titanium black is black particles having titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride.
The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and can also be treated with a water repellent material as disclosed in JP-A-2007-302836. .
The titanium black may be one or two kinds of black pigments such as complex oxides such as Cu, Fe, Mn, V, and Ni, cobalt oxide, iron oxide, and carbon black for the purpose of adjusting dispersibility and colorability. It may be contained in a combination of more than one species. In this case, the titanium black particles occupy 50% by mass or more of the pigment.

  Examples of commercially available titanium black products include Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, Ako Kasei Co., Ltd., and Tilac D manufactured by Mitsubishi Materials Corporation.

  Titanium black is produced by heating a mixture of titanium dioxide and metal titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, Japanese Patent Laid-Open No. Sho 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), etc. is not.

The average primary particle diameter of the titanium black particles is not particularly limited, but is preferably 3 to 2000 nm, more preferably 10 to 500 nm, and most preferably 10 to 100 nm from the viewpoint of dispersibility and colorability. It is.
The specific surface area of titanium black is not particularly limited, but the water repellency after surface treatment of such titanium black with a water repellent agent has a predetermined performance, and thus the value measured by the BET method is usually 5 to 150 m. ² / g approximately, and preferably from 20 to 100 m ² / g approximately.

The average primary particle diameter of the inorganic pigment according to the present invention typified by titanium black is preferably 5 nm to 0.01 mm, and the average primary particle is from the viewpoints of dispersibility, light shielding properties, and sedimentation with time. The diameter is preferably 10 nm to 1 μm.
As described above, in the black polymerizable composition of the present invention, (A) the black material may use only one kind of black pigment or black dye, a combination of a plurality of black pigments or black dyes, Two or more kinds of coloring materials such as a combination of a black pigment or black dye and a pigment or dye of another hue, or a combination of pigments or dyes of other hues other than black may be used in combination. That is, as will be described later, a black pigment and an organic pigment or dye of another hue may be used in combination as desired for the purpose of adjusting the light shielding property.
The content of the (A) black material in the black polymerizable composition is preferably 5 to 70% by mass and more preferably 10 to 50% by mass with respect to the total mass of the composition.

(A) When a pigment is used as a black material and blended in a black polymerizable composition, blending the pigment in advance with a known pigment dispersant can be formulated as a pigment dispersion. It is preferable from the viewpoint of uniformity. As the pigment dispersant (hereinafter, also simply referred to as “dispersant”), for example, a known pigment dispersant or surfactant can be appropriately selected and used.

(Pigment dispersant)
As the pigment dispersant, known compounds can be arbitrarily selected and used, and commercially available dispersants, surfactants, and the like can also be used. Specific examples of commercially available products that can be used as the dispersant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Nonionic surfactants such as octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic systems such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) Surfactant: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals) Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, Various Solsperse dispersants (manufactured by Nippon Lubrizol Co., Ltd.) such as 26000, 28000, 32000, 36000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by ADEKA Co., Ltd.) and Ionette S-20 (manufactured by Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 11 , It includes the 130,140,142,162,163,164,166,167,170,171,174,176,180,182,2000,2001,2050,2150 (BYK Chemie Co., Ltd.). In addition, amphoteric dispersants such as Hinoact T-8000E manufactured by Kawaken Fine Chemical Co., Ltd. are also included.
In addition, an oligomer or polymer having a polar group at the molecular end or side chain, such as an acrylic copolymer, can also be suitably used as the dispersant. Further, polyethyleneimine having a weight average molecular weight of 300 to 20,000 or an amino resin in which a polyester chain is added to the amino group of polyallylamine can be used as a dispersant.

  From the viewpoints of dispersibility, developability and sedimentation, preferably, the following resins described in JP 2010-106268 A previously proposed by the applicant of the present application are preferable, and in particular, from the viewpoint of dispersibility, the side chain A polymer dispersant having a polyester chain is preferable, and a resin having an acid group and a polyester chain is preferable from the viewpoint of dispersibility and resolution of a pattern formed by a photolithography method. As a preferable acid group in the pigment dispersant, an acid group having a pKa of 6 or less is preferable from the viewpoint of adsorptivity, and carboxylic acid, sulfonic acid, and phosphoric acid are particularly preferable.

The dispersion resin described in JP 2010-106268 A that is preferably used in the present invention will be described below.
A preferable dispersion resin is a graft copolymer having a graft chain selected from a polyester structure, a polyether structure, and a polyacrylate structure, in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000 in the molecule. A graft copolymer containing a structural unit represented by any one of the following formulas (1) to (5).

[In Formula (1) to Formula (5), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and X ⁶ each independently represent a hydrogen atom or a monovalent organic group, Y ¹ , Y ² , Y ³ , Y ⁴ and Y ⁵ each independently represent a divalent linking group, and Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ each independently represent a hydrogen atom or Represents a monovalent organic group. R represents a hydrogen atom or a monovalent organic group, and R having a different structure may exist in the copolymer. n, m, p, q, and r each represent an integer of 1 to 500. j and k are each independently an integer of 2 to 8. ]
Especially, the compound which has a polyester chain in a side chain shown by the said Formula (1) is preferable. As typical examples of these, Exemplified Compound 1 to Exemplified Compound 71 described in Paragraph Nos. [0046] to [0078] of JP-A-2010-106268 can be suitably used also as a dispersant in the present invention.
In addition, although the exemplary compound 1-the exemplary compound 50 are described below as a suitable dispersing agent for this invention, this invention is not restrict | limited to these. In the following exemplary compounds, a numerical value written together with each structural unit represents the content of the structural unit [mass%: appropriately described as (wt%)].

From the viewpoints of dispersibility, developability and sedimentation, a resin having a polyester chain in the side chain is preferable, and from the viewpoint of dispersibility and resolution, a resin having an acid group is further preferable. As a preferable acid group, an acid group having a pKa of 6 or less is preferable from the viewpoint of adsorptivity, and an acid group derived from carboxylic acid, sulfonic acid, or phosphoric acid is particularly preferable.
Most preferably, from the viewpoints of solubility in a dispersion solution, dispersibility, and developability, a resin in which the polyester chain is a polycaprolactone side chain and has a carboxylic acid group is preferable.
In the case of using a pigment, first, after adjusting the pigment dispersion composition using the pigment, the dispersant as described above, and an appropriate solvent, it may be added to the black polymerizable composition from the viewpoint of improving dispersibility. To preferred.

  As content of the pigment dispersant at the time of preparing a pigment dispersion, it is 1 mass%-90 mass with respect to the total solid content mass of the coloring agent (a black pigment and another coloring agent are included) in a pigment dispersion. % Is preferable, and 3% by mass to 70% by mass is more preferable.

(B) Polymerization initiator The black polymerizable composition of the present invention essentially contains a polymerization initiator that is an oxime compound .
The polymerization initiator in the black polymerizable 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.
Moreover, when starting superposition | polymerization with a heat | fever, the initiator decomposed | disassembled at 150 to 250 degreeC is preferable.

The polymerization initiator that can be used in the present invention is preferably a compound having at least an aromatic group. For example, (bis) acylphosphine oxide or esters thereof, an acetophenone compound, an α-aminoketone compound, a benzophenone compound, Benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime ester compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, benzoin ether compounds Onium salt compounds such as ketal derivative compounds and metallocene compounds, organoboron salt compounds, and disulfone compounds.
From the viewpoint of sensitivity, oxime ester compounds, acylphosphine oxide compounds, acetophenone compounds, α-aminoketone compounds, trihalomethyl compounds, hexaarylbiimidazole compounds, and thiol compounds are preferred. In this invention, the polymerization initiator which is an oxime ester compound is contained essential.
Hereinafter, examples of the polymerization initiator that is an oxime compound suitable for the present invention and other polymerization initiators will be given, but the present invention is not limited thereto.

Specific examples of the acetophenone compound include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and p-dimethylaminoacetophenone. 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-methyl -1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl- 2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] Examples include -1-butanone and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one. Among them, as a commercially available compound that is preferably used, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [trade name “Irgacure-907 (manufactured by Ciba Specialty Chemicals) )].
In addition, α-alkylaminophenone [Irgacure-379 (manufactured by Ciba Specialty Chemicals)] and the like are also preferably mentioned as commercially available initiators.

  As the trihalomethyl compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6-tris (Monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (Trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

  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) biidazole, 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.

  As an acylphosphine oxide compound, for example, [2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide] is available under the trade name of Darocur TPO (manufactured by Ciba Japan), and [bis (2, 4,6-trimethylbenzoyl) -phenylphosphine oxide] is available under the trade name Irgacure 819 (manufactured by Ciba Japan).

Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Examples of the commercially available products include IRGACURE OXE 01 (1.2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)]), IRGACURE OXE manufactured by Ciba Specialty Chemicals. 02 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime)) and the like are preferable.
Furthermore, the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A can also be suitably used.
Most preferred examples include an oxime compound having a specific substituent described in JP-A-2007-269977 and an oxime compound having a thioaryl group disclosed in JP-A-2009-191061.
The following oxime compounds are also preferably used.

  The oxime compound 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 particularly preferably has high absorbance at 365 nm and 455 nm.

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 3,000 to 300,000, more preferably from 5,000 to 300,000, more preferably from 10,000 to 200,000, from the viewpoint of sensitivity. It is particularly preferred that
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

The photoinitiator which contains an oxime compound essentially may be used individually by 1 type, and may use 2 or more types together.
The content of the photopolymerization initiator in the polymerizable composition of the present invention is preferably 0.01% by mass to 30% by mass, more preferably 0.1% by mass to 20% by mass, and 0.1% by mass to 15%. Mass% is particularly preferred.

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

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, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 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.

Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are via ethylene glycol and propylene glycol residues are preferable. These oligomer types can also be used.
Also, urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, Urethane compounds having an ethylene oxide skeleton described in JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, by using 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, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed. Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp), 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.
In addition, 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 a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.
Also suitable are dipentaerythritol hexaacrylate, succinic acid monomer of dipentaerythritol pentaacrylate, dipentaerythritol triacrylate, and the like.
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.
(B) Although there is no restriction | limiting in particular as long as sufficient hardening reaction advances as content in the black polymeric composition of a polymeric compound, For example, it is 3 to 100 parts of total solids in conversion of mass. 55 parts are preferable, More preferably, it is 10-50 parts. (B) When the content of the polymerizable compound is within the above range, a sufficient curing reaction proceeds.

(E) Other additives In addition to the essential components (A) to (D) and the pigment dispersant, various additives can be used in the black polymerizable composition of the present invention depending on the purpose. .
(E-1) Binder polymer having a structure different from that of component (D) In the black polymerizable composition, for the purpose of improving the film properties, the structure different from that of the component (D), if necessary. (E-1) may be used as long as the effects of the present invention are not impaired. It is preferable to use a linear organic polymer as the binder. As such a “linear organic polymer”, a known one can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer.
For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. , JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a resin obtained by homo- or copolymerization of a monomer having a carboxyl group, acid anhydride Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride, etc. It is done. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane-based binder polymers containing acid groups described in Japanese Patent No. 271741 and Japanese Patent Application No. 10-116232 are very excellent in strength and are advantageous in terms of suitability for low exposure.
In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance of film strength and developability. In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.
The content in the case of using (E-1) another binder polymer that can coexist in the total solid content of the black polymerizable composition of the present invention is preferably 0.1 to 10.0% by mass, and suppresses pattern peeling. From the viewpoint of coexistence of development residue suppression, 0.3 to 6.0% by mass is more preferable, and 1.0 to 5.0% by mass is more preferable.

(E-2) Other colorant In the present invention, it is possible to use a colorant other than inorganic pigments such as known organic pigments and dyes in order to develop desired light-shielding properties.
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, and the like. Among these, pigments that can be preferably used include the following. However, the present invention is not limited to these.
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

The dye that can be used as the colorant is not particularly limited, and a known dye can be selected and 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 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.
The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

(E-3) Organic solvent The black polymerizable composition of the present invention can generally be constituted using an organic solvent. The organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the polymerizable composition are satisfied, but in particular, considering the solubility, coating property, and safety of the UV absorber and the binder. It is preferable to select the kind and amount so as to obtain an appropriate viscosity solid content concentration. Moreover, when preparing the polymeric composition in this invention, it is preferable that at least 2 type of organic solvent is included.

  Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. , Alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), alkyl 3-oxypropionate Esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) )), 2- Xylpropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy) Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2- Methyl methyl propionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. And as ethers For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone and aromatic hydrocarbons such as toluene, Xylene and the like are preferred.

  It is also preferable to mix two or more of these organic solvents from the viewpoints of the solubility of the alkali-soluble resin and the improvement of the coated surface. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

In the case of using the organic solvent in the polymerizable composition of the present invention, the content is preferably such that the total solid concentration of the composition is 5 to 80% by mass from the viewpoint of coatability, and 5 to 60% by mass. % Is more preferable, and 10 to 50% by mass is particularly preferable.
In addition, when the black polymerizable compound of the present invention is applied to spray coating, it can be spray coated and included in the black polymerizable composition from the viewpoint of suppressing dripping when applied to a curved surface. The amount of the organic solvent is preferably such that the total solid content excluding the solvent is in the range of 20 to 35% by mass, that is, in the range of 65 to 80% by mass.

(E-4) Sensitizer The black polymerizable composition may contain a sensitizer for the purpose of improving the radical generation efficiency of the polymerization initiator (B) 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 is preferably in the range of 0.1 to 30% by mass and preferably in the range of 1 to 20% by mass with respect to the mass of the total solid content of the black polymerizable composition from the viewpoint of sensitivity and storage stability. Is more preferable, and the range of 2 to 15% by mass is still more preferable.
(E-5) Polymerization inhibitor A small amount of polymerization inhibitor may be added to the black polymerizable composition in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the composition. 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 polymerizable composition.
If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and may be unevenly distributed on the surface of the coating film during the drying process after coating. . The amount of the higher fatty acid derivative added is preferably from about 0.5 to about 10% by weight of the total composition.

(E-6) Adhesion improver An adhesion improver can be added to the black polymerizable composition in order to improve the adhesion to a hard surface such as a support. 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, 3-methacryloxypropyldimethoxymethylsilane, γ-aminopropyltriethoxysilane, and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyldimethoxymethylsilane are preferable.
0.5-30 mass% is preferable in the total solid of a black polymeric composition, and, as for the addition amount of an adhesion improving agent, 0.7-20 mass% is more preferable.
In particular, when the resist of the present invention forms a glass substrate lens, it is preferable to add an adhesion improver from the viewpoint of improving sensitivity.

(E-7) Surfactant Various surfactants may be added to the black polymerizable 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 polymerizable 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 polymerizable 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 within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a black polymerizable composition.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (above, manufactured by Asahi Glass Co., Ltd.), Solsperse 20000 (Nippon Rouble) Zole Co., Ltd.).

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, etc. It is.

  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 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 surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.
Only one type of surfactant may be used, or two or more types may be combined.
The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the black polymerizable composition. .

(E-8) Other additives Furthermore, for black polymerizable compositions, the sensitivity of the sensitizing dye and initiator to active radiation is further improved, or the inhibition of polymerization of the photopolymerizable compound by oxygen is suppressed. A co-sensitizer may be contained for the purpose. Moreover, you may add well-known additives, such as surfactant, a diluent, a plasticizer, a fat-sensitizing agent, as needed, in order to improve the physical property of a cured film.

  The black polymerizable composition of the present invention comprises (A) a black material (preferably as a pigment dispersion composition containing a black metal-containing inorganic pigment and a pigment dispersant), (B) a polymerization initiator, and (C). A polymerizable compound and various additives that are used in combination as required can be contained together with (E-3) an organic solvent, and an additive such as a surfactant can be mixed therewith as necessary.

Since the black polymerizable composition of the present invention has the above-described configuration, it can be cured with high sensitivity and can form a light-shielding film having excellent light-shielding properties. In addition, since (D) an alkali-soluble binder polymer containing a specific acid group is contained, a high-definition light-shielding pattern is formed, which is useful for forming a light-shielding film for a wafer level lens.
In forming the light-shielding film, since it is preferable to apply to the solid surface by spray coating, as described later, from the viewpoint of preventing dripping when applied to a curved surface, the total solid content excluding the solvent is excluded. The content is preferably in the range of 20% by mass to 35% by mass.

<Wafer level lens>
The black polymerizable composition of the present invention is suitably used for forming a light shielding film for a wafer level lens.
Hereinafter, a wafer level lens to which the black polymerizable composition of the present invention is applied will be described.

FIG. 1 is a plan view showing an example of the configuration of a wafer level lens. FIG. 2 is a cross-sectional view of the wafer level lens shown in FIG.
As shown in FIG. 2, the wafer level lens includes a substrate 10 and a plurality of lenses 12 arranged on the substrate 10. The plurality of lenses 12 are arranged one-dimensionally or two-dimensionally with respect to the substrate 10. In addition, a light shielding film 14 is provided between the plurality of lenses 12 to prevent light transmission from places other than the lenses. The black polymerizable composition of the present invention is used for forming the light shielding film 14.
In the present embodiment, a configuration in which a plurality of lenses 12 are two-dimensionally arranged with respect to the substrate 10 as illustrated 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.
Here, an example is given, but the wafer level lens according to 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.
The energy curable resin composition used for the wafer level lens may be either a resin composition that is cured by heat or a resin composition that is cured by irradiation with active energy rays (for example, 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 used for forming the wafer level lens 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. An epoxy resin 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.
A phenol resin 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.

Examples of the thermosetting resin used for forming the wafer level lens include an epoxy resin, a siloxane resin, and a silyl group-containing resin. 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, and Toray Dow Examples thereof include SR-7010 manufactured by Corning.
Examples of the thermoplastic resin used for forming the wafer level lens include a polycarbonate resin, a polysulfone resin, and a polyether sulfone resin. Polycarbonate 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. A polysulfone resin 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 optical glass has a linear expansion coefficient of 4.9 to 14.3 [10 ⁻⁶ / K] at 20 ° C., and a refractive index of 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.

  From the viewpoint of moldability such as mold shape transfer suitability, it is preferable that the resin has appropriate fluidity before curing. Specifically, it is liquid at room temperature and has a viscosity of about 1000 to 50000 mPa · s.

  On the other hand, it is preferable to have 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, an alicyclic structure such as cyclohexane, norbornane, tetracyclododecane, an aromatic ring structure such as benzene and naphthalene, a cardo structure such as 9,9′-biphenylfluorene, 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, JP-A-5-20 027, 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, and refractive index characteristics.

  From the viewpoint of shape transfer accuracy, a resin composition having a small volume shrinkage due to the curing reaction is preferable. The curing shrinkage rate of the resin composition used in the present invention 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, 2004-302293, and 2007). No. -21247, etc., 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, particularly preferably 1,000 to. 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 in the range of 100 to 5,000. And (2) contains non-reactive substances (organic / inorganic fine particles, non-reactive resins, etc.). Fat composition (for example, described in JP-A-6-298883, JP-A-2001-247793, JP-A-2006-225434, etc.), (3) Resin composition containing a low-shrinkage crosslinking reactive group (for example, ring-opening) A polymerizable group (for example, an epoxy group (for example, described in JP-A No. 2004-210932), an oxetanyl group (for example, described in JP-A No. 8-134405), an episulfide group (for example, JP-A No. 2002-105110) ), Cyclic carbonate groups (for example, described in JP-A-7-62065), etc., ene / thiol curing groups (for example, described in JP-A 2003-20334), hydrosilylation curing groups (For example, described in JP-A-2005-15666) etc.), (4) Rigid skeleton resin (fluorene, adamantane, isophorone, etc.) (5) Resin composition containing two types of monomers having different polymerizable groups to form an interpenetrating network structure (so-called IPN structure) (E.g., described in JP-A-2006-131868), (6) resin compositions containing expandable substances (e.g., described in JP-A-2004-2719, JP-A-2008-238417, etc.) and the like. And 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 the wafer level lens according to the present invention, two or more types of resin compositions having different Abbe numbers are desired.
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.
Such a resin is preferably an aliphatic resin, particularly a resin having an alicyclic structure (for example, a resin having a cyclic structure such as cyclohexane, norbornane, adamantane, tricyclodecane, tetracyclododecane, specifically, for example, JP-A-10-152551, JP-A-2002-212500, JP-A-2003-20334, JP-A-2004-210932, JP-2006-199790, JP-2007-2144, JP-2007-284650. And the resin described in JP-A-2008-105999.

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.
As such a resin, a resin having an aromatic structure is preferable. For example, a resin having a structure such as 9,9′-diarylfluorene, naphthalene, benzothiazole, benzotriazole (specifically, for example, JP-A-60-38411). Publication No. 10-67977, No. 2002-47335, No. 2003-238842, No. 2004-83855, No. 2005-325331, No. 2007-238883, International Publication 2006. / 095610 publication, Japanese Patent No. 2537540 publication, etc.) are preferable.

It is also preferable to use an organic-inorganic composite material in which inorganic fine particles are dispersed in a matrix for the purpose of increasing the refractive index and adjusting the Abbe number as the resin used for forming the wafer level lens. It is an aspect. Examples of the inorganic fine particles 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, zinc sulfide and the like can be mentioned.
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.
In particular, it is preferable to disperse fine particles such as lanthanum oxide, aluminum oxide, and zirconium oxide for the high Abbe number resin, and titanium oxide, tin oxide, zirconium oxide, and the like for the low Abbe number resin. It is preferable to disperse the fine particles. 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, the inorganic fine particles are doped with different metals, the surface layer is coated with different metal oxides such as silica and alumina, silane coupling agents and titanate cups. 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 particle size of the inorganic fine particles is usually about 1 nm to 1000 nm, but if it is too small, the properties of the substance may change. If it is too large, the influence of Rayleigh scattering becomes remarkable, so 1 nm to 15 nm is preferable. 2 nm to 10 nm are more preferable, and 3 nm to 7 nm are particularly 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-A No. 2006-160992 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 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 photocatalytic activity reduction and water absorption reduction, the inorganic fine particles are doped with different metals, the surface layer is coated with different metal oxides such as silica and alumina, silane coupling agents, The surface may be modified with an acid coupling agent, an organic acid (carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid, etc.) or a dispersant having an organic acid group.

  If the number average particle size of the inorganic fine particles is too small, the properties of the substance may change. In addition, when the refractive index difference between the resin matrix and the inorganic fine particles is large, if the number average particle size of the inorganic fine particles is too large, the influence of Rayleigh scattering becomes significant. For this reason, 1 nm-15 nm are 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-A No. 2006-160992 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.

  The content of the inorganic fine particles with respect to the resin is preferably 5% by mass or more, more preferably 10 to 70% by mass, and particularly preferably 30 to 60% by mass from the viewpoint of transparency and high refractive index.

  As the resin used as the matrix used in the organic-inorganic composite material, any of the ultraviolet curable resin, thermosetting resin, and thermoplastic resin described above can be used as the material for the wafer level lens. 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 terminals or side chains. Examples thereof include resins having functional groups and thermoplastic resins described in Japanese Patent Application Nos. 2008-197054 and 2008-198878. If necessary, additives such as a plasticizer and a dispersant can be added to the organic-inorganic composite material.

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

  In addition, the resin composition to be used in the present invention appropriately contains additives such as known release agents such as silicon-based, fluorine-based, and long-chain alkyl group-containing compounds and antioxidants such as hindered phenols. May be.

  In the present invention, a curing catalyst or an initiator can be blended in the resin composition used for forming the 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, etc. Can do. The amount of these curing reaction accelerators to be added varies depending on the type of catalyst and initiator, the difference in the curing reactive site, etc., and cannot generally be specified, but in general, the total amount of the curing reactive polymerizable composition is not limited. About 0.1-15 mass% is preferable with respect to solid content, and about 0.5-5 mass% is more preferable.

  The resin composition used for producing the wafer level lens according to the present invention can be produced by appropriately blending the above components. At this time, if other components can be dissolved in the 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. A resin composition can be produced by dissolving each component. The solvent that can be used in the resin composition is not particularly limited and may be appropriately selected as long as the composition is 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.

[Formation of wafer level lens]
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 linear expansion coefficient as the material forming the lens 12 but very close. When the linear expansion coefficients of the material forming the lens 12 and the material forming the substrate 10 are the same or approximate to each other, during reflow mounting of the wafer level lens on the imaging unit, heating caused by different linear expansion coefficients The distortion and cracking of the lens 12 can be suppressed.
Although not shown, an infrared filter (IR filter) may be formed on the light incident side surface of the substrate 10.

  FIG. 3 is a view showing a state in which a resin (denoted as M in FIG. 3) as a molding material is supplied to the substrate. As shown in FIG. 3, the molding material M is dropped onto the portion of the substrate 10 where the lens is to be 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, as shown in FIG. 4A, a mold 60 for molding a lens is disposed. The mold 60 is provided with recesses 62 for transferring the shape of the lens 12 according to the desired number of lenses 12.

  As shown in FIG. 4B, the mold 60 is pressed against the molding material M on the substrate 1, and the molding material M is deformed following the shape of the recess. 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. .

  After the molding material M is cured, the substrate 1 and the lens 12 are released from the mold 60 as shown in FIG. 4C.

5A to 5C are schematic cross-sectional views showing a process of providing a light shielding film on a substrate on which a lens is molded.
[Formation of light-shielding film: preparation method of black layer]
Next, a method for producing a patterned light-shielding film, that is, a black layer will be described.
In the method for producing a black layer of the present invention, a black polymerizable composition layer is formed by applying the black polymerizable composition according to any one of claims 1 to 9 to a solid surface by spray coating. A step and a step of applying energy to the formed black polymerizable composition layer and curing it. When forming the light shielding film of the wafer level lens as in this embodiment, the black layer becomes the light shielding film of the wafer level lens by using the wafer level lens as the solid.

The light-shielding film forming method includes a light-shielding coating layer forming step in which the black polymerizable composition of the present invention is coated on the substrate 10 to form a black polymerizable composition coating layer 14A, and the coating layer 14A is masked. 16 includes an exposure step of pattern exposure through 16 and a development step of developing the exposed coating layer to remove uncured portions and forming a patterned light-shielding film 14. The formation of the patterned light-shielding film can be arbitrarily performed before or after the lens 12 is manufactured.
Hereafter, each process in the manufacturing method of this invention is demonstrated.

<Black polymerizable composition coating layer forming step>
In the coating layer forming step, as shown in FIG. 5A, a black polymerizable composition is coated on the substrate 10 to form a coating layer 14A having a low light reflectance made of the curable composition. At this time, the light shielding layer 14 </ b> A is formed so as to cover all of 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, 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 1 as necessary for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the surface of the substrate 1.

As a method for applying the black polymerizable composition to 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. However, the spray coating method is preferable from the viewpoint of the coating property with respect to the substrate having unevenness.
Specific examples of the coating layer used in the spray coating method include an ultrasonic spray coating apparatus, a two-fluid spray coating apparatus, and a one-fluid spray coating apparatus. By forming a light-shielding film by spray coating using these coating layer bases, it is possible to improve the film property of the concavo-convex part and obtain good light-shielding properties.

  The film thickness immediately after application of the black polymerizable 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 layer 14A (black polymerizable composition coating layer) applied on the substrate 10 can be dried (prebaked) 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 thickness after drying of the black polymerizable composition (hereinafter, referred to as “dry thickness” as appropriate) can be arbitrarily selected from performance such as desired 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 layer 14A (black polymerizable composition coating layer) formed in the 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 exposure in this step, pattern exposure of the coating layer 14A is performed through a predetermined mask pattern, and only the portion irradiated with light in the 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 coating layer 14A in the region excluding the lens surface 12a is cured by light irradiation, and this 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 portion in the exposure, that is, the uncured region of the coating layer 14A is eluted in the alkaline aqueous solution, and only the region cured by light irradiation is left. In this example, only the coating layer 14A formed on the lens surface 12a is removed, and the cured light shielding film 14 is formed in other regions. (See FIG. 5C).
As the alkali agent contained in the developer 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, an organic alkali developer is desirable 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 the like, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like. The concentration of these alkali agents is 0.001% by mass to 10%. An alkaline aqueous solution diluted with pure water so as to have a mass%, preferably 0.01 mass% to 1 mass%, is preferably used as the developer.
The development temperature is usually 20 ° C. to 40 ° C., and the development time is in the range of 10 seconds to 300 seconds. These can be repeatedly developed as necessary.
Since the black polymerizable composition of the present invention has the above-described configuration, it is excellent in alkali resistance, severe current conditions, and even when the remaining film of the non-image area is completely eliminated, the strength of the image area is reduced. The resulting light shielding film has an advantage that the peeled image is suppressed, and a light shielding film having excellent image forming property, high definition and high strength is formed.
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 processing, the excess developer is sufficiently washed and removed with pure water, and further subjected to a drying step.

  In the manufacturing method of the present embodiment, after the above-described coating layer forming step, exposure step, and development step are performed, the formed light shielding pattern is heated (post-baked) and / or exposed as necessary. It may include a curing step for curing.

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 or lens. For example, when the substrate is made of glass, 180 ° C. to 240 ° C. is preferably used in the above temperature range.
In this post-baking process, the light-shielding film 14 formed after the 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. It can be done with a 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 1 has been described as an example. However, a configuration in which a plurality of lenses 12 are molded on both surfaces may be used. In other words, the light shielding layer 14 is patterned on both surfaces except for the lens surface.

  FIG. 6 is a diagram showing another configuration example of the wafer level lens. The wafer level lens of FIG. 6 has a configuration (monolithic type) in which the substrate 10 and the lens 12 are simultaneously molded with the same molding material. As the molding material, the same materials 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 lens 20 is formed on the other surface (lower surface in the drawing). A plurality of are formed. The light shielding layer 14 is patterned in a region excluding the lens surface 12a of the substrate 1, that is, the surface of the substrate 10 and the surface of the lens edge portion 12b. The above-described procedure can be applied to the patterning of the light shielding layer 14.

  Next, another procedure for patterning the light shielding layer will be described. In the above-described example, the light shielding layer is patterned on the substrate on which the lens is provided. However, in the procedure described below, the light shielding layer is patterned on the substrate and then the lens is molded on the substrate.

  7A to 7C are schematic views showing another process for forming a patterned light-shielding film. FIG. 8A to FIG. 8C are schematic views showing a process of forming the lens 12 after forming the patterned light-shielding film 14 first.

  First, as shown in FIG. 7A, a coating layer forming step is performed in which a black polymerizable composition is coated on the substrate 10 to form a coating layer 14A.

  Thereafter, the coating layer 14 </ b> A 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 the black polymerizable composition can be arbitrarily selected from performances such as desired light shielding properties, and is generally in the range of 0.1 μm or more and less than 50 μm.

  Next, as illustrated in FIG. 7B, an exposure process is performed in which the coating layer 14 </ b> A formed in the light shielding 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, only the portion irradiated with light in the coating layer 14A is cured by pattern exposure of the coating layer 14. Here, a mask pattern that irradiates light only to the 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 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 coating layer 14A in the region corresponding to the lens opening 14a of the lens 12 that is an uncured region of the coating layer 14A in the pattern exposure is eluted into the alkaline aqueous solution. In addition, the photocured coating layer 14 </ b> A in the region other than the region of the lens opening 14 a of the lens 12 remains on the substrate 10 to form the light shielding film 14. (See FIG. 7C). As the alkali agent, the same procedure as described above can be used. Thereafter, the excess developer is washed away and dried.

  Also in this embodiment, after performing the above-described coating layer forming step, exposure step, and development step, if necessary, a curing step for curing the formed light-shielding film by the above-described post-baking and / or exposure is performed. Also good.

Next, the manufacturing process of the wafer level lens which forms the light shielding film 14 and then forms the lens 12 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 layer 14 adjacent to the opening so as to cover a region corresponding to the lens opening 14 a of the lens 12.

  After supplying the molding material M to the substrate 10, as shown in FIG. 8B, a mold 80 for molding a lens is disposed. 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 1, 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 10a of the lens 12 as shown in FIG. 2, but also as shown in FIG. 8C. The film 14 may be provided in a region excluding the lens opening 14 a of the lens 12.

The wafer level lens is formed in a pattern on at least one surface of the substrate 10 and has a light shielding film 14 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 including an imaging element, 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.

  As in the configuration shown in Patent Document 2, in the case where a structure with an uneven surface is provided around the lens, light incident on the structure is reflected or diverges, and thus problems such as ghosts are likely to occur. There is concern. Therefore, as shown in FIG. 2, if the light shielding layer 14 patterned in the region excluding the lens surface 10a of the lens 12 is provided, light can be shielded outside the lens surface 10a, and the optical performance can be improved. .

Hereinafter, the present invention will be described in detail with reference to specific examples, but the present invention is not limited to these examples.
<Preparation of titanium black dispersion (TB dispersion 1)>
The component shown in the following composition I was subjected to a high viscosity dispersion treatment with a two-roll to obtain a dispersion. The viscosity of the dispersion at this time was 40,000 mPa · s.
In addition, you may knead | mix for 30 minutes with a kneader before a high-viscosity dispersion process.

(Composition I)
-Average primary particle size 75 nm Titanium black 13M-C 40 parts (Mitsubishi Materials Co., Ltd.) (Pigment Black 35)
8 parts of propylene glycol monomethyl ether acetate solution of benzyl methacrylate (BzMA) / methacrylic acid (MAA) copolymer (BzMA / MAA = 60/40 [molar ratio], Mw: 30,000, solid content: 40% by mass )
・ Solsperse 5000 (made by Nihon Lubrizol) 2 parts

To the obtained dispersion, components shown in the following composition II were added and stirred for 3 hours using a homogenizer under the condition of 3,000 rpm. The obtained mixed solution 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 (hereinafter referred to as TB dispersion). This is expressed as Liquid 1.).
At this time, the viscosity of the mixed solution was 6.8 mPa · s.

(Composition II)
10 parts of propylene glycol monomethyl ether acetate solution of benzyl methacrylate (BzMA) / methacrylic acid (MAA) copolymer (BzMA / MAA = 70/30 [molar ratio], Mw: 30000, solid content: 40% by mass)
・ 200 parts of propylene glycol monomethyl ether acetate

<Preparation of titanium black dispersion (TB dispersion 2)>
(Synthesis of Dispersant B-1)
According to the production method described in JP 2010-106268 A, paragraphs [0338] to [0340], Dispersant B-1 having the following structure was obtained.
A component shown in the following composition III was subjected to a high viscosity dispersion treatment with a two-roll to obtain a dispersion. The viscosity of the dispersion at this time was 40,000 mPa · s.
In addition, you may knead | mix for 30 minutes with a kneader before a high-viscosity dispersion process.

(Composition III)
-Average primary particle size 40nm titanium black 40 parts-Dispersant B-1 5 parts

Components shown in the following composition IV were added to the obtained dispersion, and the mixture was stirred for 3 hours using a homogenizer under the condition of 3,000 rpm. The obtained mixed solution 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 (hereinafter referred to as TB dispersion). This is expressed as Liquid 2.).
At this time, the viscosity of the mixed solution was 6.8 mPa · s.

(Composition IV)
・ Dispersant B-1 5 parts ・ Propylene glycol monomethyl ether acetate 200 parts

<Adjustment of carbon black dispersion (CB)>
Carbon black dispersion was performed in the same manner as TB dispersion I, except that an equivalent amount of carbon black (carbon black MA-100R (manufactured by Mitsubishi Kasei Kogyo Co., Ltd.)) was used instead of titanium black used in TB dispersion I. Got the liquid

<Preparation of silver tin dispersion (ST dispersion)>
In 200 ml of pure water kept at 60 ° C., 15 g of tin colloid (average particle system: 20 nm, solid content: 20% by weight, manufactured by Sumitomo Osaka Cement Co., Ltd.), silver colloid (average particle system: 7 nm, solid content: 20% by weight, A solution prepared by dissolving 60 g of Sumitomo Osaka Cement Co., Ltd. and 0.75 g of polyvinylpyrrolidone in 100 ml of water was 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. Using this powder, a dispersion was prepared in the same manner as titanium black.

[Examples 1 to 4, Reference Example 5]
1. Preparation of black polymerizable composition The components of the following composition A-1 were mixed with a stirrer to prepare a black polymerizable composition A-1.
(Composition A-1)
-Binder polymer [(D) specific binder or comparative binder] 1.6 parts [compound described in Table 1 below]
Dipentaerythritol hexaacrylate [(C) polymerizable compound] 2.0 parts Pentaerythritol triacrylate [(C) polymerizable compound] 1.0 part Polymerization initiator [Table (B) polymerization shown in Table 1 below Initiator] 0.3 part dispersion (pigment dispersion composition containing (A) black material) 24 parts propylene glycol monomethyl ether acetate [organic solvent] 10 parts cyclohexanone [organic solvent] 8 parts

≪Preparation and evaluation of light-shielding film for solid-state imaging device≫
The black polymerizable composition obtained above was applied to a glass wafer by a spin coating method, and then heated at 120 ° C. for 2 minutes on a hot plate to obtain a black polymerizable composition coating layer.
Next, the obtained coating layer was exposed at 500 mJ / cm ² using an i-line stepper.
The photosensitive layer after the exposure was repeatedly subjected to paddle development 5 times at 23 ° C. for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide. Thereafter, rinsing was performed with a spin shower, followed by washing with pure water to obtain a patterned light-shielding film.
About the obtained light shielding film pattern, the frequency | count of development when an exposure part generate | occur | produces peeling using an optical microscope is shown below.
If it is 4 times or more, it is judged that the developer resistance is good.

In addition, the binder polymer of Table 1 is a compound shown below.
B-1: Polyhydroxystyrene (Nippon Soda Co., Ltd. VP-2500)
PKa of acid group: 10.0
B-2: Novolac resin (Sumitite Resin P-1 manufactured by Sumitomo Bakelite Co., Ltd.)
PKa of acid group: 10.0

The pKa of the acid group included in the binder polymer (B-3) is 7.6, and the pKa of the acid group included in the comparative binder polymer (HB-1) is 2.1.
The polymerization initiators described in Table 1 Ri compound der shown below, I-3 is Ru compared polymerization initiator der.

  From the results in Table 1 above, it can be seen that the wafer level lens having the light-shielding film using the black polymerizable composition of the present invention has improved developer resistance.

[Examples 6 , 7, 9, 10 and Reference Example 8 ]
1. Preparation of black polymerizable composition The components of the following composition A-2 were mixed with a stirrer to prepare a black polymerizable composition A-2.
(Composition A-2)
-Binder polymer [(D) specific binder or comparative binder] 2 parts [compound described in Table 2 below]
Succinic acid-modified monomer of dipentaerythritol pentaacrylate [(C) polymerizable compound] 2.0 parts Pentaerythritol triacrylate [(C) polymerizable compound] 2.0 parts 3-methacryloxypropyldimethoxymethylsilane 0 .1 part [Adhesion improver]
・ Polymerization initiators listed in Table 2 below [(B) photopolymerization initiator] 0.4 parts ・ Dispersion [(A) Black material-containing dispersion composition] 24 parts ・ Propylene glycol monomethyl ether acetate [organic solvent] 10 Part ・ Cyclohexanone [Organic solvent] 8 parts

≪Preparation and evaluation of light-shielding film for solid-state imaging device≫
A transparent resin having a cylindrical hole having a diameter of 50 μm, coated with a composition V of 15 μm on a glass wafer, exposed to a pattern with a high-pressure mercury lamp using a 50 μm hole mask so as to have a cylindrical shape with a diameter of 50 μm. A layer was formed. Then, the wafer provided with the transparent resin layer which formed the hole by heating with a hotplate at 200 degreeC for 5 minute (s) was produced.
Thereafter, each black polymerizable composition obtained above is spray-coated on the wafer on which the transparent resin layer has been formed using a two-fluid spray coating apparatus, dried at 120 ° C. for 2 minutes, and an average film A black polymerizable composition layer having a thickness of 3 μm was obtained. In addition, the formed black polymerizable composition layer was uniformly formed on the surface of the glass wafer and the surface of the transparent resin layer even in the structure having such irregularities.
Furthermore, using a photomask having a light-shielded hole portion having a diameter of 50 μm, the hole forming region of the transparent resin layer formed above and the hole portion of the photomask are positioned together, and the black polymerizable composition layer From above, using a high-pressure mercury lamp, exposure was performed at an exposure amount of 1000 mJ / cm ² together with the holes. By exposure, the black polymerizable composition layer is cured in a region other than the hole forming portion, and the black polymerizable composition layer in the hole forming portion exists in an uncured state by the hole mask.

(Composition V)
Allyl methacrylate / methacrylic acid (70/30) Mw = 50,000 1.6 parts Dipentaerythritol hexaacrylate [polymerizable compound] 2.0 parts Pentaerythritol triacrylate [polymerizable compound] 1.0 part IRGACURE OXE1 [polymerization initiator (I-1)] 0.3 part / propylene glycol monomethyl ether acetate 5 parts

The coating layer after the exposure was repeatedly subjected to paddle development at 23 ° C. for 60 seconds using a 0.3% aqueous solution of tetramethylammonium hydroxide [developing step]. Thereafter, rinsing was performed with a spin shower, followed by washing with pure water to obtain a patterned light-shielding film.
The above development process was repeated until the formed light-shielding film was peeled off, and the number of development was determined. The larger the number of times, the better the developer resistance.
Further, the residue in the hole portion is removed by performing development twice, and when no residue is seen after the development twice, it is judged as ◯ and it is judged that the developability is good. When a residue was seen after two developments, it was evaluated as x.
The results are shown in Table 2 below.

  As is apparent from Table 2, when the light-shielding film was formed using the black polymerizable composition of the present invention, the generation of development residues was suppressed even in the recesses in the holes, and the formed light-shielding film It was confirmed that the developer resistance was also excellent.

Claims (12)

(A) Black material, (B) Polymerization initiator which is an oxime compound , (C) Polymerizable compound, and (D) Main chain structure is selected from (meth) acrylic polymer, styrene resin, and phenol resin. Phenolic hydroxyl group, 2-methoxyphenol group, 2-chlorophenol group, methyl 2-hydroxybenzoate, 4-methylphenol group, 1,3-benzenediol group, 1-naphthol group, 1,2-benzenediol Group, benzenesulfonamide group, N-acetylphenylbenzenesulfonamide group, 4-aminobenzenesulfonamide group, N-phenyl-4-aminobenzenesulfonamide group, and N- (4-acetylphenyl) -4-aminobenzene alkali-soluble binder poly pKa selected from sulfonamide group has a greater than 5 functional groups Black polymerizable composition containing over. (A) a black material, (B) a polymerization initiator that is an oxime compound, (C) a polymerizable compound, and (D) an acrylic resin having a functional group greater than 5 and having a benzenesulfonamide group, poly A black polymerizable composition containing an alkali-soluble binder polymer selected from hydroxystyrene, novolac resin, and resol resin. The black polymerizable composition according to claim 1 or 2 , wherein the (A) black material is titanium black. The black polymerizable composition according to any one of claims 1 to 3, wherein the functional group having a pKa greater than 5 in the (D) alkali-soluble binder polymer is a phenolic hydroxyl group or a sulfonamide group. . The black polymerizable composition according to any one of claims 1 to 4 , wherein the (D) alkali-soluble binder polymer is selected from the group consisting of a novolak resin and polyhydroxystyrene. The black polymerizable composition according to any one of claims 1 to 5 , wherein the (D) alkali-soluble binder polymer is a polymer containing the following structural unit.

Furthermore, the black polymeric composition of any one of Claims 1-6 containing an organic solvent.   Furthermore, the dispersion resin chosen from the graft copolymer containing the structural unit represented by either of following formula (1)-Formula (5) is contained in any one of Claims 1-7. Black polymerizable composition.

  In formula (1) to formula (5), X ¹ , X ² , X ³ , X ⁴ , X ⁵ And X ⁶ Each independently represents a hydrogen atom or a monovalent organic group; ¹ , Y ² , Y ³ , Y ⁴ And Y ⁵ Each independently represents a divalent linking group; ¹ , Z ² , Z ³ , Z ⁴ And Z ⁵ Each independently represents a hydrogen atom or a monovalent organic group. R represents a hydrogen atom or a monovalent organic group, and R having a different structure may exist in the copolymer. n, m, p, q, and r each represent an integer of 1 to 500. j and k are each independently an integer of 2 to 8. Black polymerizable composition according to any one of the light-blocking region according claim 1 for use in the formation section 8 of the wafer level lens. The black polymerizable composition according to any one of claims 1 to 9 , which can be applied by spraying. Applying the black polymerizable composition according to any one of claims 1 to 10 by spray coating to a solid surface to form a black polymerizable composition layer;
A step of applying energy to the formed black polymerizable composition layer and curing it;
Method for producing a black layer containing The method for producing a black layer according to claim 11 , wherein the solid surface is a peripheral surface of a wafer level lens, and the black layer is a light-shielding region formed at a peripheral portion of the wafer level lens.