CH705872B1 - A black polymerizable composition and a method for producing a black coating. - Google Patents

Abstract

The invention provides a black polymerizable composition having excellent resistance to alkaline developer, a wafer nested lens, and the like. The black polymerizable composition according to the invention comprises at least: A) a black material; B) a polymerization initiator; C) a polymerizable compound; D) an alkali-soluble binder polymer having an average molecular weight of at least 30,000 and a polymerizable group on one of its side chains, and having an acid group in a molecule thereof.

Description

Technical area

The present invention relates to a black polymerizable composition comprising a specific binder polymer soluble in an alkaline medium, in particular a black polymerizable composition used to form a light shielding region of a lens array nested in a wafer ( wafer-level), wherein a plurality of lenses are disposed on a substrate, and a method of producing a black layer using the black polymerizable composition.

Technological background

[0002] Recently, compact and low profile (slim) imaging units have been mounted on mobile terminals of electronic instruments such as cell phones or personal digital assistants (PDAs). These imaging units generally include solid-state imaging devices such as an image sensor of the Charge Coupled Device (CCD) type or an image sensor of the Solid-state type. Complementary Metal-Oxide Semiconductor (CMOS), and a lens for forming an image of the subject on semiconductor imaging devices.

[0003] Thanks to the reduction in the size and thickness of mobile terminals and the widespread use of mobile terminals, the further reduction in the size and thickness of an imaging unit mounted on mobile terminals is required and the improvement of the productivity thereof is also required. With respect to these requirements, a method of mass production of imaging units is known in which a lens substrate with a plurality of lenses formed thereon and a sensor substrate with a plurality of solid-state imaging devices. formed thereon are integrally combined, and the lens substrate and the sensor substrate are cut so as to have a lens and a solid state imaging device in each cut portion. In addition, the adoption of a method of forming a lens on a wafer makes it possible to perform various simple training methods including, for example, a method in which, for example, only the lenses are produced on a wafer in glass which is cut to a size of combination of respective lenses with sensors, followed by combination with pre-separated imaging devices to produce respective imaging units; a process where several lenses are formed only from a resin using a mold, which are combined on a sensor substrate and then cut; and a method in which a lens is cut to a size of combination with respective sensors, followed by combination with pre-separated imaging devices, to produce respective imaging units. Hereinafter, in the present description, each of the plurality of lenses formed on a lens substrate is referred to as a wafer-level nested lens, and a group of lenses formed on a lens substrate, including the lens. lens substrate, is referred to as an array of nested wafer-level (or wafer-level) lenses.

[0004] As an array of wafer-nested lenses, there is known in the prior art a wafer-nested lens array with multiple lenses formed thereon by applying drop by drop a hardenable resin material to the surface of a parallel plate (substrate) formed of a light transmitting material such as glass, and curing the resin when it is arranged in a prescribed shape using a mold (for example, see Japanese Patent Publication No. 3,926,380 and International Application Publication No. WO 2008/102648). In some cases, a light shielding section formed, for example, from a black film or a metal film may be formed in a different region from the lens portion of a wafer or wafer nested lens. part of the lens in order to control the amount of light passing through it. The light shielding section is generally formed by coating a curable light shielding composition or by depositing metals.

As another array of wafer-nested lenses, there is also known an array of wafer-nested lenses which is obtained by forming several through holes on a silicon substrate, by arranging spherical lens materials which have been formed separately in the respective through holes, bonding the lens materials to the substrate by welding, then polishing lens materials to form a plurality of lenses (see US Patent No. 6,426,829). In a lens obtained by this production method, the black film or the metallic film described above can be formed in order to control the amount of light passing through it.

[0006] In a case where a light shielding region is formed by deposition of a metal, improvement is required both in productivity and in performance, from the viewpoint of problems such as process complexities or lens bending after deposition.

[0007] On the other hand, a black polymerizable composition has been used in a coating process to exhibit the light shielding property (see Japanese Patent Application Publication (JP-A) No. 2010-8656 and 2006-276,421). In a case where a black polymerizable composition has sufficient protection against light in a visible region, the transmission of radiation selected from g-rays, h-rays, i-rays, and / or the like, which are sources exposure to light used for curing the black polymerizable composition, is not sufficient. For this reason, the film is not sufficiently hardened in the depth, and therefore, after the image-shaped exposure, the problems arose such as flaking in the film in an alkaline developing step, in which an unexposed part must be removed.

[0008] Thus, research concerning these problems relating to resistance to alkaline developer has not yet been sufficiently carried out.

Summary of the invention

[0009] The present invention is made in view of the aforementioned aspects, and its object is to approach objects as described below. That is, one aspect of the invention is to provide a black polymerizable composition which has resistance to alkaline developer, and therefore, has excellent light protection. It is another aspect of the invention to provide a black polymerizable composition capable of being applied by spraying. It is yet another aspect of the invention to provide a method of making a black layer, which is useful for the light shielding region of a wafer-nested lens, using the black polymerizable composition.

In general, a resin containing a carboxylic acid as a group soluble in an alkaline medium is used in a curable composition. However, when the development is carried out under relatively severe conditions so as to remove the residue from an unexposed part, problems such as peeling of an image part have occurred. Meanwhile, when using the curable composition for an aperture of a lens, broad light protection, ranging from the visible region to the infrared region is required. When a light shielding film is formed using a black polymerizable composition, imaging exposure is generally performed with a light source from 250 nm to 500 nm, followed by development using a developer. alkaline. However, since the curable composition includes a black material capable of shielding light at a wavelength of 250 nm to 500 nm, the light transmission from the light exposure source is insufficient, and therefore, the light transmission. depth of the film formed is not sufficiently hardened in some cases. Therefore, when the development is carried out under relatively severe conditions in order to prevent reduction of the residual film, a strongly acidic carboxylic acid can cause the developer to penetrate into the image part, and therefore, there is a risk that the Reduction in the resistance of the image portion may lead to the peeling of the light shielding film (black film). Further, when the black polymerizable composition (or the curable composition) is used for an opening or the like of a wafer-nested lens, it is possible to use a method in which a black polymerizable composition is deposited on a glass wafer. , then a lens is formed thereon, a method in which a lens is formed on a glass wafer, and then a black polymerizable composition is applied thereto, or the like. However, especially in the case where a black polymerizable composition is applied after a lens has been formed, it is effective to apply the black polymerizable composition to the substrate structure by spray coating. In other words, the inventors of the present invention have extensively studied various black polymerizable compositions, and therefore, have found a black polymerizable composition having resistance to alkaline developer, and therefore, having excellent protection against light. The inventors have also found a black polymerizable composition capable of being applied by spraying. Further, the inventors have found a method for producing a black layer, which is useful in the light shielding region of a wafer-nested lens, using the black polymerizable composition. The embodiments of the specific examples of the invention are as follows: <1> A black polymerizable composition, comprising: (A) a black material; (B) a polymerization initiator; (C) a polymerizable compound; and (D) an alkaline soluble binder polymer having a weight average molecular weight of at least 30,000 and having a polymerizable group at a side chain thereof. <2> The black polymerizable composition according to <1>, wherein the black material (A) is titanium black. <3> The black polymerizable composition according to <1> or <2>, wherein the alkaline-soluble binder polymer (D) is an alkaline-soluble binder polymer having a weight average molecular mass ranging from 50,000 to 100,000 and having a polymerizable group on a side chain thereof. <4> The black polymerizable composition according to any one of points <1> to <3>, which is used to form a light shielding region of a wafer-fitted lens. <5> The black polymerizable composition according to any of the points <1> to <4>, which is capable of being applied by spraying. <6> The black polymerizable composition according to any one of items <1> to <5>, wherein the total solid content in the black polymerizable composition is 20% by mass to 35% by mass. <7> The black polymerizable composition according to any one of points <1> to <6>, wherein the polymerizable group included in the alkaline soluble binder polymer (D) is an acrylic group, a methacrylic group, a group styryl, an allyl group, an acrylamide group, a methacrylamide group, a vinyl group or a vinyl ether group. <8> The black polymerizable composition according to any one of points <1> to <7>, in which the content of the binder polymer soluble in alkaline medium (D) is from 5% by mass to 75% by mass relative to the total solid content of the black polymerizable composition. <9> A process for producing a black layer, the process comprising: applying, by spray coating, the black polymerizable composition according to any of the points <1> to <8> to a surface of a solid to form a layer of black polymerizable composition, and applying energy to the formed layer of black polymerizable composition to harden the formed layer of black polymerizable composition. <10> The method of producing a black layer according to point <9>, wherein the surface of the solid is a surface of a peripheral part of a wafer-nested lens, and the black layer is a protection region against the light formed in the peripheral part of a lens fitted with a wafer.

[0011] According to one aspect of the invention, a black polymerizable composition which has resistance to alkaline developer, and therefore, which exhibits excellent protection against light is provided. Further, according to another aspect of the invention, a black polymerizable composition capable of being applied by spraying is provided. Further, according to yet another aspect of the invention, a method for producing a black layer, which is useful for the light shielding region of a wafer-nested lens, is provided using the polymerizable composition. black.

Brief description of the drawings

[0012] FIG. 1 is a view showing an example of an array of wafer-nested lenses. Fig. 2 is a cross-sectional view of the wafer-nested lens array shown in FIG. 1, which is taken along the A – A line. Fig. 3 is a view showing the feed state of a molding material for forming a lens on a substrate. Figs. 4A to 4C are views showing the process of forming lenses on a substrate using a mold. Figs. 5A to 5C are schematic views illustrating the process of forming a patterned light shielding film on the substrate having lenses formed thereon. Fig. 6 is a view showing an example of an array of wafer-nested lenses. Figs. 7A to 7C are schematic views showing another embodiment of the process of forming a light shielding film. Figs. 8A to 8C are schematic views showing the process of forming lenses on a substrate having a patterned light shielding film.

Description of embodiments

[0013] Hereinafter, the black polymerizable composition according to the invention will be described in detail. The explanation of the constituent elements described below is made on the basis of the representative embodiments of the invention, but the invention is not limited to these embodiments. In the description, the term "step" or "process" is not only an independent step, but also includes a case of performing a predetermined action of the step, even if it cannot be clearly distinguished from the others. steps. In addition, in the description, the range of numerical values expressed using "to" denotes a range comprising a minimum value and a maximum value described before and after the "to".

Binding polymer soluble in alkaline medium (D) The black polymerizable composition according to the invention comprises an alkaline soluble binder polymer having a weight average molecular mass of 30,000 and having a polymerizable group at a side chain thereof. Examples of the polymer which constitutes the main chain of the binder polymer soluble in an alkaline medium (D) used in the invention include (meth) acrylic polymers, polyurethane resins, polyvinyl alcohol resins, polyvinyl butyral resins, polyvinyl formal resins, styrene resins, polyamide resins, polyester resins, epoxy resins and phenolic resins, such as a novolak resin or a resol resin. In particular, (meth) acrylic polymers, styrene resins, and phenolic resins are preferable. Further, from the viewpoint of sensitivity and resolution, (meth) acrylic polymers and polyurethane resins are preferable, and (meth) acrylic polymers are most preferable.

The "(meth) acrylic polymer (s)" in the present invention relates to a copolymer having, as a polymerization component, a (meth) acrylic acid, an ester (meth) acrylic (eg, an alkyl ester, an aryl ester, an allyl ester, or the like), a (meth) acrylamide, or a (meth) acrylic acid derivative such as a (meth) acrylamide derivative. In the description, when describing "acrylic" and / or "methacrylic", "(meth) acrylic" can be used in some cases. "Polyurethane resin" in the invention refers to a polymer produced by a condensation reaction of a compound having two or more isocyanate groups and a compound having two or more hydroxyl groups. The "polyvinyl butyral resin" in the present invention relates to a polymer synthesized by subjecting a polyvinyl alcohol obtained by saponification of part or all of the vinyl acetate to a reaction (acetal formation reaction ) with a butyl aldehyde under acidic conditions, as well as a polymer having an acid group or the like introduced therein, for example, a process involving the reaction of the remaining hydroxyl group with a compound having an acid group or the like.

[0016] The "styrene resin" in the present invention relates to a polymer obtained by copolymerization (for example, radical polymerization) of an aromatic compound such as benzene, naphthalene, anthracene or a heterocycle, in in which an alkenyl group such as a vinyl group is directly attached, and (meth) acrylic acid and / or a (meth) acrylic acid derivative. The aromatic compound may be substituted with, for example, a hydroxyl group, a carboxyl group, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an amino group, a carbonyl group, an ether group, an alkoxycarbonyl group, an oxycarbonyl group, a cyano group, an aryl group, an alkoxy group, a sulfide group, a mercapto group, or the like. As for the polymerization, it is possible to carry out radical polymerization, cationic polymerization, or anionic polymerization. Further, after polymerization, if necessary, alkali treatment, acid treatment, or the like can be carried out to obtain a desired styrene resin.

[0017] Any of the other resins can be used for the polymer constituting the main chain of the binder polymer soluble in an alkaline medium in the invention. For example, the polyurethane resins described in paragraphs [0029] to [0108] of JP-A No. 2005-250,438 and the like, a resin having an amide and a polymerizable group in a molecule thereof described in paragraphs [0009] to [0019] of JP-A No. 2010-39 121 and the like, and a resin obtained by reacting a resin having, as a main component, acrylic acid and a (meth) acrylic ester with an epoxy resin containing an unsaturated compound group described in paragraphs [0014] to [0015] of JP-A No. 2000-191737 and the like, can be used.

[0018] The binder polymer soluble in an alkaline medium in the invention preferably has a high molecular weight and is preferable in terms of inhibiting the elution of an image part which is a part exposed in a developer during development, and has a polymerizable group to improve curing. The weight average molecular weight of the alkaline soluble binder polymer in the invention is at least 30,000. When the weight average molecular weight is less than 30,000, the resistance of the part of the image to the developer is not sufficient. Further, from the viewpoint of developability of the image portion and the non-image portion, the weight average molecular weight of the alkaline soluble binder polymer is preferably 30,000 to 500,000, preferably from 40,000 to 200,000, and even more preferably from 50,000 to 100,000. According to the invention, the weight average molecular weight relates to a value measured in terms of styrene by means of a gel permeation chromatography (GPC) process.

[0019] The alkaline soluble binder polymer in the invention has a polymerizable group at a side chain of the polymer. Examples of the polymerizable group included in the side chain include an acrylic group, a methacrylic group, a styryl group, an allyl group, an acrylamide group, a methacrylamide group, a vinyl group, and a vinyl ether group. From the standpoint of stability and reactivity, an acrylic group, a methacrylic group, and an allyl group are preferred, and a methacrylic group is more preferable. The amount of the polymerizable group included in the side chain is preferably 10 mol% to 80 mol%, in total monomer units each having a polymerizable group in the polymers, and from the viewpoint of sensitivity, suitability. development, and stability, it is more preferably from 30 mol% to 60 mol%.

[0020] Here, the examples of the method of introducing a polymerizable group into the binder polymer soluble in an alkaline medium comprise a process in which a part of the carboxylic acids in the binder is reacted with a compound having a cyclic ether and a (meth) acrylic group, such as glycidyl methacrylate, so as to introduce the polymerizable group, as described in paragraph [0014] of JP-A No. 2000-187322 and the like; a process in which a resin having an acrylic acid and a (meth) acrylic ester as main components is reacted with an epoxy group containing an unsaturated compound, and a binder in which a monomer having a hydroxyl group is used as a component copolymerization is reacted with a methacrylic anhydride or an acrylic anhydride or acrylic chloride or methacrylic chloride, as described in JP-A No. 2000 191 737; or a process in which a binder in which a monomer having a hydroxyl group is used as a copolymerization component is allowed to coexist with methacrylic acid or acrylic acid, and subjected to dehydration / condensation, and a process wherein a monomer having a methacrylic acid derivative and / or an acrylic acid derivative on a side chain is polymerized and subjected to a treatment with a base, as described in paragraph [0028] of JP-A No. . 2005-47,947 and the like.

[0021] The binder polymer soluble in an alkaline medium in the invention has a functional group which expresses the alkaline solubility. As a functional group which imparts alkaline solubility to the binder polymer, it is necessary that the binder polymer comprises an acidic group of a molecule thereof. Examples of preferred acidic groups include a carboxylic acid group, a phosphoric acid group, a monophosphoric ester group, a sulfonic acid group, a sulfinic acid group, a sulfonamide group, a phenolic hydroxyl group, a thiol group, an alkyl acetate group. acetyl, and their derivatives. From the viewpoint of sensitivity, stability, and developability, the acid group is preferably a carboxylic acid group. When the alkaline-soluble binder polymer in the invention has an alkaline-soluble group, the acid value is preferably from 5 mg KOH / g to 150 mg KOH / g, and more preferably 30 mg KOH / g. KOH / g to 100 mg KOH / g. Regarding the method of introducing the functional group which confers alkaline solubility to the binder polymer, when the polymerization is carried out by radical polymerization, the functional group which confers alkaline solubility to the binder polymer can be introduced by polymerization of a compound having a group acid and a polymerizable group such as an ethylene group, such as methacrylic acid, acrylic acid, vinylbenzoic acid, or vinylphenol. In addition, the introduction of the functional group can also be achieved by polymerizing acetoxyvinyl phenol, followed by hydrolysis. In the case of a urethane binder, for example, a method in which a diol having a carboxylic acid moiety and a diisocyanate compound are subjected to a polycondensation reaction to introduce an acid group can be used.

When a polymer which constitutes the main chain of the binder polymer soluble in an alkaline medium in the invention is a (meth) acrylic polymer, a polymer having a carboxylic acid group can be obtained by radical polymerization. Examples of a monomeric acid containing a group which can be used in the radical polymerization may include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, etc. phthalic acid monohydroxyethyl acrylate, monoacrylate ω-carboxy-polycaprolactone, ethyl acrylate β-carboxy, succinic acid 2-acryloyloxyethyl, hexahydrophthalate 2-acryloyloxyethyl, phthalic acid methacrylate monohydroxyethyl methacrylate, monohydroxyethyl methacrylate carboxy-polycapro-lactone, methacrylate (β-carboxyethyl, succinic acid 2-methacryloyloxy-ethyl, hexahydrophthalic acid 2-methacryloyloxyethyl, and 4-carboxystyrene, and examples of the monomer having an acid anhydride include an acid Anhydrous maleic In addition, other useful monomers can be used. Examples of a monomer capable of being copolymerized with the acid group containing monomers include points (1) to (12) below:

[0023] (1) Acrylic esters and methacrylic esters, each having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate , 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, or 4-hydroxybutyl methacrylate;

[0024] (2) Alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, 2-chlorethyl acrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate , vinyl acrylate, 2-phenyl vinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, or propargyl acrylate;

[0025] (3) Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, methacrylate d ' hexyl, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, methyl 3, 4-epoxycyclohexyl methacrylate, vinyl methacrylate, 2- methacrylate phenyl vinyl, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, or propargyl methacrylate; (4) Acrylamides or methacrylamides such as acrylamide, methacrylamide, N-methylolacrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acrylamide, N-nitrophenyl acrylamide, N-ethyl- N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide, N acrylamide, N-diallyl, N-methacrylamide, N-diallyl , acrylamide allyl, or methacrylamide allyl;

Vinyl ethers (5) such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, l octyl vinyl ether, or phenyl vinyl ether; (6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, or vinyl benzoate; (7) Styrenes such as styrenes, α-methylstyrene, methylstyrene, chloromethylstyrene, or p-acetoxystyrene; (8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, or phenyl vinyl; (9) Olefins such as ethylene, propylene, isobutylene, butadiene, or isoprene;

[0027] (10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, and the like; (11) Unsaturated imides such as maleimide, N-acryloyl acrylamide, N-acetyl methacrylamide, N-propionyl methacrylamide, or N- (p-chlorobenzoyl) methacrylamide; and (12) Methacrylic acid monomers, each having a heteroatom attached to its α-position, such as the compounds described in JP-A Nos. 2002-309,057 and 2002-311,569, and the like.

[0028] Other suitable examples thereof include (meth) acrylic polymers, each having an allyl group or a vinyl ester group and a side chain carboxyl group thereof, and alkali soluble resins. each having a double bond on a side chain, as described in JP-A No. 2000-187,322, and alkaline soluble resins, each having an amide group on a side chain, as described in JP-A No. 2001-242 612. Most of the preferable examples of the alkaline soluble binder polymer are shown below.

[0029]

[0030]

[0031]

[0032] In the invention, the binder polymers soluble in alkaline medium can be used alone or in combination of two or more types thereof. The content of binder polymer soluble in an alkaline medium is preferably from 5% by mass to 75% by mass, more preferably from 10% by mass to 70% by mass, and even more preferably from 10% by mass to 60% by mass. mass, based on the total solid content of the black polymerizable composition, in terms of good intensity of part of an image and good anti-developer resistance. "Total solid content" as used in the invention refers to a total amount of the components of the black polymerizable composition, except the solvent.

[0033] Dark Matter (A) The black polymerizable composition according to the invention comprises a black material. Examples of the black material (A) used in the present invention include combinations of a black pigment, a black dye, a red pigment, a blue pigment, a green pigment, a yellow pigment, an orange pigment, a purple pigment, a cyan pigment, a magenta pigment, a gray pigment, and the like, or combinations of a red dye, a blue dye, a green dye, a yellow dye, an orange dye, a violet dye, a cyan dye, a dye magenta, a gray dye, and the like. From the viewpoint of light protection, storage stability, safety and the like, a black pigment is preferably used. Examples of black pigment include inorganic pigments such as black titanium or black carbon. Examples of a commercially available carbon black (C.I. Pigment Black 7) product include carbon black MA-100 R (trade name, manufactured by Mitsubishi Chemical Corporation). Specific examples of the inorganic pigment other than carbon black include metallic pigments, black titanium, China white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, red iron oxide, yellow chromium, zinc chromate (such as potassium zinc chromate and tetroxy chromate zinc), ultramarine blue, Prussian blue (ferric potassium ferrocyanide), gray zircon, yellow praseodymium, yellow titanium chrome, green chrome, peacock, Victoria green, iron blue (n 'having no relation to Prussian blue), zirconium vanadium blue, chrome pewter rose, manganese rose and salmon pink. Examples of inorganic black pigments include a metal oxide and a metal nitride containing one or two or more types of metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. These pigments can be used alone or as a mixture of two or more types. In particular, these pigments can be used not only alone, but also in a mixture of several types of pigments, in order to express the property of protecting against light in a region of wavelengths ranging from ultraviolet to ultraviolet. infrared.

[0034] From the viewpoints of light protection and hardening property, metallic pigment and titanium black are preferable. The metallic pigment is preferably a metallic pigment containing at least one of silver, tin, and the like, or a mixture of silver and tin. From the viewpoint of protection against light in the range from ultraviolet to infrared, titanium black is most preferred.

[0035] The titanium black used in the invention is a black particle having a titanium atom. Preferred examples of these include a suboxide of titanium and titanium oxynitride. A titanium black particle can be used as such, or the surface thereof can be optionally modified from the standpoint of, for example, improvement of dispersibility and suppression of aggregation. The titanium black particle can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Alternatively, the titanium black particle can be treated with a water repellent material as described in Japanese Open Patent Application (JP-A) No. 2007-302,836. Further, titanium black may contain one or a combination of two or more types of a composite oxide of Cu, Fe, Mn, V, Ni, and the like, and a black pigment such as cobalt oxide, l iron oxide, carbon black, or aniline black, in order to adjust the dispersion and coloring. In this case, the titanium black particles are 50% by mass or more of the inorganic pigment (A).

Examples of commercially available titanium black products include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R and 13R-N (trade names, manufactured by Mitsubishi Material Corporation) and TILACK D (trade name, manufactured by Ako Kasei Co., Ltd.)

[0037] Titanium black can be produced, for example, by a process in which a mixture of titanium dioxide and metallic titanium is heated and reduced in a reducing atmosphere (see, for example, JP-A No. 49- 5,432), by a process in which titanium tetrachloride is hydrolyzed at high temperature to obtain ultrafine titanium dioxide and the resulting titanium dioxide is reduced in a reducing atmosphere containing hydrogen (see, for example, JP- A No. 57-205,322), by a process in which titanium dioxide or titanium hydroxide is reduced at high temperature in the presence of ammonia (see, for example, JP-A No. 60-65,069, JP-A No. 61-201 610), and by a process in which a vanadium compound is bonded to titanium dioxide or titanium hydroxide and the resultant is then reduced at high temperature in the presence of ammonia ( see, e.g., JP-A No. 61-201 610), but the invention is not limited to these methods.

The particle diameter of titanium black is not particularly limited, but it is preferably 3 nm to 2,000 nm, more preferably 10 nm to 500 nm, and even more preferably 10 nm to 100 nm , from the point of view of dispersibility and colorability. Further, the average primary diameter of the titanium black particles is not particularly limited, but is preferably 3 nm to 2000 nm, more preferably 10 nm to 500 nm, and even more preferably 10 nm to 100 nm. nm, from the point of view of dispersibility and coloring. A specific area of titanium black is not specifically limited. However, in order for the hydrophobic property to have a prescribed efficiency after the titanium black is surface treated with a hydrophobic agent, it is preferable that the titanium black has a specific surface area measured by the BET method in general of the order of 5 m <2> / g to 150 m <2> / g, and preferably from about 20 m <2> / g to 100 m <2> / g.

[0039] The average particle diameter of the inorganic pigment in the invention is preferably 5 nm to 0.01 mm, and from the point of view of dispersion, the light shielding property, and the sedimentation property in over time, the average diameter of the particles is preferably from 10 nm to 1 μm. The black polymerizable composition according to the invention may comprise a single single species of dark matter, or a combination of two or more types thereof. Further, as described below, an organic pigment, dye, or the like can be used in combination therewith, if desired, for the purpose of adjusting the light shielding or the like. The content of dark matter in the black polymerizable composition is preferably from 5% by mass to 70% by mass, and more preferably from 10% by mass to 50% by mass, relative to the total solid content.

[0040] Pigment dispersant When the black polymerizable composition is formulated using a pigment as the black material (A), it is preferable that the pigment is dispersed in advance with a known pigment dispersant to prepare a pigment dispersion, and the pigment dispersion is mixed, from the point of view of the uniformity of the composition obtained. As a pigment dispersant (hereinafter also referred to simply as a "dispersant"), for example, a known pigment dispersant or a surfactant can be suitably selected and used.

More specifically, the different types of compounds can be used as a dispersant. Examples of these include: cationic surfactants such as organosiloxane polymer KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), (co) polymer of (meth) acrylic acid POLYFLOW No. 75, No. 90, No. 95 (trade names, manufactured by Kyoeisha Chemical Co., Ltd.), or W001 (trade name, available from Yusho Co., Ltd.); nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate or, a sorbitan fatty acid ester; anionic surfactants such as W004, W005 or W017 (trade names, manufactured by Yusho Co., Ltd); polymer dispersants such as EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKA POLYMER 401, EFKA POLYMER 450 (trade names, manufactured by BASF Corporation), DISPERSE AID 6, DISPERSE AID 8 , DISPERSE AID 15, or DISPERSE AID 9100 (trade names, manufactured by San Nopco Limited); various SOLSPERSE dispersants such as SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, 32000 or 36000 (trade names, manufactured by The Lubrizol Corporation); ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (trade names, manufactured by ADEKA Corporation); IONET S-20 (trade name, manufactured by Sanyo Chemical Industries, Ltd) and DISPERBYK 101, 103, 106, 108, 109, 111, 112, 116, 130, 140, 142, 162, 163, 164, 166, 167, 170, 171, 174, 176, 180, 182, 2000, 2001, 2050, 2150 (trade names, manufactured by BYK-Chemie). Further, other examples of the dispersant include oligomers and polymers having a polar group at one end or a side chain of the molecule, such as acrylic copolymers. On the other hand, amphoteric dispersants such as HINOACT T-8000E (trade name, manufactured by Kawaken Fine Chemicals Co., Ltd.) can be suitably used. From the viewpoint of dispersion, developability and settling property, a resin shown below, as described in JP-A No. 2010-106,268, is preferable, in particular, From the viewpoint of dispersion, a polymeric dispersant having a polyester chain on a side chain is preferable. From the viewpoint of dispersibility and resolution of a pattern formed by photolithography, a resin having an acid group and a polyester chain is preferable. 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 adsorption capacity, and the carboxylic acid, sulfonic acid, or acid. phosphoric is particularly preferable. From the viewpoint of the solubility in a dispersing solution, the dispersibility, and the developability, a resin having a polycaprolactone side chain such as a polyester chain and having a carboxylic acid group is most preferable.

[0042] Hereinafter, the dispersant as described in document JP-A-No. 2010-106,268, which is preferably used in the invention, will be explained. A preferred dispersant is a graft copolymer which has the number of atoms in the molecule other than hydrogen atoms ranging from 40 to 10,000, which has a graft chain selected from a polyester structure, a polyether structure, and a polyether structure. of polyacrylate, and which comprises any one of the structural units represented by the formulas (1) to (4) shown below, and the graft copolymer which comprises a structural unit represented by any one of the following formulas (1 A), (2A), (3A), (3B), and (4) is more preferable.

[0043]

[0044] In formulas (1) to (4), each of X <1>, X <2>, X <3>, X <4> and X <5> each independently represent a hydrogen atom or a monovalent organic group. From the viewpoint of limitation of synthesis, each of X <1>, X <2>, X <3>, X <4> and X <5> each independently preferably represent a hydrogen atom or a group. alkyl having 1 to 12 carbon atoms, preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group. In formulas (1) to (4), each of Y <1>, Y <2>, Y <3> and Y <4> independently represents a divalent linking group, and their structures are not particularly limited. Specific examples of the divalent linking groups represented by Y <1>, Y <2>, Y <3> and Y <4> include the linking groups represented by the following structures (Y-1) to (Y-21) . In the following structures (Y-1) to (Y-21), A represents a bond between Y <1> and W <1>, Y <2> and W <2>, Y <3> and W <3> , and Y <4> and W <4>, respectively, in formulas (1) to (4), and B indicates a bond between Y <1>, Y <2>, Y <3>, Y <4> and those fragments which are present in the opposite position from W <1>, W <2>, W <3>, W <4>, respectively, in formulas (1) to (4). Of the structures shown below, the structures of (Y-2) and (Y-13) are preferable in terms of ease of synthesis.

[0045]

[0046] In formulas (1) to (4), Z <1>, Z <2>, Z <3> and Z <4> each independently represent a monovalent organic group, and their structures are not particularly limited. Specific examples thereof include an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group or a heteroaryloxy group, an alkylthioether group, an arylthioether group or a heteroarylthioether group, and an amino group. Of these, as the monovalent organic groups represented by Z <1>, Z <2>, Z <3> and Z <4>, those having steric hydrophobic property are preferable particularly from the viewpoint of improved dispersion. It is preferable that the organic groups represented by Z <1> to Z <3> each independently represent an alkyl group having 5 to 24 carbon atoms or an alkoxy group having 5 to 24 carbon atoms, and particularly preferably an alkoxy group having a branched alkyl group having 5 to 24 carbon atoms or an alkoxy group having a cyclic alkyl group having 5 to 24 carbon atoms. The organic group represented by Z <4> is preferably an alkyl group having 5 to 24 carbon atoms, and particularly preferably a branched alkyl group having 5 to 24 carbon atoms or a cyclic alkyl group having 5 to 24 carbon atoms. In formulas (1) to (4), n, m, p, and q are each an integer from 1 to 500. In formulas (1) and (2), j and k each independently represent an integer from 2 to 8, and j and k, in formulas (1) and (2) are preferably an integer from 4 to 6 and preferably 5, from the viewpoint of dispersion stability and developability.

[0047] R <3> in formula (3) represents a branched or linear alkylene group. R <3> in formula (3) is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms. R <4> in formula (4) represents a hydrogen atom or a monovalent organic group, and the structure of the monovalent organic group is not particularly limited. Preferred examples of R <4> in formula (4) include a hydrogen atom, an alkyl group, an aryl group and a heteroaryl group, and more preferably a hydrogen atom and an alkyl group. When R <4> in formula (4) is an alkyl group, the alkyl group is preferably a straight chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, preferably a straight chain alkyl group having 1 to 20 carbon atoms, and particularly preferably a straight chain alkyl group having 1 to 6 carbon atoms . Further, with respect to R <4> in formula (4), two or more types of R <4> having different structures can be mixed and used in a graft copolymer.

In the graft copolymer, the content (for example, the total content) of the structural units represented by formulas (1) to (4) is preferably in the range ranging from 10% to 90%, and more preferably from 30% to 70%, relative to the total mass of the graft copolymer. When the structural units represented by formulas (1) to (4) are included in these ranges, the dispersibility of the pigment is high and the developability is good when a light shielding film is formed.

[0049] The graft copolymer can comprise two or more types of graft copolymers having different structures.

[0050] The structural unit represented by the formula (1) is preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability and developability. The structural unit represented by the formula (2) is preferably a structural unit represented by the following formula (2A) from the standpoint of dispersion stability and development capacity.

[0051]

In formula (1A), X <1>, Y <1>, Z <1> and n have the same definitions as X <1>, Y <1>, Z <1>, and n in the formula (1), respectively, and the preferable ranges thereof (including examples thereof and the like) are also the same. In formula (2A), X <2>, Y <2>, Z <2> and m have the same definitions as X <2>, Y <2>, Z <2>, and m in formula (2 ), respectively, and the preferable ranges thereof (including examples thereof and the like) are also the same. The structural unit represented by the formula (3) is preferably a structural unit represented by the following formula (3A) or (3B) from the standpoint of dispersion stability and developability.

[0053]

In formula (3A) or (3B), X <3>, Y <3>, Z <3>, and p have the same definitions as X <3>, Y <3>, Z <3> , and p in formula (3), respectively, and preferable ranges thereof (including examples thereof and the like) are also the same.

[0055] It is preferable that the graft copolymer has the structural unit represented by the formula (1A).

[0056] Specific examples of the graft copolymer include the compounds shown below. Further, in the exemplary compounds shown below, numerical values shown with the respective structural units denote the contents (% by mass: suitably referred to as (wt%)) of the corresponding structural units.

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

As the dispersant in the invention, a compound having a polyester chain such as exemplary compound 72 is preferably used.

The content of the dispersant used in the preparation of a pigment dispersion in the invention is preferably from 1% by mass to 90% by mass, and preferably 3% by mass to 70% by mass, relative to to the total solid content mass of the colorant (including black pigment and other colorants) in the pigment dispersion.

Polymerization initiator (B) The polymerizable black composition of the invention comprises a polymerization initiator. The polymerization initiator used in the polymerizable composition according to the invention is not particularly limited as long as it is capable of initiating the polymerization of a polymerizable compound by application of light and / or heat, and can be chosen appropriately depending on the application. However, in the case of initiating the polymerization by light, a polymerization initiator having photosensitivity to rays ranging from a region of ultraviolet radiation to visible light is preferably used. Further, when the polymerization is initiated by heat, an initiator which decomposes at 150 ° C to 250 ° C is preferably used.

[0095] The polymerization initiator used in the present invention is preferably a compound having at least one aromatic group. Examples include (bis) acylphosphine oxides or their esters, acetophenone compounds, α-aminoketone compound, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime ester compounds, hexaarylbiimidazole compounds, trihalomethyl compounds, azo compounds, organic peroxides, a metallocene compound, onium salt compounds such as a diazonium compound, an iodonium compound, a sulfonium compound, or an azinium compound, organic compounds of the boron salt, and disulfone compounds. From the standpoint of sensitivity, oxime ester compounds, acetophenone compounds, acylphosphine oxide compounds, α-aminoketone compounds, trihalomethyl compounds, hexaarylbiimidazole compounds, and Thiol compounds are preferable, and acylphosphine oxide compounds, oxime ester compounds, α-aminoketone compounds and the like are more preferable. Examples of the polymerization initiator preferably used in the invention are described below, but the invention is not limited thereto.

[0096] Specific examples of the acetophenone compound include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4 - isopropyl-2-hydroxy-2-methylpropiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholino-phenyl) -butanone-1, 2-tolyl-2 -dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-methyl-1- (4-memylthiophenyl) -2 -morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, and 2-methyl-1- (4-methyl thiophenyl) -2-morpholinopropane-1-one. Of these, 2-methyl-1- (4-methylethiophenyl) -2-morpholinopropan-1-one, which is preferably used in the invention, is available under the trade name "IRGACURE 907" (manufactured by BASF).

More preferable examples of the trihalomethyl compound include an s-triazine derivative having at least one mono-, di-, or trihalo-substituted methyl group bonded to an s-triazine ring. Specific examples of these include 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 (trichloromethyl) -s-triazine, 2- (3,4epoxyphenyl) -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-bi (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-benzy l-4-thio, 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, and 2-methoxy-4,6-bis (tribromomethyl) -s-triazine.

Examples of the hexaarylbiimidazole compound include various compounds such as those described, for example, in Japanese Patent Application (JP-B) No. 6-29,285, and U.S. Patents Nos. 3,479,185, 4,311,783 and 4,622,286. Specific examples of these include 2,2 ́-bis (o-chlorophenyl) -4,4 ́, 5,5 ́-tetraphenylbiimidazole, 2,2 ́-bis (o-bromophenyl) -4,4 ́, 5,5 ́-Tetraphenylbiimidazole, 2,2 ́-bis (o, p-dichlorophenyl) -4,4 ́, 5,5 ́-tetraphenylbiimidazole, 2,2 ́-bis (o-chlorophenyl) -4,4 ́, 5,5 ́-tetra (m-methoxyphenyl) biimidazole, 2,2 ́-bis (o, o'-dichlorophenyl) -4,4 ́, 5,5 ́-tetraphenylbiimidazole, 2,2 ́-bis (o- nitrophenyl) -4,4 ́, 5,5 ́-tetraphenylbiimidazole, 2,2 ́-bis (o-methylphenyl) -4,4 ́, 5,5 ́-tetraphenylbiimidazole, and 2,2 ́-bis (o- trifluorophenyl) -4,4 ́, 5,5 ́-tetraphenylbiimidazole.

Examples of the oxime ester compound include compounds described in JCS Perkin II (1979) 1653-1660, JCS Perkin II (1979) 156-162, Journal of Photopolymer Sciences and Technology (1995) 202- 232, JP-A No. 2000-66,385, JP-A No. 2000-80,068, and JP-T No. 2004-534,797. Preferred examples of the commercially available products include IRGACURE OXE 01 (1, 2-octanedione, 1- [4- (phenylthio) -, 2- (o-benzoyloxime)]), and IRGACURE OXE 02 (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- 3-yl] -, 1- (o-acetyloxime)), both of which are manufactured by BASF Corporation. In addition, the cyclic oxime compounds described in JP-A Nos. 2007-231000 and 2007-322 744 can also be suitably used.

[0100] Examples of acylphosphine oxide include the compounds described in JP-A No. 5-345790 and the compounds described in paragraph [0027] of JP-A No. 6-298818. specific examples of these include bis (2,4,6-trimethylbenzoyl) isobutylphosphine oxide, bis (2,6-dimethoxy) -n-butylphosphine oxide, and 2,6-dimethoxybenzoyl-2,4,6- trimethylbenzoyl-n-butylphosphine oxide. Further, preferred examples of the commercially available products include DAROCURE TPO (trade name, manufactured by BASF Corporation) which is 2,4,6-trimethylbenzoyl-diphenyl-phosphinoxide.

[0101] Examples of α-aminoketone compounds include 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, which is available under the trade name "IRGACURE 379 (manufactured by BASF Corporation)".

[0102] Polymerization initiators can be used alone or in combination of two or more types thereof. The content of the polymerization initiator in the black polymerizable composition according to the invention is preferably from 0.01% by mass to 30% by mass, more preferably from 0.1% by mass to 20% by mass, and particularly preferably from 0.1% by mass to 15% by mass, relative to the total solid content of the polymerizable black composition.

[0103] (C) Polymerizable compound The black polymerizable composition according to the invention comprises a polymerizable compound. As the polymerizable compound (C), a compound which has at least one addition-polymerizable ethylenically unsaturated group and has a boiling point of 100 ° C or more under normal pressure is preferably used.

[0104] Examples of compounds having at least one additionally polymerisable ethylenically unsaturated group and a boiling point of 100 ° C or more under normal pressure include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, or phenoxyethyl (meth) acrylate; polyethylene glycole di (meth) acrylate, trimethylolethane, tri (meth) acrylate, neopentylglycole 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, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerol or trimethylolethane, followed by (meth) acrylation thereof, compounds obtained by poly (meth) acrylation of pentaerythritol or dipentaerythritol, urethane acrylates described in JP-B No. 48-41 708, No. 50 -6,034 and JP-A No. 51-37,193, polyester acrylates disclosed in JP-A No. 48-64,183 and JP-B No. 49-43,191 and No. 52-30,490 and epoxy acrylates produced by a reaction between epoxy resins and (meth) acrylic acids. Further, the compounds described as photocurable monomers and oligomers in the Journal of the Membership Society of Japan, Vol. 20, n ° 7, pp. 300-308 can also be used.

[0105] In addition, the compounds obtained by adding ethylene oxide or propylene oxide to the polyfunctional alcohol mentioned above, followed by (meth) acrylation, which are described in document JP- A No. 10-62,986 such as compounds represented by general formulas (1) and (2) together with specific examples thereof, can also be used.

[0106] In particular, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and compounds in which their acryloyl groups are linked via an ethylene glycol or propylene glycol residue, are preferable. Oligomers of these compounds can be used. Further, urethane acrylates as described in JP-B No. 48-41 708, JP-A No. 51-37193 and JP-B No. 2-322 932-16765, and compounds of urethane and having ethylene oxide backbones as described in JP-B No. 58-49,860, No. 56-17,654, No. 62-39,417 and No. 62-39,418 are also preferable. . Further, by the use of the addition polymerizable compounds having an amine or sulfide structure in their molecule described in JP-A No. 63-277 653, No. 63-260 909 and No. 1-105 238, a black polymerizable composition having an extremely high photosensitive speed can be obtained. Examples of commercially available products thereof include urethane oligomers UAS-10 and UAB-140 (both trade names, manufactured by Sanyo-Kokusaku Pulp Co., Ltd.), UA-7200 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (trade name, manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (trade names, manufactured by Kyoeisha Chemical Co., Ltd), and KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, and KAYARAD DPCA-120 (trade name, manufactured by Nippon Kayaku Co., Ltd.) Further, ethylenically unsaturated compounds having an acidic group are a preferable solution. Examples of commercially available products thereof include TO-756 which is a trifunctional acrylate containing a carboxyl group and TO-1382 which is a pentafunctional acrylate containing a carboxyl group (both trade names, manufactured by Toagosei Co., Ltd.)

[0107] On the other hand, the succinic acid modified monomers of dipentaerythritol hexaacrylate or dipentaerythritol pentaacrylate, pentaerythritol triacrylate, and the like are also preferable. As the polymerizable compound used in the invention, a tetrafunctional or higher functional acrylate compound is more preferable.

[0108] The polymerizable compounds can be used alone or in combination of two or more types thereof. The content of the polymerizable compound in the black polymerizable composition is not particularly limited as long as the sufficient curing reaction is carried out, but it is preferably 3 wt% to 55 wt%, and more preferably 10 wt%. mass at 50% by mass, based on 100 parts by mass of the total solid content.

[0109] (E) Other additives The black polymerizable composition according to the invention may further contain various additives depending on the objects, in addition to the essential components from (A) to (D) and the pigment dispersant mentioned above. (E-1) Binder polymer having a structure different from that of component (D) In the black polymerizable composition, an additional binder polymer (hereinafter also referred to simply as the additional binder polymer (E-1)) having a structure different from that of component (D) can be further used as desired, with the It is an object to improve the characteristics of film or the like, in a range in which the characteristics of the black polymerizable composition according to the invention are not impaired.

[0110] Here, a linear organic polymer is preferably used as the binder polymer. Like the "linear organic polymer", any known linear organic polymer can be used. Preferably, a linear organic polymer which is soluble or swellable in water or weakly alkaline water is chosen to allow development in water or development in weakly alkaline water. The linear organic polymer is chosen not only as a coating agent for the formation of the film, but also depending on the type of the developer such as water, weakly alkaline water, or an organic solvent.

[0111] For example, development in water is possible when a water-soluble organic polymer is used. Examples of such linear organic polymers include radical polymers each having a carboxylic acid group in the side chain, such as those described in, for example, JP-A No. 59-44 615, JP-B No. 54- 34 327, No. 58-12 577 and No. 54-25 957, and JP-A No. 54-92 723, No. 59-53 836 and No. 59-71 048, that is to say, a resin obtained by homopolymerization or copolymerization of a monomer having a carboxyl group, a resin obtained by homopolymerization or copolymerization of a monomer having an acid anhydride and then hydrolysis, half-esterification or half-amidation the anhydride unit acid and epoxy acrylate obtained by modifying the epoxy resin with an unsaturated monocarboxylic acid and acid anhydride. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene, and examples of the monomer having an acid anhydride which includes maleic anhydride. Likewise, acidic cellulose derivatives having a carboxylic acid group in the side chain can be used. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group and the like are useful.

[0112] On the other hand, urethane binder polymers containing an acid group, as described in JP-B No. 7-12004, No. 7-120 041, No. 7-120 042, No. 8 -12,424 and JP-A No. 63-287,944, No. 63-287,947 and No. 1-271,741, Japanese Patent Application No. 10-116,232, etc., are advantageous in terms of suitability. low exposure because they have extremely high resistance. Acetal modified polyvinyl alcohol binding polymers having an acid group as described in European Patents (EP) No. 993,966 and No. 1,204,000, JP-A No. 2001-318,463, and the like are preferable because of the excellent balance between film strength and developability. As other water-soluble linear organic polymers, polyvinyl pyrrolidone, polyethylene oxide, or the like is useful. To increase the strength of a cured film, alcohol soluble nylon, 2,2-bis- (4-hydroxyphenyl) -propane polyethers and epichlorohydrin, and the like are also useful. The content of the additional binder polymer coexisting with respect to the total solid content of the black polymerizable composition according to the invention is preferably from 0.1% by mass to 7.0% by mass, and from the point of view of compatibility between the inhibition of peel pattern and the inhibition of development residues, it is preferably from 0.3% by mass to 6.0% by mass, and even more preferably from 1.0% by mass to 5, 0% by mass.

[0113] (E-2) Colorants other than components (A) In the invention, other dyes other than component (A) can be used in addition, if necessary, to achieve a desired light shielding property. Examples of organic pigments that can be used as a colorant together with component (A) include pigments described in paragraphs [0030] to [0044] of JP-A No. 2008-224 982, CI Pigment Green 58, and a dye obtained by changing a C1 substituent of CI Pigment Blue 79 to an OH substituent. In particular, examples of pigments which can preferably be used include: C.I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, and 185; C.I. Pigment Orange 36; C.I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, and C.I. Pigment Violet 19, 23, 29, and 32; C.I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, and 66; C.I. Pigment Green 7, 36, 37, and 58; and C.I. Pigment Black 1. However, the colorants which can be used together with the component (A) are not limited thereto.

[0114] The dye which can be used as an additional dye is not particularly limited, and a dye selected from the known dyes can be used. Examples of dyes include the dyes described in JP-A No. 64-90 403, JP-A No. 64-91 102, JP-A No. 1-94 301, JP-A No. 6-11 614, Japanese Patent No. 2,592,207, US Patent No. 4,808,501, US Patent No. 5,667,920, US Patent No. 5,059,500, JP-A No. 5-333,207, JP-A No. 6-35 183, JP-A No. 6-51 115, JP-A No. 6-194 828, JP-A No. 8-211 599, JP-A No. 4-249 549, JP-A No. 10-123 316, JP-A No. 11-302 283, JP-A No. 7-286 107, JP-A No. 2001-4 823, JP-A No. 8-15 522, JP-A No. 8-29 771, JP-A No. 8-146 215, JP-A No. 11-343 437, JP-A No. 8-62 416, JP-A No. 2002-14 220, JP-A No. 2002-14 221, JP-A No. 2002-14 222, JP-A No. 2002-14 223, JP-A No. 8-302 224, JP-A No. 8-73 758, JP-A No. 8-179 120 and JP-A No. 8-151,531. Furthermore, dyes having the chemical structures of a pyrazole azo dye, an anilinoazo dye, a triphenylmethane dye, an anthraquinone dye, an anthrapyridone dye, a benzylidene dye, an oxonol dye, a pyrazoletriazoleazo dye, a pyridoneazo dye , a cyanine dye, a phenothiazine dye, a pyrrolopyrazoleazomethine dye, a xanthene dye, a phthalocyanine dye, a benzopyran dye, an indigo dye, or the like can also be used.

[0115] [0115] (E-3) Organic solvent A solvent can be added to the black polymerizable composition according to the invention. The organic solvent is basically not particularly limited as long as the solubility of each component and the coating property of the black polymerizable composition are satisfied, but it is preferably selected depending on the ultraviolet ray absorbent to be used, binder solubility, coating property, and safety. Further, in order to prepare the black polymerizable composition according to the invention, at least two kinds of organic solvents are preferably contained.

[0116] Preferred examples of the organic solvent 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, ethyl lactate, alkyl oxyacetate (e.g., methyl oxyacetate, ethyl oxyacetate, oxyacetate butyl (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl, ethyl ethoxyacetate and ethoxyacetate)), 3-oxypropionate alkyl esters (eg, 3-oxypropionate ethyl and 3-oxy-propanoate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate)), alkyl 2-oxypropionate esters (eg methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate (eg methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, and ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy- 2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate , ethyl 2-oxobutanoate; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol, monomethyl ether, ethylene glycol monoethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, l '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 or monopropyl glycol ether acetate ; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, or 3-heptanone; and aromatic hydrocarbons such as toluene or xylene.

[0117] Two or more kinds of these organic solvents are preferably mixed from the standpoints of the solubility of the UV absorber and the alkaline soluble resin, of improving the profile of a coated surface, and the like. In such a case, it is particularly preferable to use a mixed solution comprising two or more elements selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate cellosolve, ethyl lactate, l 'diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butylcarbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

[0118] The content of the organic solvent in the black polymerizable composition is preferably an amount such that the total solid concentration of the composition is from 5% by mass to 80% by mass, preferably 5% by mass to 60% by mass. mass, and in particular preferably 10 wt% to 50 wt%, from the viewpoint of the coating property.

[0119] (E-4) Surfactant From the standpoint of improving the application property, any of the various surfactants can be added to the black polymerizable composition according to the invention. As a surfactant, various surfactants such as a fluorine-containing surfactant (fluorinated surfactant), a nonionic surfactant, a cationic surfactant, an anionic surfactant, or a silicone surfactant can be used.

[0120] In particular, when the black polymerizable composition according to the invention contains a fluorinated surfactant, the liquid characteristics (in particular, the fluidity) of the coating liquid prepared using the black polymerizable composition is further improved, whereby the uniformity or film-forming property is further improved. In other words, when a film is formed using a coating liquid which contains a black polymerizable composition containing a fluorinated surfactant, the interfacial tension between the surface to be coated and the coating liquid is lowered, and the wettability of the surface. to be coated is improved, leading to improved coating ability of the coating liquid to the surface to be coated. For this reason, even if a thin film of several µm is formed by using a small amount of the coating liquid, the formation of a film having a uniform film thickness with low thickness differentiation is preferably carried out.

[0121] The fluorine content in the fluorinated surfactant is preferably 3 wt% to 40 wt%, more preferably 5 wt% to 30 wt%, and in particular preferably 7 wt% to 25 wt. % by mass. A fluorinated surfactant having a fluorine content ratio within these ranges is effective in the uniformity of the coating film thickness and the liquid saving property, and the solubility in the colored photosensitive composition. is also good.

[0122] Examples of the fluorinated surfactant include MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFAC F141, MEGAFAC F142, MEGAFAC F143, MEGAFAC F144, MEGAFGAC F30, MEGAFAC F144, MEGAFGAC F47, MEGAFAC F144, MEGAFGAC F47 , MEGAFAC F482, MEGAFAC F554, MEGAFAC F780, and MEGAFAC F781 (all trade names, manufactured by DIC Corporation), FLUORAD FC430, FLUORAD FC431, and FLUORAD FC171 (all trade names, manufactured by Sumitomo 3M Limited), and SURFLON S-382 , SURFLON SC-101, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC1068, SURFLON SC-381, SURFLON SC-383, SURFLON S393, and SURFLON KH-40 (all trade names, manufactured by Asahi Glass Co., Ltd.)

[0123] Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (eg, glycerin propoxylate, and glycerin ethoxylate), polyoxyethylene. lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, fatty acid desorbitan ester (such as PLURONIC L10, L31, L61, L62, 10R5, 17R2, and 25R2, TETRONIC 304, 701, 704, 901, 904, or 150R1 (trade names, manufactured by BASF Corporation)), and SOLFPERSE 20000 (trade name, manufactured by Lubrizol Corporation , Japan).

[0124] Specific examples of the cationic surfactant include phthalocyanine derivative (trade name: EFKA-745, manufactured by Morishita & Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co. , Ltd), a (meth) acrylic (co) polymer POLYFLOW No. 75, 90 and 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (trade name, manufactured by Yusho Co., Ltd.)

[0125] Specific examples of the anionic surfactant include W004, W005 and W017 (trade names, manufactured by Yusho Co., Ltd.)

[0126] Examples of the silicone surfactant include TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, and TORAY SILICONE SH8400 (trade names, all manufactured by Dow Corning Toray Co., Ltd), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (trade names, all manufactured by Momentive Performance Materials Inc), KP341, KF6001, and KF6002 (trade names, all manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK307, BYK323 and BYK330 (trade names, manufactured by BYK Chemie). The surfactants can be used alone or in combination of two or more types thereof. The amount of the surfactant to be added is preferably 0.001 wt% to 2.0 wt%, and preferably 0.005 wt% to 1.0 wt%, based on the total mass of the black polymerizable composition. .

[0127] (E-5) Sensitizer The black polymerizable composition may further contain a sensitizer for the purpose of improving the efficiency of radical generation of polymerization initiator, and achieving longer wavelength at photosensitive wavelengths. As the sensitizer used in the invention, a sensitizer which sensitizes the polymerization initiator used therewith by an electron transfer mechanism or an energy transfer mechanism is preferable. Preferred examples of the sensitizer include the compounds described in paragraphs [0085] to [0098] of JP-A No. 2008-214,395. The content of the sensitizing agent is preferably in the range of 0.1 wt% to 30 wt%, and more preferably in the range of 1 wt% to 20 wt%, and even more preferably in the range of 2% by mass to 15% by mass, relative to the total solid mass of the black polymerizable composition, from the point of view of sensitivity and of storage stability.

[0128] Polymerization inhibitor (E-6) It is preferable to add a small amount of a polymerization inhibitor to the black polymerizable composition so as to prevent unwanted heat polymerization of the polymerizable compound during preparation or storage of the composition. As the polymerization inhibitor, a known thermal polymerization inhibitor can be used. Examples of these include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl- 6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), and cerous salts of N-nitrosophenyl hydroxylamine. The amount of the thermal polymerization inhibitor to be added is preferably from about 0.01 wt% to about 5 wt%, based on the total solid content of the polymerizable black composition. Further, a higher fatty acid or a derivative thereof such as behenic acid or a behenic acid amide can be added to be present on the surface of the coating film during the drying process after coating, so that inhibition of polymerization by oxygen is inhibited. The amount of the higher fatty acid or its derivative to be added is preferably from about 0.5 wt% to about 10 wt% based on the total composition.

[0129] (E-7) Adhesion improving agent An adhesion improver can be added to the black polymerizable composition according to the invention, in order to improve the adhesiveness of the surface of a hard material such as a backing. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent. Preferred examples of the silane coupling agent include γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxy silane, γ-acryloxypropyl-trimethoxy silane, γ-acryloxypropyl triethoxy silane, γ-mercaptopropyl trimethoxy silane, silane γ-aminopropyl triethoxy, trimethoxy phenyl silane and silane 3 methacryloxypropyl-dimethoxymethyl. More preferred examples include 3-methacryloxypropyl dimethoxymethyl silane and γ-methacryloxypropyl trimethoxy silane. The amount of the adhesion improving agent to be added is preferably from 0.5% by mass to 30% by mass, and more preferably from 0.7% by mass to 20% by mass, relative to the content. total solid of the black polymerizable composition of the invention. In particular, when the resistant substance (for example, the black polymerizable composition) according to the present invention is used for forming a lens on a glass substrate, it is preferable to add an adhesion improving agent to the resistance. from the point of view of improving sensitivity.

[0130] (E-8) Other additives The black polymerizable composition according to the invention may further contain a co-sensitizer for the purpose of, for example, further improving the sensitivity of a sensitizing dye or initiator to actinic radiation, or of preventing inhibition of actinic radiation. polymerization of a photopolymerizable compound caused by oxygen. Further, in order to improve the physical properties of the cured coating film, known additives such as a surfactant, diluent, plasticizer or oil sensitizer can be added, if necessary.

[0131] The black polymerizable composition according to the invention contains at least (A) the black material (preferably, a pigment dispersion composition containing a pigment dispersant), (B) the polymerization initiator, (C) the polymerizable compound, and (D) the alkaline soluble binder polymer, which are mentioned above, and, optionally, may further contain any of the various additives and an organic solvent (E-3), and may be prepared by mixing these components and, where appropriate, by additives such as a surfactant.

[0132] When the black polymerizable composition according to the invention has such a configuration, a light shielding film having excellent resistance to alkaline developer is formed. For this reason, the black polymerizable composition is useful for forming the light shielding region of a wafer-nested lens. Further, to form a light shielding film, it is preferable to apply the black polymerizable composition to a solid surface by spray coating, as described below. Therefore, from the standpoint of preventing liquid drainage when the black polymerizable composition is deposited on a curved surface, the total solid content in the black polymerizable composition is preferably 20% by mass to 35% by mass, from more preferably from 21% by mass to 33% by mass, and preferably from 25% by mass to 30% by mass.

[0133] Lens fitted with a wafer The wafer-fitted lens of the invention may include a light shielding film (eg, a black layer) formed from the black polymerizable composition of the invention. Hereinafter, the wafer-fitted lens according to the invention will be described.

[0134] FIG. 1 is a view showing an example of the configuration of a wafer-nested lens array having multiple wafer-nested lenses. As shown in fig. 1, the array of wafer-fitted lenses comprises a substrate 10, and lenses 12 disposed on the substrate 10. In FIG. 1, the plurality of lenses 12 are arranged two-dimensionally with respect to the substrate 10, but they can also be arranged in one dimension. Fig. 2 is a cross-sectional view of the wafer-nested lens array shown in FIG. 1, which is taken along the A-A line. As shown in fig. 2, in the wafer-nested lens array, a light shielding film 14 which prevents transmission of light into regions other than the lenses 12 is formed between the plurality of lenses 12 provided on the substrate 10. The wafer-fitted lens according to the invention comprises a lens 12 present on the substrate 10, and the light protection film 14 provided on the peripheral part of the lens. The curable black composition according to the invention is used in forming the light shielding film 14, thereby forming a light shielding region.

[0135] Hereinafter, a configuration of the wafer-nested lens array, in which a plurality of lenses 12 are arranged two-dimensionally with respect to the substrate 10, as shown in FIG. 1, will be described by way of example.

[0136] The lens 12 is generally formed from the same material as that of the substrate 10, and can be formed integrally on the substrate 10 or can be made as a separate structure and attached to the substrate. Here, an example of the wafer-nested lens according to the invention is cited, but the wafer-nested lens according to the invention is not limited thereto, and various embodiments such as one which has a multi-layered structure or one which is separated into lens modules by cutting, can be used.

[0137] Examples of materials for forming lens 12 include glass. There are different types of glass, and glass is preferably used as a material for a lens having a high power because a glass having a high refractive index can be selected from different types of glass. In addition, glass has the advantages of excellent heat resistance and strength for mounting reflow on an imaging unit.

[0138] Examples of other materials for forming lens 12 include resins. A resin has excellent machinability, and is suited in that the surface of the lens is easily and inexpensively formed using, for example, a mold or die.

[0139] The wafer-fitted lens is preferably formed using an energy curable resin. The energy curable resin can be any resin which can be cured by heating or a resin which can be cured by irradiation with rays of active energy (eg, application of heat, radiation of ultraviolet rays , or electron ray radiation). In view of the reflow mounting of an imaging unit, a resin having a relatively high softening point, for example, 200 ° C or more, is preferable, and a resin having a softening point of 250 ° C or more. more is more preferable. The preferable resin as the lens material will be described below.

[0140] Examples of an ultraviolet curable resin include an ultraviolet curable silicone resin, an ultraviolet curable epoxy resin, and an ultraviolet curable acrylic resin. The epoxy resin which can be used in the invention has a coefficient of linear expansion of 40 to 80 [10 <–> <6> / K] and has a refractive index of 1.50 to 1.70, and preferably from 1.50 to 1.65.

[0141] Examples of a thermosetting resin include a thermosetting silicone resin, an epoxy thermosetting resin, a thermosetting phenolic resin, and an acrylic thermosetting resin. For example, the silicone resin which can be used has a coefficient of linear expansion of 30 to 160 [10 <–> <6> / K] and has a refractive index of 1.40 to 1.55. For example, the epoxy resin which can be used has a coefficient of linear expansion of 40 to 80 [10 <–> <6> / K] and has a refractive index of 1.50 to 1.70, and preferably of 1.50 to 1.65. The phenol resin which can be used has a coefficient of linear expansion of 30 to 70 [10 <–> <6> / K] and has a refractive index of 1.50 to 1.70. The acrylic resin which can be used has a coefficient of linear expansion of 20 to 60 [10 <–> <6> / K] and has a refractive index of 1.40 to 1.60, and preferably 1.50. at 1.60.

[0142] A commercially available product can be used as a thermosetting resin. Specific examples thereof include SMX-7852 and SMX-7877 (both trade names, manufactured by Fuji Polymer Industries Co., Ltd.), IVSM-4500 (trade name, manufactured by Toshiba Corporation), and SR-7010 ( trade name, manufactured by Dow Corning Toray Co., Ltd.)

[0143] Examples of a thermoplastic resin include a polycarbonate resin, a polysulfone resin, and a sulfonated polyester resin. The polycarbonate resin which can be used has a coefficient of linear expansion of 60 to 70 [10 <–> <6> / K] and has a refractive index of 1.40 to 1.70, and preferably 1, 50 to 1.65. The polysulfone resin which can be used has a coefficient of linear expansion of 15 to 60 [10 <–> <6> / K] and has a refractive index of 1.63. Polyether sulfonated resin, which can be used, has a coefficient of linear expansion of 20 to 60 [10 <–> <6> / K] and has a refractive index of 1.65.

[0144] Furthermore, optical glass generally has a coefficient of linear expansion of 4.9 to 14.3 [10 <–> <6> / K] at 20 ° C and has a refractive index of 1.4 to 2.1 wavelength of 589.3 nm. In addition, quartz glass has a coefficient of linear expansion of 0.1 to 0.5 [10 <–> <6> / K] and has a refractive index of approximately 1.45.

[0145] It is preferable that the curable resin composition suitable for use in forming a lens has a suitable fluidity before curing, from the standpoint of formability as well as the shape transferability of the mold. More specifically, it is preferable that the curable resin composition is liquid at normal temperature and has a viscosity of about 1000 mPa⋅s to about 50,000 mPa⋅s.

[0146] On the other hand, it is preferable that the curable resin composition capable of being used to form a lens has heat resistance so that it does not suffer from heat deformation through a reflow process. after hardening. From this point of view, a glass transition temperature of the cured material is preferably 200 ° C or more, more preferably 250 ° C or more, and most preferably 300 ° C or more. In order to impart such high heat resistance to the resin composition, it is necessary to suppress mobility at the molecular level. Examples of an effective method for this purpose include (1) increasing the cross-bond density per unit volume, (2) using a resin having a rigid ring structure (e.g., a resin having an alicyclic structure such as cyclohexane, norbornane, or tetracyclododecane, an aromatic structure such as benzene or naphthalene, a cardo structure such as fluorene 9,9'-biphenyl, or a spiro structure such as spirobiindane, in particular, for example, the resins described in JP-A No. 9-137 043-A, No. 10-67 970, No. 2003-55 316, No. 2007-334 018 and No. 2007-238 883, and the like) , and (3) homogeneously dispersing a high Tg material such as an inorganic fine particle (eg, those described in JP-A No. 5-209,027 and No. 10-298,265). These methods can be used singly or in combination of several types, and are preferably adjusted within a range not detrimental to other properties such as fluidity, shrinkage rate, or refractive index.

[0147] From the viewpoint of the degree of accuracy of transfer to form, a curable resin composition which exhibits a low volume shrinkage ratio by a curing reaction is preferable. The cure shrinkage ratio of the resin composition used in the invention is preferably 10% or less, more preferably 5% or less, and more preferably 3% or less.

[0148] Examples of the resin composition having a low cure shrinkage ratio include the following (1) to (6): (1) a resin composition containing a high molecular weight curing agent (eg, prepolymer) (eg, a composition as described in JP-A No. 2001-19740, JP-A No. 2004 -302,293 and JP-A No. 2007-211,247), wherein the number average molecular weight of the high molecular weight curing agent is preferably in a range of 200 to 100,000, more preferably in a range of ranging from 500 to 50,000 and more preferably within a range of 1,000 to 20,000 and a value obtained by calculating the number average of the molecular weight of the curing agent / the number of reactive curing groups in the curing agent is preferably in a range of 50 to 10,000, more preferably in a range of 100 to 5,000 and particularly preferably in a range of 200 to 3,000; (2) a resin composition containing a non-reactive material (eg, an organic fine particle, an inorganic fine particle, or a non-reactive resin) (eg, the composition as described in JP-A No. 6 -298,883, JP-A No. 2001-247,793 and JP-A No. 2006-225,434); (3) a resin composition containing a relatively weak reactive cross-link shrinkage group (for example, a ring-opening polymerizable group such as an epoxy group (for example, that described in JP-A No. 2004). -210,932), an oxetanyl group (eg, that described in JP-A No. 8-134,405), an episulfide group (eg, that described in JP-A No. 2002-105,110) , a cyclic carbonate group (eg, that described in JP-A No. 7. -62065), an ene / thiol curing group (eg, that described in JP-A No. 2003-20334) , a hydrosilylation curing group (eg, that described in JP-A No. 2005-15666); (4) a resin composition containing a resin having a rigid backbone (eg, fluorene, adamantane, or isophorone) (eg, that described in JP-A No. 9-137 043); (5) a resin composition which contains two kinds of monomers having different polymerizable groups and which forms an interpenetrating network structure (IPN structure) (for example, that described in JP-A No. 2006-131,868); and (6) a resin composition containing an expandable material (eg, the composition described in JP-A No. 2004-2719 and JP-A No. 2008-238,417). Further, it is preferable to use a combination of two or more of the shrinkage reduction curing means (for example, a resin composition which contains a prepolymer containing a ring-opening polymerizable group and fine particles), point of view of optimization of physical properties.

[0149] For forming the wafer-nested lens according to the invention, two or more types of resin compositions having different high and low Abbe numbers, respectively, are preferred. In a resin having a relatively high Abbe number, the Abbe number (vd) is preferably 50 or more, more preferably 55 or more, and more preferably 60 or more. The refractive index (nd) of the resin is preferably 1.52 or more, more preferably 1.55 or more, and more preferably 1.57 or more. The resin is preferably an aliphatic resin, and is more preferably a resin having an alicyclic structure (eg, a resin having a cyclic structure such as cyclohexane, norbornane, adamantane, tricyclodecane, or tetracyclododecane, in particular , for example, the resins described in JP-A No. 10-152,551, JP-A No. 2002-212,500, JP-A No. 2003-20,334, JP-A No. 2004-210,932, JP-A No. 2006-199790, JP-A No. 2007-2144, JP-A No. 2007-284,650 and JP-A No. 2008-105,999).

[0150] In a resin having a relatively low Abbe number, the Abbe number (vd) is preferably 30 or less, more preferably 25 or less, and more preferably 20 or less. The refractive index (nd) of the resin is preferably 1.60 or more, more preferably 1.63 or more, and particularly preferably 1.65 or more. The resin is preferably a resin having an aromatic structure, and more preferably, for example, a resin containing a structure of 9,9'-diarylfluorene, naphthalene, benzothiazole, benzotriazole, or the like (more specifically, for example, the resins described in JP-A No. 60-38 411, JP-A No. 10-67,977, JP-A No. 2002-47,335, JP-A No. 2003-238,884, JP-A No. . 2004-83,855, JP-A No. 2005-325,331, JP-A No. 2007-238,883, WO 2006/095,610 and Japanese Patent No. 2,537,540).

[0151] In the resin composition used to form a wafer-nested lens, it is preferable to use an organic or inorganic composite material containing inorganic fine particles dispersed in a matrix, from the viewpoints of increasing d 'a refractive index or setting of the Abbe number. Examples of inorganic fine particles in the organic or inorganic composite material include fine oxide particles, fine particles of sulfide, fine particles of selenide, and fine particles of telluride. Specific examples of these include fine particles of zirconium oxide, titanium oxide, zinc oxide, tin oxide, niobium oxide, cerium oxide, aluminum oxide, lanthanum oxide, yttrium oxide, zinc sulfide or the like.

[0152] The inorganic fine particles can be used alone or in combination of two or more types thereof. In addition, inorganic fine particles can be made from a composite of several components. In order to reduce, for example, photocatalytic activity and water absorption, the inorganic fine particles can be doped with a heterogeneous metal, or a surface layer thereof can be coated with a heterogeneous metal oxide such as that silica or alumina, or the surface thereof, can be modified using a silane coupling agent, a titanate coupling agent, an organic acid (eg, carboxylic acids, sulfonic acids, phosphoric acids and phosphonic acids), a dispersant having an organic acid group, or the like. The average primary particle size number of the inorganic fine particles can generally range from about 1 nm to 1000 nm. When the particle size is too small, there are cases when the physical properties are changed. When the particle size is too large, the effect of Rayleigh scattering is pronounced. In this regard, the average size number of the primary particles is preferably 1 nm to 15 nm, more preferably 2 nm to 10 nm and particularly preferably 3 nm to 7 nm. Further, a narrower particle size distribution of the inorganic fine particles is preferable. The monodisperse particle has various definitions, and for example, the range of values defined as described in JP-A No. 2006-160,992 corresponds to a preferable particle size distribution range. The average primary particle size number described above can be measured using, for example, an X-ray diffraction device (XRD), an electron transmission microscope (TEM), or the like.

[0153] The refractive index of inorganic fine particles at 22 ° C and at a wavelength of 589.3 nm is preferably 1.90 to 3.00, more preferably 1.90 to 2.70 , and particularly preferably from 2.00 to 2.70.

[0154] The content of inorganic fine particles in the organic-inorganic composite materials is 5 wt% or more, more preferably 10 wt% to 70 wt%, and particularly preferably 30 wt% to 60 wt. % by mass, based on the resin which is a matrix for inorganic fine particles, from the viewpoint of transparency and a higher refractive index.

[0155] Examples of the matrix resin used in the organic-inorganic composite material include an ultraviolet curable resin, a thermosetting resin, a thermoplastic resin having a relatively high Abbe number, and a resin having a number d. 'Relatively weak abbe, which are described above as wafer-nested lens materials. Further, examples of the resin include a resin having a refractive index greater than 1.60, such as those disclosed in JP-A No. 2007-93 893, a block copolymer consisting of a hydrophobic segment and a hydrophilic segment, such as those described in JP-A No. 2007-211 164, a resin having a functional group capable of forming an arbitrary chemical bond with an inorganic fine particle, at one end or the side of the chain. a polymer, such as those described in JP-A No. 2007-238,929, Japanese Patent Applications No. 2008-12,645, No. 2008-208,427, No. 2008-229,629 and No. 2008- 219,952 and a thermoplastic resin disclosed in Japanese Patent Application Nos. 2008-197,054 and No. 2008-198,878. Further, additives such as a plasticizer or a dispersant can be added to the organic-inorganic composite material, if necessary.

[0156] In this regard, the preferred combinations of the resin as a matrix and the inorganic fine particles are as follows. That is, when the resin having a relatively high Abbe number as described above is used as a matrix, it is preferable that the fine particles of lanthanum oxide, aluminum oxide, of zirconium oxide, or the like are dispersed in the resin as inorganic fine particles. When the resin having a relatively low Abbe number is used as a matrix, it is preferable that the fine particles of titanium oxide, tin oxide, zirconium oxide, or the like are dispersed in the mixture. resin as inorganic fine particles.

[0157] In order to homogeneously disperse the inorganic fine particles, it is preferable to suitably use, for example, a dispersant containing a functional group having reactivity to the resin monomer to form a matrix (for example, dispersants described in the example section of JP-A No. 2007-238884, and the like), a block copolymer formed from a hydrophobic segment and a hydrophilic segment (e.g., those described in JP- A No. 2007-211 164) or a resin having a functional group capable of forming arbitrary chemical bonds with inorganic fine particles in a chain end or side of high molecular weight (for example, those described in JP-A No. 2007-238,929 and No. 2007-238,930, and the like).

[0158] The resin composition used for forming a wafer-nested lens according to the invention can be suitably mixed with an additive such as a known release agent such as a silicon compound, a fluorine-containing compound, or a compound containing a long chain alkyl group, or an antioxidant such as hindered phenol.

[0159] The resin composition used to form a wafer-nested lens according to the invention can be mixed with a curing catalyst or an initiator, if necessary. Specific examples thereof include a compound which promotes a curing reaction (by radical polymerization or by ionic polymerization) by the action of heat or rays of active energy, as described in paragraphs [0065] to [0066] of JP-A No. 2005-92 099. The amount of curing reaction promoter to be added may vary depending on the type of catalyst or initiator, or the type of a reactive curing moiety, and therefore the amount cannot be not be settled unconditionally. However, the amount is preferably about 0.1 wt% to 15 wt%, and more preferably about 0.5 wt% to 5 wt%, based on the total solid content of the composition. of resin.

[0160] The resin composition used in the production of wafer-nested lens according to the invention can be suitably made by mixing the components mentioned above. At this time, when components other than a lower molecular weight liquid monomer (reactive diluent) dissolve in the monomer, no separate solvent should be added, while in the case where the components do not dissolve in the monomer liquid of lower molecular weight, the respective components can be dissolved in a solvent, to thereby prepare a resin composition. The solvent which can be used in the resin composition is not specifically limited, and can be appropriately selected as long as no precipitation is generated in the resulting composition, and homogeneous dissolution and dispersion are obtained. Specific examples of the solvent include ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone), esters (eg, ethyl acetate and butyl acetate), ethers ( eg, tetrahydrofuran and 1,4-dioxane), alcohols (eg methanol, ethanol, isopropyl alcohol glycol, butanol, and ethylene), aromatic hydrocarbons (eg, toluene and xylene) and water. When the resin composition contains the solvent, it is preferred that the composition is cast on a substrate and / or a mold, and the solvent is dried, followed by a transfer operation to the shape of the mold.

[0161] The substrate 10 can be formed from the same material as the molding material of the lens 12. Alternatively, the substrate 10 can be formed from a material different from the molding material of the lens 12 as long as the substrate 10 is formed of a material transparent to visible light, such as glass. In this case, it is preferable that the material for forming the substrate 10 has the same or substantially the same coefficient of linear expansion as that of the material for forming the lens 12. In a case where the coefficient of linear expansion of the material for forming the lens 12 is the same or substantially the same as that of the material for forming the substrate 10, the deformation or breakage of the lens 12 during heating, which is caused due to different linear expansion ratios, is suppressed in the wafer-nested lens reflow mounting on an imaging unit.

[0162] Although not shown in FIGS. 1 and 2, an infrared filter (IR filter) may be formed on the surface of the optical incidence face of the substrate 10.

[0163] Hereinafter, with reference to FIGS. 3 to 8C, specific description will be given of the configuration and production of a wafer-nested lens, with reference to a method of making an array of wafer-nested lenses.

[0164] The configuration and production of a wafer-fitted lens (1) Lens formation First of all, with reference to fig. 3 and 4A to 4C, a method for forming a lens 12 on a substrate 10 is described. Here, fig. 3 is a view showing the feed state of a molding material (referred to as "M" in Fig. 3) which is a resin composition for forming a lens, on a substrate 10. Figs. 4A to 4C are schematic views showing the procedures for molding a lens 12 onto a substrate 10 using a mold 60.

[0165] As shown in FIG. 3, the molding material M is applied drop by drop, using a dispenser 50, to areas of the substrate 10 on which the lenses 12 are to be formed. The molding material M in an amount necessary for the formation of a lens 12 is supplied to each of the areas to which the lenses are to be supplied.

[0166] After the molding material M is supplied to the substrate 10, the mold 60 for forming a lens 12 is disposed above the surface of the substrate 10, on which the molding material M has been supplied, as shown. fig. 4A. Here, several concave portions 62 for transferring the shape of a lens 12 are provided in the mold 60 according to a desirable number of lenses 12.

[0167] Subsequently, as shown in FIG. 4B, the mold 60 is pressed onto the molding material M on the substrate 10, so that the molding material M is deformed into the shape of the concave parts 62. Then, the molding material M is hardened while the mold 60 is pressed onto the molding material M, by irradiating heat or ultraviolet light from outside the mold 60 when the molding material M is a thermosetting resin or an ultraviolet curable resin.

[0168] After the molding material M is hardened, the substrate 10 and the lenses 12 are demolded 60 as shown in FIG. 4C.

[0169] The formation of the protective film against light With reference to fig. 5A to 5C, a method of forming a light shielding film 14 in the peripheral portion of the lenses 12 will be described. Here, figs. 5A to 5C are schematic cross-sectional views showing the processes of forming a light shielding film 14 on the substrate 10 on which lenses 12 have been formed.

[0170] A method of forming a light shielding film 14 comprises at least: applying the black curable composition according to the invention to the substrate 10 to form a light shielding coating layer 14A (which may be referred to as the "light shielding coating layer forming method") ( see Fig. 5A.); subjecting the light shielding coating layer 14A to pattern exposure through a mask 70 (which may be referred to as the "exposure process") (see Fig. 5B); and developing the light shielding coating layer 14A after exposure and then removing an uncured portion, to form a patterned light shielding film 14 (which may be referred to as the "developing process ”) (See fig. 5C).

[0171] The light shielding film 14 can be formed arbitrarily, before or after the production of the lens 12. In the following, a method of forming a patterned light shielding film after the lens 12 has been produced will be described in detail. Hereinafter, the respective steps of the method of forming a light shielding film 14 will be described.

[0172] A method of forming a light-shielding coating layer In the method of forming a light shielding coating layer, as shown in fig. 5A, the black curable composition is deposited on the substrate 10 and the lenses 12 to form a light shielding coating layer 14A having a low light reflection ratio, which is formed from the black curable composition. In this case, the light shielding coating layer 14A is formed so as to cover the entire surface of the substrate 10, and the lens surfaces 12a and the surface of the peripheral portion 12b of the lenses 12.

[0173] The substrate 10 which can also be used in this process is not particularly limited and examples thereof include soda glass, non-alkaline glass, PYREX glass (registered trademark), quartz glass. , and a transparent resin. The substrate 10 as mentioned herein refers to a configuration including both the lens 12 and the substrate 10 in an embodiment in which the lens 12 and the substrate 10 are integrally formed. On the substrate 10, an undercoat can be provided, if necessary, for improving the adhesion with the top layer, preventing material diffusion or planarization (flattening) of the surface of the substrate 10.

[0174] Examples of a method of applying the black curable composition to the substrate 10 and the lenses 12 include various coating methods such as slit coating, spray coating, inkjet method, spin coating, molded coating, roll coating, or screen printing process. The film thickness immediately after the application of the black curable composition is preferably 0.1 µm to 10 µm, more preferably 0.2 µm to 5 µm, and even more preferably 0.2 µm to 3 µm , in view of the uniformity of thickness of the coating film, and the ease of drying of the coating solvent.

[0175] The drying (precooking) of the light-shielding coating layer 14A deposited on the substrate 10 can be carried out using a hot plate, an oven or the like, at a temperature of 50 ° C at 140 ° C for 10 seconds to 300 seconds.

[0176] The thickness of the coating film after the drying of the black curable composition (hereinafter also referred to simply as "dry film thickness") can be arbitrarily chosen according to desired performance such as the property of protection against light, and is generally in a range of about 0.1 µm to less than 50 µm.

[0177] Exposure process In the exposure process, the light shielding coating layer 14A formed in the light shielding coating layer forming process is subjected to image-like exposure. Image-shaped exposure can be performed by exposure sweep, but as shown in Fig. 5B, exposure through a mask 70 having a predetermined mask pattern is preferable.

[0178] In the exposure in this method, the coating layer 14A is exposed to light through a mask having a predetermined mask pattern, so that only a light irradiated portion is cured in the coating layer 14A. . A mask pattern is used through which the surfaces of the peripheral lens portions 12b and the surface of the substrate 10 present between the lenses 12 are irradiated with light. Therefore, only the light shielding coating layer 14A present at areas other than the lens surfaces 12a is cured by irradiation of light, and the cured areas form a light shielding film 14.

[0179] Like radiation which can be used for exposure, ultraviolet rays, such as g-rays, h-rays, or i-rays are preferably used. Radiation can come from a single wavelength light source or can come from a light source with all wavelengths such as a high pressure mercury lamp.

[0180] Development process Subsequently, by carrying out alkaline developing treatment (developing process), a part which was not irradiated by light during exposure, that is, an uncured part of the light shielding coating layer 14A, is eluted in an aqueous alkaline solution, and only the parts hardened by irradiation of light remain. Specifically, when the light shielding coating layer 14A exposed as shown in FIG. 5B is developed, only the light shielding coating layer 14A which has been formed on the lens surfaces 12a is removed, and a cured light shielding film 14 is formed in the areas other than the lens surfaces 12a. , as shown in fig. 5C.

[0181] The alkaline agent contained in a developer (ie an aqueous alkaline solution) used in the development process can be any of an organic alkaline agent, an inorganic alkaline agent, and a combination of an organic alkaline agent. and an inorganic alkaline agent. It is preferable to use an organic alkaline developer in the formation of the light shielding film in the invention, from the viewpoint of the reduced probability of damaging a peripheral circuit. Examples of the alkaline agent used in a developer include organic alkali compounds (organic alkali agents) such as aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, moline , pyrrole, piperidine, or 1,8-diazabicylclo- [5,4,0] -7-undecene; and inorganic compounds (inorganic alkaline agents) such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, or potassium hydrogen carbonate. An aqueous alkaline solution obtained by diluting any of these alkaline agents with pure water at a concentration of 0.001 wt% to 10 wt%, and preferably 0.01 wt% to 1 wt%. mass, is preferably used as a developer.

[0182] In general, development is carried out at a temperature of 20 ° C to 30 ° C for a development time of 20 seconds to 90 seconds.

[0183] If a developer formed from the alkaline aqueous solution is used, generally an unexposed portion of a coating film is removed by the developer, followed by washing (rinsing) with pure water. In other words, after a development treatment, the excess developer is washed off and removed satisfactorily with pure water, and a drying step is performed thereafter.

[0184] Furthermore, the production process may further comprise, if necessary, a step of curing the formed light protection film (that is to say of the light protection pattern) by heating (by example, post-curing) and / or by exposure to light, after performing the light-shielding coating layer formation process, the exposure process, and the development process.

[0185] Post-curing is a heating treatment carried out after development, with the aim of complete curing, and is generally a thermal curing treatment at 100 ° C to 250 ° C. Conditions such as temperature and post-bake time can be suitably adjusted depending on the materials of substrate 10 or lens 12. For example, when the substrate is glass 12, the post-bake temperature is preferably 180 ° C to 240 ° C. The post-bake treatment of a light shielding film 14 formed through development can be carried out in a continuous or batch system using a heater such as a hot plate, a convection oven (a dryer hot air circulating), or a high frequency heater under the conditions mentioned above.

[0186] In the procedure mentioned above, an embodiment in which the lens 12 has a concave shape is described. However, the shape of the lens is not specifically limited thereto, and the lens may have a convex or aspherical surface. Further, in the above-mentioned procedure, an embodiment in which a wafer-nested lens having a plurality of lenses 12 formed on one side of a substrate 10 is described. However, a wafer-nested lens according to the invention may have a configuration in which a plurality of lenses 12 are formed on both sides of a substrate 10, and in this case, the light shielding layers 14 are formed on it. both sides of substrate 10 in regions other than the lens surfaces.

[0187] Configuration and production of a wafer-fitted lens (2). Fig. 6 is a view showing another exemplary configuration of a wafer-nested lens array. The matrix of wafer-fitted lenses shown in fig. 6 has a configuration (the monolithic type) in which a substrate 10 and the lenses 12 are formed at the same time using the same molding material. Examples of molding materials used to form an array of wafer-nested lenses are the same as the molding materials described above. In this embodiment, a plurality of concave lenses 12 are formed on one side (upper side of the figure) of the substrate 10, and a plurality of convex lenses 20 are formed on the other side (lower side of the figure) of the substrate. A patterned light shielding film 14 is formed in the areas of the substrate 10 excluding the surface of the lens 12A, on the side on which the plurality of concave lenses 12 are formed, i.e. , a patterned light shielding film 14 is formed on the surface of the substrate 10 and the surface of the peripheral lens portions 12b. As a modeling method used to form the light shielding film 14, one of the methods described above can be used.

[0188] Configuration and production of nested wafer lens (3) With reference to fig. 7A to 7C and in fig. 8A to 8C, another example of the configuration of a wafer-nested lens array and the procedures for the production thereof will be described below. Here, figs. 7A to 7C are schematic views showing another embodiment of the processes of forming a patterned light shielding film 14. In addition, Figs. 8A to 8C are schematic views showing the processes for molding the lenses 12 after the patterned light shielding film 14 has been formed.

[0189] In the embodiments of the array of wafer-nested lenses shown in FIGS. 3-6, the patterned light shielding film 14 is formed on the substrate 10 on which the lenses 12 have been formed. In contrast, in the embodiment described below, a patterned light shielding film 14 is first formed on a substrate 10, and then lenses 12 are molded on the substrate 10.

[0190] The formation of a protective film against light First of all, as shown in fig. 7A, a light shielding coating layer forming process in which a black curable composition is deposited on the substrate 10 to form a light shielding coating layer 14A, is carried out.

[0191] Subsequently, the light shielding coating layer 14A deposited on the substrate 10 is dried using a hot plate, an oven or the like, at a temperature of 50 ° C to 140 ° C for 10 seconds at 300 seconds. The dry film thickness of the black curable composition can be arbitrarily chosen depending on the desired results, such as the light shielding property, and is in a range of about 0.1 µm to less than 50 µm.

[0192] Then, as shown in FIG. 7B, the light shielding coating layer 14A formed in the process of forming a light shielding coating layer is patterned exposure through a mask 70. The mask 70 has a predetermined mask pattern. In this light exposure step, the light shielding coating layer 14 is subjected to pattern exposure, so that only the part which is irradiated with light is cured in the light shielding coating layer. light 14A. In this embodiment, a mask pattern is used which allows the irradiation of light to a portion of light shielding coating layer 14A in an area excluding the areas which serve as lens openings 14a of lenses 12 when. lenses 12 are molded in subsequent processes. In this way, the light shielding coating layer 14A is cured by the irradiation of light except for its parts which have become the lens openings 14a of the lenses 12. Examples of radiation which can be used in exposure include preferably ultraviolet rays, such as g-rays, h-rays, or i-rays, as in the procedures mentioned above.

[0193] Then, by performing an alkaline developing treatment (developing process), only the light-shielding coating layer 14A in the area corresponding to the lens opening 14a of the lens 12 which is an uncured area. of the light shielding coating layer 14A in the exposure pattern is eluted with an aqueous alkaline solution. At this time, as shown in fig. 7C, a photocured light shielding coating layer 14A remains on the substrate 10 except for the areas for the lens openings 14a of the lenses 12, a light shielding film 14 being formed. Here, examples of the alkaline agent in the aqueous alkaline solution as a developer are the same as those used in the methods described above. Then, after the development treatment, excess developer is washed off and removed, followed by drying.

[0194] Also in the present embodiment, a step of curing the light shielding film formed by post-curing and / or by exposure to light, as described above, can be performed, if necessary, after having carried out the light-shielding coating layer forming process, the exposure process, and the developing process.

[0195] Lens formation Next, a step of forming the lenses 12, which is performed after the light shielding film 14 is formed, will be described. As shown in fig. 8A, a molding material M for lenses 12 is applied dropwise using a dispenser 50 on a substrate 10 on which the patterned light shielding film 14 has been formed. The lens molding material M 12 is fed to cover the areas corresponding to the lens apertures 14a of the lenses 12 and also to cover a portion of the end of the light shielding film 14 adjacent to the apertures.

[0196] After the molding material M is supplied to the substrate 10, a mold 80 for forming a lens is disposed on the substrate on the side of the substrate 10, where the molding material M has been supplied, as shown in FIG. 8B. The mold 80 has several concave parts 82 for transferring the shape of the lens 12 according to the desirable number of lenses 12.

[0197] Then, the mold 80 is pressed onto the molding material M present on the substrate 10, so that the molding material M is deformed according to the shape of the concave parts. The molding material M is cured while the mold 80 is pressed onto the molding material M, by irradiating heat or ultraviolet light from outside the mold when the molding material M is a thermosetting resin or a resin. UV curable.

[0198] After the molding material M is cured, the substrate 10 and the lenses 12 are demolded 80, thus obtaining an array of wafer-fitted lenses comprising a light protection film patterned 14 on the substrate 10, as shown in fig. 8C.

[0199] As described above, the patterned light shielding film 14 included in a wafer-nested lens is formed not only in an area excluding the lens surfaces 12a of the lenses 12 as shown in FIG. 5, but the light shielding film 14 may also be provided in an area excluding the lens openings 14a of the lenses 12 as shown in FIG. 8C.

[0200] Since the wafer-fitted lens has a light shielding film 14 which has a low light reflection ratio and which is patternedly formed on at least one side of the substrate 10, the generation of reflected light is inhibited. while the light is sufficiently shielded in an area other than the lens surfaces 12a or the lens openings 14a of the lenses 12. Therefore, when the wafer-fitted lens is applied to an imaging module having a device for In solid imaging, defects such as ghosting or rounded images caused by reflected light during imaging are prevented.

[0201] Further, since the light shielding film 14 is provided on the surface of the substrate, other light shielding elements do not need to be placed in the wafer-nested lens, and a increase in production costs is suppressed.

[0202] As in the configuration described in the international application No. WO 2008/102648 mentioned above, when the surface around the lens has a concave and convex structure, the light incident on the structure is reflected or scattered, and therefore there is a risk of inducing anomalies such as ghost images. In this regard, as shown in fig. 5, when the patterned light shielding film 14 is disposed in an area excluding the lens surface 12a of the lens 12, the light is shielded in other areas than the lens surface 12a and the optical efficiency is improved.

Examples

[0203] Hereinafter, the invention is described in detail with reference to Examples, but it is not limited to the following Examples, unless departing from the spirit of the invention. Also, unless otherwise specified, "%" and "part (s)" are on a mass basis.

[0204] Preparation of the dispersion of titanium black (Dispersion TB-1) The components shown in Composition I below were subjected to a high viscosity dispersion treatment using a double roller, so as to obtain a dispersion. The viscosity of this dispersion was 40,000 mPa⋅s. Further, the components can be kneaded using a kneader for 30 minutes prior to the high viscosity dispersion treatment.

[0205] (Composition I) • 13 M-C titanium black with an average primary particle diameter of 75 nm (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd) (Pigment Black 35) 40 games • the solution of propylene glycol monomethyl ether acetate of benzyl methacrylate (BzMA) / methacrylic acid (MAA) copolymer (BzMA / MAA = 60/40 (molar ratio), Mw: 30,000, the solid content: 40% by mass) 8 parts • SOLSPERSE 5000 (manufactured by The Lubrizol Corporation) 2 parts

The elements represented in composition II below were added to the dispersion thus obtained, followed by stirring using a homogenizer for 3 hours under the conditions of 3,000 revolutions per minute. The solution thus obtained was subjected to a treatment of fine dispersion using a disperser (trade name: DISPERMAT, manufactured by Getzmann) using zirconia beads having a diameter of 0.3 mm for 4 hours, obtaining thus a dispersion of titanium black (hereinafter referred to as dispersion TB-1). The viscosity of the TB-1 dispersion was 6.8 mPa⋅s.

[0207] (Composition II) • the solution of propylene glycol monomethyl ether acetate of benzyl methacrylate (BzMA) / methacrylic acid (MAA) copolymer (BzMA / MAA = 70/30 (molar ratio), Mw: 30,000, the solid content of 40% by mass 10 parts • Propylene glycol acetate of monomethyl ether 200 games

[0208] Preparation of the dispersion of titanium black (Dispersion TB-2) The components shown in Composition III below were subjected to a high viscosity dispersion treatment using a double roller, so as to obtain a dispersion. The viscosity of this dispersion was 40,000 mPa⋅s. Further, the components can be kneaded using a kneader for 30 minutes prior to the high viscosity dispersion treatment.

[0209] (Composition III) • Titanium black having an average primary particle diameter of 40 nm (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd) 40 games • Exemplary compound 72 5 parts

The elements represented in composition IV below were added to the dispersion thus obtained, followed by stirring using a homogenizer for 3 hours under the conditions of 3,000 revolutions per minute. The solution thus obtained was subjected to a fine dispersion treatment using a disperser (trade name: DISPERMAT, manufactured by Getzmann) using zirconia beads having a diameter of 0.3 mm for 4 hours, thereby obtaining a dispersion of titanium black (hereinafter referred to as the TB-2 dispersion). The viscosity of the TB-2 dispersion was 6.8 mPa⋅s.

[0211] (Composition IV) • Composed copy 725 parts • Propylene glycol acetate of monomethyl ether 200 games

[0212]

[0213] Method of Synthesis of the Exemplary Compound 72 Exemplary compound 72 can be synthesized according to the preparation method described in paragraphs [0338] to [0340] of JP-A No. 2010-106,268.

[0214] Preparation of the carbon black dispersion (CB dispersion) A dispersion of carbon black (dispersion CB) was obtained by replacing the titanium black of dispersion TB-1 with the same mass of carbon black (carbon black MA-100 R (manufactured by Mitsubishi Chemical Corporation).

[0215] Preparation of the silver tin dispersion (ST dispersion) A solution obtained by dissolving 15 g of colloidal tin (average particle diameter: 20 nm, solid content: 20%, manufactured by Sumitomo Osaka Cement Co., Ltd.), 60 g of silver colloid (average particle diameter : 7 nm, solid content: 20% by weight, manufactured by Sumitomo Osaka Cement Co., Ltd.), and 0.75 g of polyvinylpyrrolidone in 100 ml of water was added to 200 ml of pure water with a temperature maintained at 60 ° C, thus obtaining a colloidal solution. Subsequently, the colloidal solution was stirred for 60 minutes with the temperature maintained at 60 ° C, followed by the application of ultrasonic waves for 5 minutes. Subsequently, the colloidal solution is concentrated by centrifugation to obtain a mixed solution having a solid content of 25%. The mixed liquid was then dried by a lyophilization process, thereby obtaining a powder sample. A dispersion of silver tin (ST dispersion) was obtained by replacing the titanium black in the TB-1 dispersion with the same mass of the powder sample thus obtained.

[0216] Examples 1 to 5 and Comparative Examples 1 and 2 1. Preparation of the black polymerizable composition The components of the following composition A-1 were mixed using a stirrer to prepare each of the black polymerizable compositions used in Examples 1 to 5 and Comparative Examples 1 and 2. (Composition A-1) • the binder polymer soluble in an alkaline medium (D) mentioned in the table 12.5 games • the polymerizable compound (C): dipentaerythritol hexaacrylate 2.0 parts • the polymerizable compound (C): peritaerythritol triacrylate 1.0 part • the polymerization initiator (B) mentioned in Table 1 0.3 part • the dispersion containing (A) black pigment, mentioned in table 1 24 pieces • propylene glycol monomethyl ether acetate 10 parts • cyclohexanone 8 parts

[0217] 2. Production and evaluation of light protection film (light protection area) Each black polymerizable composition obtained above was applied to a glass plate by spin coating, and heated on a hot plate at a temperature of 120 ° C for 2 minutes, to thereby obtain a black polymerizable composition coating layer. Then, the coating layer thus obtained was exposed to light in an amount of 500 mJ / cm <2> using an i-ray stepper. The coating layer after exposure was repeatedly paddled five times using an aqueous solution of 0.3% tetramethylammonium hydroxide at a temperature of 23 ° C for 60 seconds. Then, the coating layer was rinsed using a spinning bath, and further washed with pure water, so as to obtain a patterned light shielding film. For the light shielding film pattern thus obtained, the number of repeated development when the peel of an exposed part was found was determined using an optical microscope, and the results are shown in Table 1. When the number of repeated development is 4 or more, the alkaline developer resistance is judged to be good.

[0218] Table 1

The structures of the compounds B-1 to B-3 and HB-1 to HB-3 mentioned in Tables 1 and 2 are presented below. The numerical values of the composition ratios in the following structures indicate the contents (% by mass (wt%)) of the structural units. The structures of polymerization initiators 1-1 to I-3 are also shown.

[0220]

[0221]

[0222]

[0223] As shown by the results of Table 1, a wafer-nested lens having a light shielding film formed from the black polymerizable composition according to the invention exhibits excellent resistance to alkaline developer.

[0224] 23 examples 6 to 10 and comparative example 3 1. Preparation of the polymerizable black composition The components of composition A-2 described below were mixed with the aid of a stirrer, so as to obtain the black polymerizable compositions of Examples 6 to 10 and Comparative Example 3, respectively. (Composition A-2) • the binder polymer soluble in an alkaline medium (D) mentioned in the table 22.5 games • the polymerizable compound (C): succinic monomer modified by dipentaerythritol hexaacrylate acid 2.0 parts • the polymerizable compound (C): pentaerythritol triacrylate 2.0 parts • 3-methacryloxypropyl dimethoxymethylsilane 0.1 part • the polymerization initiator (B) mentioned in Table 2 0.4 part • the dispersion containing (A) a black pigment, mentioned in table 124 parts • propylene glycol monomethyl ether acetate 10 parts • cyclohexanone 8 parts

[0225] 2. Production and evaluation of light protection film (light protection area) The following composition V was deposited on a glass wafer with a film thickness of 15 µm, and subjected to exposure in a patterned fashion using a 50 µm hole mask to give a cylindrical diameter of 50 µm, by a light bulb. high pressure mercury, thereby forming a transparent resin layer having a cylindrical hole having a diameter of 50 µm. Then, the transparent resin layer was heated on a hot plate at a temperature of 200 ° C for 5 minutes, thereby obtaining a wafer comprising a transparent resin layer on which holes were formed. Then, each of the black polymerizable compositions obtained above was spray-coated using a two-fluid spray coating device on the wafer having a transparent resin layer formed thereon, and dried at 120 ° C for 2 minutes. , thereby obtaining a layer of black polymerizable composition having an average film thickness of 3 µm. It was found that the black polymerizable composition layer thus formed was uniformly formed on the surface of the glass wafer and on the surface of the transparent resin layer, even with the structures having an irregularity. In addition, the hole-forming area of the transparent resin layer and the hole part of the photographic mask are in conjunction with each other to effect positioning, and light exposure was performed using a photographic mask having a portion of light shielding holes having a diameter of 50 µm, at an exposure amount of 1,000 mJ / cm <2> using a high pressure mercury lamp or the like, from the top of the layer of black polymerizable composition. By exposure, the black polymerizable composition layer is cured in the area other than the hole-forming area formation, and the black polymerizable composition layer of the hole-forming area is present in an uncured state due to of the hole mask. (Composition V) • allyl methacrylate / methacrylic acid copolymer (molar ratio 70/30; Mw = 50,000) 1.6 parts • dipentaerythritol hexaacrylate (the polymerizable component (C)) 2.0 games • pentaerythritol triacrylate (the polymerizable component (C)) 1.0 part • IRGACURE OXE-01 (manufactured by BASF) 0.3 part • propylene glycol monomethyl ether acetate 5 parts

[0226] The coating layer after exposure to light was repeatedly subjected to paddle development using 0.3% aqueous tetramethylammonium hydroxide solution at a temperature of 23 ° C for 60 seconds. Then the coating layer was rinsed using a spin shower, and additionally washed with pure water, thereby obtaining a patterned light shielding film. The number of developments at which the peel was observed is shown in Table 2. A higher number of developments is believed to indicate better resistance to alkaline developer. Further, the residue of the cylindrical transparent resin layer part was developed twice, and a case in which no residue was found is indicated as "A", and a case in which residues were found is. indicated as "B", respectively, in Table 2. The results are shown in Table 2.

[0227] Table 2

[0228] As apparent from the results in Table 2 above, in a wafer-fitted lens having a light protection film formed by the black polymerizable composition according to the invention, the amount of residue in a non-part. image has been reduced, and peeling of the image portion has been eliminated, which means excellent resistance to alkaline developer. Further, it has been found that the black polymerizable composition according to the invention is capable of being applied by spraying.

[0229] In the results described above, it was found that the black polymerizable composition according to the invention has excellent resistance to alkaline developer. It has also been found that a black polymerizable composition capable of being applied by spraying is provided.

[0230] Japanese patent applications No. 2010-225,100 and 2011-003,422 are incorporated therein by reference. All publications, patent applications, and technical standards mentioned in the description are incorporated herein by reference in the same proportions as if each individual publication, patent application, or technical standard were specifically and individually indicated for insertion by reference. .

Claims (14)

1. Black polymerizable composition comprising: A) a black material; B) a polymerization initiator; C) a polymerizable compound; and D) an alkaline soluble binder polymer having a weight average molecular weight of at least 30,000, having a polymerizable group at a side chain thereof, and having an acid group in a molecule thereof. 2. A black polymerizable composition according to claim 1, wherein the black material A) comprises titanium black. 3. A black polymerizable composition according to claim 1 or 2, wherein the alkaline soluble binder polymer D) is an alkali soluble binder polymer having a weight average molecular weight of 50,000 to 100,000 and having a one-chain polymerizable group. side of it 4. Black polymerizable composition according to one of claims 1 to 3, which is capable of being applied by spraying. 5. Black polymerizable composition according to one of claims 1 to 4, wherein the total solid content in the black polymerizable composition is from 20% by mass to 35% by mass. 6. Black polymerizable composition according to one of claims 1 to 5, wherein the polymerizable group included in the binder polymer soluble in alkaline medium D) comprises an acrylic group, a methacrylic group, a styryl group, an allyl group, a group. acrylamide, a methacrylamide, a vinyl group or a vinyl ether group. 7. Black polymerizable composition according to one of claims 1 to 6, wherein the binder polymer soluble in alkaline medium D) is a (meth) acrylic polymer having an allyl group or a vinyl ester group and having a carboxyl group at its chains. lateral. 8. Black polymerizable composition according to one of claims 1 to 7, wherein the binder polymer soluble in an alkaline medium D) is a binder polymer in an alkaline medium selected from the group consisting of the following schemes B-1, B-2 and B-3: 9. Black polymerizable composition according to one of claims 1 to 8, wherein the content of binder polymer soluble in an alkaline medium D) is from 5% by mass to 75% by mass relative to the total solid content of the polymerizable composition. black. 10. The black polymerizable composition according to one of claims 1 to 9, further comprising a dispersant, wherein the dispersant is a graft copolymer which has a number of atoms, excluding hydrogen atoms, from 40 to 10,000. , which has a graft chain selected from the group consisting of a polyester structure, a polyether structure and a polyacrylate structure, and which comprises any of the structural units represented by the following formulas (1) to (4): wherein in formulas (1) to (4), each of W <1>, W <2>, W <3> and W <4> independently represents an oxygen atom or NH; each of X <1>, X <2>, X <3>, X <4> and X <5> independently represents a hydrogen atom or a monovalent organic group; Y <1>, Y <2>, Y <3> and Y <4> each independently represents a divalent linking group; Z <1>, Z <2>, Z <3> and Z <4> each independently represents a monovalent organic group; and n, m, p and q are each independently an integer of 1 to 500; and wherein in formulas (1) and (2), j and k each independently represent an integer of 2 to 8. 11. A black polymerizable composition according to one of claims 1 to 10, wherein the polymerization initiator (B) is an oxime polymerization initiator having a structure represented by: 12. A method of manufacturing a black layer, the method comprising: applying, by spray coating, the black polymerizable composition according to any of claims 4 to 11 on a surface of a solid to form a layer of black polymerizable composition, and supplying energy to the formed layer of black polymerizable composition to harden the formed layer of black polymerizable composition. 13. The method of manufacturing a black layer according to claim 12, wherein the surface of the solid is a surface of a peripheral portion of a nested lens of a wafer, and the black layer is a protection zone against light formed in the peripheral part of the lens. 14. Use of the black polymerizable composition according to one of claims 1 to 11 to form a light shielding zone of a nested lens of a wafer.