JP5583389B2 - Black curable composition for wafer level lens and wafer level lens - Google Patents

Description

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

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

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

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

  As a method for forming a light-shielding region using a photolithography method, a light-shielding composition is applied on a lens and a substrate such as a glass substrate, and a portion to be the light-shielding region is exposed and cured, and then alkali development is performed. The method of forming the light-shielding area | region comprised with the light shielding film by removing the light-shielding composition of an unexposed part with a liquid is mentioned. In the case of forming a light-shielding region by photolithography, it is important to suppress residual residues generated by development outside the light-shielding film formation region after removal of the light-shielding composition in the unexposed area. . However, when a conventional light-shielding composition is used, it is very difficult to suppress the development residue remaining outside the light-shielding film formation region.

Patent Document 4 describes a photosensitive composition containing a light-blocking material such as carbon black and titanium black and a specific polymerization initiator as a photosensitive composition for forming a black matrix of a liquid crystal display, It describes that a polymer dispersant such as polyethyleneimine, urethane resin, and acrylic resin can be used as the dispersant for the light shielding material. However, in Patent Document 4, there is no description regarding the use of a wafer level lens, and the photosensitive composition described in the same document has a high development speed to an alkaline developer, and the pattern shape on the lens deteriorates. Therefore, it is difficult to use for the formation of the light shielding region in the wafer level lens.
Thus, as a curable composition used for forming a light-shielding region in a wafer level lens, a satisfactory composition has not yet been provided, and further improvement has been demanded.

Japanese Patent No. 3926380 International Publication No. 2008/102648 Pamphlet US Pat. No. 6,426,829 JP 2005-338328 A

This invention is made | formed in view of the said conventional condition, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a black curable composition for a wafer level lens that can form a cured film having excellent light shielding properties and can reduce residue remaining from the black curable composition outside the region where the cured film is formed. To provide things.
In addition, a further object of the present invention is to provide a wafer level lens in which the amount of light is appropriately adjusted and can be easily manufactured by providing a light-shielding film formed of the black curable composition for a wafer level lens of the present invention. There is to do.

  As a result of intensive studies, the present inventor has found that the above problem can be solved by a black curable composition containing a specific resin, and has completed the present invention.

Means for solving the above-mentioned problems are as follows.
<1> (A) Titanium black , (B) Polyethyleneimine, polyallylamine, or a dispersion resin that is a condensation product of polyvinylamine and polyester, (C) a polymerization initiator, (D) a polymerizable compound, and (E) A black curable composition for wafer level lenses containing an alkali-soluble resin.
<2> (A) An inorganic pigment that is titanium black, (B) a dispersion of a primary or secondary amino group-containing compound and a polyester, and an amine value of 5 mg KOH / g to 100 mg KOH / g, (C A black curable composition for a wafer level lens, comprising: a) a polymerization initiator, (D) a polymerizable compound, and (E) an alkali-soluble resin.
<3> The coloring for a wafer level lens according to <1>, wherein the amine value of the dispersion resin which is a condensate of (B) polyethyleneimine, polyallylamine or polyvinylamine and polyester is 5 mgKOH / g to 100 mgKOH / g. Curable composition.
<4> The wafer level lens coloring according to <2>, wherein the condensate of the (B) primary or secondary amino group-containing compound and the polyester is a condensate of polyethyleneimine, polyallylamine or polyvinylamine and the polyester. Curable composition.
<5> The black curable composition for a wafer level lens according to any one of <1> to <4>, wherein the amine value of the (B) dispersion resin is 60 mgKOH / g to 78 mgKOH / g.
<6> The wafer level lens according to any one of <1> to <5>, wherein the (B) dispersion resin has a weight average molecular weight (polystyrene equivalent value by GPC method) of 5,000 to 50,000. Colored curable composition.
< 7 > The black curable composition for a wafer level lens according to any one of <1> to < 6 >, further comprising (F) an organic pigment.
< 8 > The method according to any one of <1> to < 7 >, wherein the polymerization initiator (C) is at least one polymerization initiator selected from an oxime ester compound and a hexaarylbiimidazole compound. Black curable composition for wafer level lens.
<9> The black curable composition for wafer level lenses according to <8>, wherein the (C) polymerization initiator is an oxime ester compound.
< 10 > The black-curing property for a wafer level lens according to any one of <1> to < 9 >, wherein the (E) alkali-soluble resin is an alkali-soluble resin having a polymerizable double bond in a side chain. Composition.
< 11 > A wafer provided with a light-shielding film obtained by using the black curable composition for a wafer level lens according to any one of <1> to < 10 > on a peripheral portion of a lens present on a substrate. Level lens.

According to the present invention, there is provided a black curable composition for a wafer level lens, which can form a cured film having excellent light shielding properties and can reduce residue remaining from the black curable composition outside the region where the cured film is formed. Can be provided.
In addition, according to the present invention, there is provided a wafer level lens in which the amount of light is appropriately adjusted and can be easily manufactured by providing the light shielding film formed of the black curable composition for a wafer level lens of the present invention. Can do.

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

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

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

[Black curable composition for wafer level]
The black curable composition for wafer level of the present invention (hereinafter also referred to as “the black curable composition of the present invention” as appropriate) comprises (A) an inorganic pigment, (B) a primary or secondary amino group-containing compound . It contains a dispersion resin that is a condensate with polyester, (C) a polymerization initiator, and (D) a polymerizable compound.
The black curable composition for wafer level of the present invention is used for forming a light-shielding cured film (hereinafter also referred to as “light-shielding film” as appropriate) in a wafer level lens.

  Here, “light shielding” in this specification means the ability to suppress transmission of light having a wavelength of 400 nm to 800 nm.

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

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

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

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

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

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

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

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

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

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

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

As for the particle size of the inorganic pigment in the present invention, the average primary particle size is preferably 5 nm to 0.01 mm, and from the viewpoint of dispersibility, light-shielding properties, and sedimentation with time, the average primary particle size is 10 nm to More preferably, it is 1 μm.
The particle size of titanium black suitably used as an inorganic pigment is not particularly limited, but from the viewpoint of dispersibility and colorability, the average primary particle size is preferably 3 nm to 2000 nm, more preferably 10 nm to 500 nm. And most preferably 10 nm to 100 nm.

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

  The content of the inorganic pigment in the black curable composition is preferably 5 to 70% by mass and more preferably 10 to 50% by mass with respect to the total mass of the composition.

  When an inorganic pigment is contained in a black curable composition, a pigment dispersion obtained by dispersing an inorganic pigment in advance using a dispersion resin (B) is a condensate of a primary or secondary amino group-containing compound and polyester. It is preferable to prepare and use the pigment dispersion for the preparation of the black curable composition from the viewpoint of the uniformity of the resulting black curable composition.

(B) Dispersion resin which is condensate of primary or secondary amino group-containing compound and polyester The black curable composition of the present invention is a dispersion resin (condensate of primary or secondary amino group-containing compound and polyester ( Hereinafter, it is also referred to as “specific resin” as appropriate.

The black curable composition of the present invention contains a specific resin as one of its essential components, thereby forming a light-shielding film that has been a problem when forming a light-shielding region of a wafer level lens by photolithography. The developability outside the region is improved, and the residue remaining from the black curable composition is reduced.
Although this mechanism of action is not yet clear, it is estimated as follows.
When a light-shielding film provided with a wafer level lens is formed by photolithography using a curable composition containing an inorganic pigment, the occurrence of residues in the unexposed area (outside the area where the light-shielding film is formed) is curable. It is considered that the cause is that only the developing component in the composition is removed with an alkaline developer, and the inorganic pigment remains undeveloped. This phenomenon occurs because the bond between the inorganic pigment and the lens, glass substrate, etc. constituting the non-shielding region of the light-shielding film is stronger than the bond strength between the inorganic pigment and the developing component. I believe.
On the other hand, the specific resin in the present invention has a high density of nitrogen atoms (primary or secondary amino groups) that can be combined with inorganic pigments and alkali developing components, and therefore, residues remaining outside the formation region of the light shielding film are not present. I think it will be less. Furthermore, since the specific resin has a very flexible polyester chain, the permeability of the developer is high, and this is considered to be effective in suppressing residual residues.

The specific resin is a condensate of (B-1) a primary or secondary amino group-containing compound and (B-2) polyester, which will be described in detail below.
The molecular weight of the specific resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and most preferably 6,000 to 20,000 in terms of weight average molecular weight (polystyrene conversion value by GPC method). preferable.
When the molecular weight of the specific resin is within the above range, the dispersion stability and developability are further improved.

  The specific resin preferably has an amine value of 2 to 150 mgKOH / g, and most preferably 5 to 100 mgKOH / g. When the amine value of the specific resin is within this range, the dispersion stability becomes better.

  Here, the amine value is the number of mg of KOH equivalent to the amount of hydrochloric acid required to neutralize all basic groups in 1 g of the sample compound. In this specification, the amine value was measured by titration using a 0.1 N perchloric acid acetic acid solution.

(B-1) Primary or secondary amino group-containing compound Primary or secondary amino group-containing compound which is one of the constituent elements of the specific resin, hereinafter also referred to as “amino group-containing compound” as appropriate. ) Is a compound having a primary or secondary amino group in the molecular structure. The compound having a primary or secondary amino group is preferably an oligomer or polymer having a repeating unit having a primary or secondary amino group amino group.

  The molecular weight of the amino group-containing compound is preferably a number average molecular weight of 200 to 10,000, more preferably 300 to 3,000, and further preferably 500 to 1,500. When the molecular weight is in this range, the developability outside the light-shielding film forming region such as on the lens and the glass substrate is further improved.

  In particular, the amino group-containing compound preferably has an amine value of 500 to 1,400 mgKOH / g, more preferably 900 to 1400 mgKOH / g. When the amine value is within this range, the developability outside the light-shielding film forming region on the lens and the glass substrate is further improved.

Specific examples of the amino group-containing compound include, for example, polyethyleneimine (amine value: 1303 mgKOH / g), polyallylamine (amine value: 983 mgKOH / g), polydiallylamine (amine value: 577 mgKOH / g), polyvinylamine (amine value). And a compound having a known primary or secondary amino group, such as a polycondensate of metaxylylenediamine and epichlorohydrin (amine value: 292 mgKOH / g). The amine value here can be calculated by the following formula.
Amine value (mgKOH / g) = 56,100 / (molecular weight of primary or secondary amino group-containing compound)

  Commercially available products may be used as the amino group-containing compound, such as SP-003, SP-006, SP-012, SP-018, SP-200 (and above, polyethyleneimine manufactured by Nippon Shokubai Co., Ltd.), PAA -001, PAA-003 (above, polyallylamine produced by Nittobo Spinning Co., Ltd.), GASKAMINE 328 (above, polycondensate of metaxylylenediamine and epichlorohydrin produced by Mitsubishi Gas Chemical Co., Inc.), etc. Can be mentioned.

  As the amino group-containing compound, polyethyleneimine, polyallylamine and polyvinylamine are preferable, and polyethyleneimine is most preferable from the viewpoint of dispersion stability.

(B-2) Polyester As polyester which is one of the constituent elements of the specific resin, (I-1) polycondensation of carboxylic acid and lactone, (I-2) polycondensation of hydroxy group-containing carboxylic acid, or (I -3) A polyester obtained by polycondensation of a dihydric alcohol and a divalent carboxylic acid (or cyclic acid anhydride) is preferred.
Hereinafter, the polyester obtained by the polycondensation reaction of the above (I-1) to (I-3) will be described in detail.

  The carboxylic acid used in the polycondensation of (I-1) is preferably an aliphatic carboxylic acid (a linear or branched carboxylic acid having 1 to 30 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, etc. , N-hexanoic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, palmitic acid, 2-ethylhexanoic acid, cyclohexane acid, etc.), a hydroxy group-containing carboxylic acid (straight chain of 1 to 30 carbon atoms or Branched hydroxy group-containing carboxylic acids are preferred, such as glycolic acid, lactic acid, 3-hydroxypropionic acid, 4-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, ricinoleic acid, 12-hydroxydodecanoic acid, 12-hydroxystearic acid, 2,2-bis (hydroxymethyl) butyric acid, etc.), straight chain aliphatic carboxylic acid having 6 to 20 carbon atoms or carbon Hydroxy group-containing carboxylic acid having 1 to 20 is particularly preferred. These carboxylic acids may be used alone or in combination of two or more.

  As the lactone used in the polycondensation of (I-1), known lactones can be used. For example, β-propiolactone, β-butyrolactone, γ-butyrolactone, γ-hexanolactone, γ-octano Examples include lactone, δ-valerolactone, δ-hexalanolactone, δ-octanolactone, ε-caprolactone, δ-dodecanolactone, α-methyl-γ-butyrolactone, and particularly ε-caprolactone is reactive. -It is preferable from the viewpoint of availability. These lactones may be used alone or in combination of two or more.

  In the case of obtaining a polyester by the polycondensation reaction of (I-1), the charging ratio at the time of the reaction between the carboxylic acid and the lactone cannot be uniquely determined because of the molecular weight of the target polyester chain, but the carboxylic acid: lactone = 1: 1-1: 1,000 are preferred, and 1: 3-1: 500 are most preferred.

  The hydroxy group-containing carboxylic acid used in the polycondensation of (I-1) is the same as the hydroxy group-containing carboxylic acid in (IV-1), and the preferred range is also the same.

  The dihydric alcohol used in the polycondensation of (I-3) is preferably a linear or branched aliphatic diol (a diol having 2 to 30 carbon atoms, such as ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol). 1,2-propanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, etc., and particularly aliphatic having 2 to 20 carbon atoms Diols are preferred.

  The divalent carboxylic acid used in the polycondensation of (I-3) is preferably a linear or branched divalent aliphatic carboxylic acid (a divalent aliphatic carboxylic acid having 1 to 30 carbon atoms is preferable. Acid, maleic acid, adipic acid, sebacic acid, dodecanedioic acid, glutaric acid, suberic acid, tartaric acid, oxalic acid, malonic acid, and the like, and a divalent carboxylic acid having 3 to 20 carbon atoms is particularly preferable. In addition, acid anhydrides equivalent to these divalent carboxylic acids (for example, succinic anhydride, glutaric anhydride, etc.) may be used.

  When the polyester is obtained by the polycondensation of (I-1), it is preferable to charge the divalent carboxylic acid and the dihydric alcohol at a molar ratio of 1: 1. This makes it possible to introduce a carboxylic acid at the terminal.

The synthesis of the polyester by the polycondensation reaction of (I-1) to (I-3) is preferably performed by adding a catalyst. As the catalyst, a catalyst that functions as a Lewis acid is preferable. For example, a Ti compound (eg, Ti (OBu) ₄ , Ti (O—Pr) _4, etc.), a Sn compound (eg, tin octylate, dibutyltin oxide, dibutyltin laurate) Monobutyltin hydroxybutyl oxide, stannic chloride, monobutyltin dioxide, etc.), protonic acids (for example, sulfuric acid, paratoluenesulfonic acid, etc.) and the like. The catalyst amount is preferably from 0.01 to 10 mol%, most preferably from 0.1 to 5 mol%, based on the number of moles of all monomers. The reaction temperature is preferably 80 to 250 ° C, and most preferably 100 to 180 ° C. Although reaction time changes with reaction conditions, it is 1 to 24 hours in general.

  The number average molecular weight of the polyester can be measured as a polystyrene converted value by the GPC method. The number average molecular weight of the polyester is 1,000 to 1,000,000, preferably 2,000 to 100,000, and most preferably 3,000 to 50,000. When the molecular weight of the polyester is within this range, both dispersibility and developability can be achieved.

  From the viewpoint of developability on the lens and outside the formation region of the light-shielding film such as a glass substrate, the polyester which is a component of the specific resin is (I-1) polycondensation of carboxylic acid and lactone, and (I-2) Polyesters obtained by polycondensation of hydroxy group-containing carboxylic acids are preferred, and (I-1) polyesters obtained by polycondensation of carboxylic acids and lactones are more preferred. Among the polyesters obtained by polycondensation of (I-1), a condensate of carboxylic acid and ε-caprolactone is most preferable.

  The specific resin preferably further contains an alkali-soluble group. By containing an alkali-soluble group, the developability of the developability outside the formation region of the light shielding film is further improved.

As the alkali-soluble group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and —COCH ₂ COCH ₃ are preferable, and a carboxylic acid group is particularly preferable.

  When specific resin has an alkali-soluble group, it is preferable that an acid value is 5-100 mgKOH / g, and 5-50 mgKOH / g is the most preferable.

  As a method for introducing an alkali-soluble group into a specific resin, an amino group present in a structure derived from a primary or secondary amino group-containing compound, and an alkali-soluble group precursor (for example, cyclic acid anhydride, diketene, etc.) A reaction method is preferred.

As a method for synthesizing the specific resin, a method in which polyester and a primary or secondary amino group-containing compound are mixed and heated to condense is preferable. The reaction temperature is preferably 80 to 150 ° C, more preferably 100 to 130 ° C. The reaction time is preferably 1 to 10 hours, more preferably 2 to 5 hours. The reaction atmosphere is preferably carried out in a nitrogen atmosphere.
In addition, in the Example mentioned later, the synthesis example of specific resin was shown as synthesis examples 4-19.

  In the specific resin, the content ratio between the structure derived from the primary or secondary amino group-containing compound and the structure derived from the polyester is preferably 2: 100 to 20: 100 in terms of mass ratio, and 5: 100 to 15: 100. Is most preferred. By being in this range, the dispersion stability in the black curable composition is further improved.

  As content in the black curable composition of specific resin, the range of 1 mass%-50 mass% is preferable with respect to solid content of a black curable composition, and the range of 5 mass%-30 mass% is more preferable. . Within this range, the adhesion of the light-shielding film on the lens periphery or the substrate is preferably improved.

  The black curable composition of the present invention may contain other pigment dispersant (hereinafter also simply referred to as “other pigment dispersant”) together with the specific resin. As other pigment dispersants, for example, known pigment dispersants and surfactants can be appropriately selected and used. Commercially available dispersants, surfactants and the like may be used as other pigment dispersants.

  Other pigment dispersants are preferably polymer compounds having a heterocyclic ring in the side chain. Such a polymer compound includes a polymer unit derived from a monomer represented by the general formula (1) described in JP-A-2008-266627, or a monomer composed of maleimide or a maleimide derivative. A polymer is preferred. Such other pigment dispersants are described in detail in paragraphs [0020] to [0047] of JP-A-2008-266627, and the dispersants described herein can be suitably used in the present invention.

Specific examples of commercially available products that can be used as other pigment dispersants include, for example, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow no. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene Nonionic surfactants such as octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; anionic systems such as W004, W005, and W017 (manufactured by Yusho Co., Ltd.) Surfactant: EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Ciba Specialty Chemicals) Polymer dispersants such as Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, Various Solsperse dispersants (manufactured by Nippon Lubrizol Corp.) such as 26000, 28000, 32000, 36000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka Co., Ltd.) and Isonet S-20 (Sanyo Kasei Co., Ltd.), Disperbyk 101, 103, 106, 108, 109, 111, 112, 116, 30,140,142,162,163,164,166,167,170,171,174,176,180,182,2000,2001,2050,2150 (BYK Chemie Co., Ltd.) and the like.
In addition, an oligomer or a polymer having a polar group at the molecular terminal or side chain, such as an acrylic copolymer, can also be suitably used as another pigment dispersant.

  When other pigment dispersants are used, the pigment dispersant is preferably 5 to 20% by mass and more preferably 5 to 10% by mass with respect to the inorganic pigment.

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

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

  More specific examples of the oxime ester compound include polymerization initiators described in paragraph numbers [0081] to [0100] and [0101] to [0139] of JP-A-2006-78749. .

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

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

  Here, since the oxime ester compound has a small absorption in the region of 380 nm to 480 nm and has a small coloration, particularly yellow coloration, an image having a high color purity when used in a color filter for an image display device which is the main use of the present invention. Is obtained. In addition, when used in a color separation color filter for a solid-state image pickup device, which is another application, a color signal with high resolution can be obtained, so that a solid-state image pickup device with high resolution can be obtained.

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

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

  As for content of the polymerization initiator in the black curable composition of this invention, 0.1-30 mass% is preferable in the total solid of a black curable composition, 1-25 mass% is more preferable, 2-20 Mass% is particularly preferred. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

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

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

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

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

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

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

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

(E) Alkali-soluble resin The black curable composition of this invention contains alkali-soluble resin.
The alkali-soluble resin that can be used in the present invention is a linear organic polymer, and at least 1 in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having two groups that promote alkali solubility (for example, carboxyl group, phosphoric acid group, sulfonic acid group, hydroxyl group, etc.).

  More preferable as the alkali-soluble resin is a polymer having a carboxylic acid in the side chain, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-54-25957, A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, maleic acid as described in JP-A-59-53836 and JP-A-59-71048 Copolymers, partially esterified maleic acid copolymers, etc., as well as those of acrylic copolymers such as acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having a hydroxyl group with an acid anhydride added. It is done.

  The acid value of the alkali-soluble resin is preferably 20 to 200 mgKOH / g, preferably 30 to 150 mgKOH / g, and more preferably 50 to 120 mgKOH / g.

  The alkali-soluble resin is particularly preferably a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith.

Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
As alkyl (meth) acrylate and aryl (meth) acrylate, CH ₂ ═C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ³ Represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. ], Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl ( (Meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyalkyl (meth) acrylate (alkyl is an alkyl having 1 to 8 carbon atoms) Group), hydroxyglycidyl methacrylate, tetrahydrofurfuryl methacrylate and the like.

As the alkali-soluble resin, a resin having a polyalkylene oxide chain in the molecular side chain is also preferable. The polyalkylene oxide chain may be a polyethylene oxide chain, a polypropylene oxide chain, a polytetramethylene glycol chain, or a combination thereof, and the terminal is a hydrogen atom or a linear or branched alkyl group.
1-20 are preferable and, as for the number of repeating units of a polyethylene oxide chain and a polypropylene oxide chain, 2-12 are more preferable. Examples of the acrylic copolymer having a polyalkylene oxide chain in the side chain include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meta). ) Acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, and the like, and compounds in which these terminal OH groups are alkyl-blocked, such as methoxypolyethylene glycol mono (meth) acrylate, ethoxypolypropylene glycol mono (meth) acrylate, methoxypoly ( An acrylic copolymer having ethylene glycol-propylene glycol) mono (meth) acrylate or the like as a copolymerization component may be mentioned.

In addition, as the vinyl compound, CH ₂ = CR ² R ⁴ [wherein R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Represents. Specific examples include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like.
These other copolymerizable monomers can be used singly or in combination of two or more. Other preferable copolymerizable monomers are alkyl (meth) acrylate (alkyl is an alkyl group having 2 to 4 carbon atoms), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene.

  Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.

  These acrylic resins preferably have an acid value in the range of 20 to 100 mgKOH / g from the viewpoint of the residue and the pattern shape of the light-shielding film in the wafer level lens, and have an acid value in the range of 30 to 80 mgKOH / g. Most preferred. In addition, the weight average molecular weight Mw (polystyrene conversion value measured by GPC method) of the acrylic resin is used in order to realize a viscosity range in which the black curable composition of the present invention can be easily used in a process such as coating. In order to ensure the strength, it is preferably 2,000 to 100,000, more preferably 3,000 to 50,000.

In order to make the acid value of acrylic resin into the range specified above, it can carry out easily by adjusting the copolymerization ratio of each monomer appropriately. Further, the range of the mass average molecular weight can be easily set by using an appropriate amount of a chain transfer agent according to the polymerization method when the monomers are copolymerized.
The acrylic resin can be produced, for example, by a radical polymerization method known per se. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an acrylic resin by radical polymerization can be easily set by those skilled in the art. Is possible.

  The addition amount when adding the alkali-soluble resin to the black curable composition of the present invention is preferably 5 to 90% by mass, more preferably 10 to 60% by mass, based on the total solid content of the composition. . If the alkali-soluble resin is within this range, it is preferable because an appropriate film strength is improved and the solubility during development can be easily controlled. Moreover, it is preferable at the point which becomes easy to obtain the coating film of desired thickness. In particular, a good coating can be obtained with a high yield for slit coating suitable for coating on a wide substrate having a large area.

Moreover, in order to improve the crosslinking efficiency of the black curable composition in this invention, it is preferable to use alkali-soluble resin which has a polymerizable double bond in the side chain of a polymer.
In particular, an alkali-soluble resin containing a (meth) acryloyl group in the side chain is preferably used. Thereby, the sensitivity is improved and the residue outside the light shielding film forming region is reduced. The reduction of the residue is presumed to be because the unsaturated bond of the (meth) acryloyl group is adsorbed with the inorganic pigment.

Examples of the polymer containing a polymerizable double bond are shown below. However, the polymer is not limited to the following as long as it contains an alkali-soluble group such as a COOH group and an OH group and a carbon-carbon unsaturated bond.
(1) Urethane modification obtained by reacting an isocyanate group and an OH group in advance, leaving one unreacted isocyanate group and reacting at least one (meth) acryloyl group with an acrylic resin containing a carboxyl group Polymerized double bond-containing acrylic resin (2) Unsaturated group-containing acrylic resin obtained by reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule (3) Acid Pendant type epoxy acrylate resin (4) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing an OH group with a dibasic acid anhydride having a polymerizable double bond Among the above, in particular, (1) and (2 ) Is preferred.

The acid value of the alkali-soluble resin having a polymerizable double bond in the present invention is preferably 30 to 150 mgKOH / g, more preferably 35 to 120 mgKOH / g. The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 3,000 to 30,000.
Specific examples of the alkali-soluble resin having a polymerizable double bond include, for example, a copolymer of 2-hydroxyethyl acrylate, methacrylic acid, and a monomer such as an acrylic or vinyl compound copolymerizable with these. , A compound obtained by reacting an epoxy ring having reactivity with an OH group and a compound having a carbon-carbon unsaturated bond group (for example, a compound such as glycidyl acrylate) can be used.
In the reaction with the OH group, a compound having an acid anhydride, an isocyanate group, or an acryloyl group in addition to the epoxy ring can be used. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring described in JP-A-6-102669 and JP-A-6-1938 is saturated or unsaturated polybasic. A reaction product obtained by reacting an acid anhydride can also be used. In addition, the repeating unit having a polymerizable group of an alkali resin having a polymerizable double bond is preferably contained in an amount of 5 to 60% by mass, more preferably 10 to 40% by mass, based on the resin.

  Examples of the compound having both an alkali solubilizing group such as a COOH group and an intercarbon unsaturated group include, for example, Dynar NR series (manufactured by Mitsubishi Rayon Co., Ltd.); Ltd .; Biscort R-264, KS resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.); Cyclomer P series, Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.); Ebecryl 3800 (Daicel) And UCB Co., Ltd.).

  The alkali-soluble resin used in the present invention is most preferably a resin obtained by modifying a copolymer of alkyl (meth) acrylate or styrene and (meth) acrylic acid with glycidyl (meth) acrylate. As the alkyl (meth) acrylate, a (meth) acrylic acid ester having an alkyl having 1 to 10 carbon atoms is preferable. For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, Examples include 2-ethylhexyl (meth) acrylate and benzyl (meth) acrylate.

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

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

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

  In the present invention, in a combination of an inorganic pigment and an organic pigment, at least one selected from an inorganic pigment, titanium black, an orange pigment, a red pigment, and a violet pigment, as a combination that achieves both curability and light shielding properties. A combination with an organic pigment is preferred, and a combination of titanium black and a red pigment is most preferred.

(G) Sensitizer The black curable composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the polymerization initiator and increasing the photosensitive wavelength.
As the sensitizer that can be used in the present invention, a sensitizer that is sensitized by an electron transfer mechanism or an energy transfer mechanism to the polymerization initiator used in combination is preferable.
Preferable examples of the sensitizer include compounds described in paragraph numbers [0085] to [0098] of JP-A-2008-214395.
The content of the sensitizer is preferably in the range of 0.1 to 30% by mass and preferably in the range of 1 to 20% by mass with respect to the mass of the total solid content of the black curable composition from the viewpoint of sensitivity and storage stability. Is more preferable, and the range of 2 to 15% by mass is still more preferable.

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

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

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

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

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

<Wafer level lens>
The wafer level lens of this invention has the light shielding film obtained using the black curable composition of this invention in the peripheral part of the lens which exists on a board | substrate.
The wafer level lens of the present invention will be described below with reference to the drawings.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these. Unless otherwise specified, “%” and “part” are based on mass.

In addition, as polyallylamine, what concentrated the aqueous solution containing this was used.
Examples of polyvinylamine include J.M. Am. Chem. Soc. 1976, 98, 5996. The aqueous solution of polyvinylamine hydrochloride synthesized by the method described in 1) was made hydrochloric acid-free using Amberlite (R) IRA-938 (MP, manufactured by Biomedicals) and concentrated (number average molecular weight 2,500).

(Synthesis Example 1) Synthesis of Polyester (i-1) 4.2 g of n-octanoic acid, 200 g of ε-caprolactone, and 0.1 g of monobutyltin dioxide were mixed, heated at 160 ° C. for 8 hours, and then cooled to room temperature. And polyester (i-1) was obtained. The molecular weight measured by the GPC measurement method was a number average molecular weight of 15,000 and a weight average molecular weight of 21,000.

Synthesis Example 2 Synthesis of Polyester (i-2) Under a nitrogen stream, 100 g of 12-hydroxystearic acid, 0.1 g of titanium (IV) tetrabutoxide, and 300 g of xylene are mixed, and water generated at an external temperature of 160 ° C. is mixed. The reaction was carried out while distilling through a Dean-Stark tube. When the molecular weight measured by GPC measurement was 18,000 and the weight average molecular weight was 23,000, the heating was stopped to obtain polyester (i-2).

(Synthesis Example 3) Synthesis of Polyester (i-3) Under a nitrogen stream, 307 g of adipic acid, 110 g of neopentyl glycol, 57 g of 1,4-butanediol, and 26 g of ethylene glycol are mixed, and water generated at an external temperature of 160 ° C. Was reacted while distilling through a Dean-Stark tube. When the molecular weight measured by GPC measurement was 16,000 and the weight average molecular weight was 24,000, the reaction was stopped to obtain polyester (i-3).

(Synthesis Example 4) Synthesis of Resin (A-1) Polyethyleneimine (“SP-006” manufactured by Nippon Shokubai Co., Ltd., number average molecular weight 600) 10 g and 100 g of polyester (i-1) were mixed, and at 120 ° C. Heated for 3 hours. Thereafter, the mixture is allowed to cool to 65 ° C., and propylene glycol monomethyl ether acetate is slowly added to obtain a 30% by mass propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) solution of resin (A-1) which is a specific resin. It was.

(Synthesis Examples 5-12) Synthesis of Resins (A-2) to (A-9) In Synthesis Example 4, the type of polyethyleneimine was changed to the type of amino group-containing compound described in Table 1, and polyester (i- Except having changed the kind of 1) into the polyester of Table 1, it carried out similarly to the synthesis example 4, and obtained 10 mass% PGMEA solution of resin (A-2)-(A-9) which is specific resin. .

  For the specific resins (A-1) to (A-9) obtained in Synthesis Examples 1 to 12, the weight average molecular weight and number average molecular weight measured by the GPC measurement method, and the amine value measured by the aforementioned method It is written together with 1.

(Synthesis example 13) Synthesis | combination of resin (A-10) In the synthesis example 8, except having changed reaction temperature and reaction time into heating at 140 degreeC for 10 hours, operation similar to the synthesis example 4 is performed, and specific resin is used. A certain resin (A-10) was obtained.
Regarding the molecular weight of the specific resin (A-10) measured by GPC measurement, the weight average molecular weight was 7,000 and the number average molecular weight was 4,000. The amine value of the resin (A-10) was 5 mgKOH / g.

(Synthesis Example 14) Synthesis of Resin (A-11) In Synthesis Example 4, the same operation as in Synthesis Example 4 was performed except that the reaction temperature and reaction time were changed to heating at 140 ° C for 24 hours, and this was a specific resin. Resin (A-11) was obtained.
Regarding the molecular weight of the resin (A-11) measured by GPC measurement, the weight average molecular weight was 6,000 and the number average molecular weight was 3,000. The amine value of the resin (A-11) was 2 mgKOH / g.

(Synthesis Example 15) Synthesis of Resin (A-12) In Synthesis Example 1, except that 20 g of polyethyleneimine was used, the same operation as in Synthesis Example 1 was performed to obtain a resin (A-12) which is a specific resin. .
Regarding the molecular weight of the resin (A-12) measured by the GPC measurement method, the weight average molecular weight was 6,000 and the number average molecular weight was 3,000. The amine value of the resin (A-12) was 160 mgKOH / g.

(Synthesis Example 16) Synthesis of Resin (A-13) Resin (A-13) which is a specific resin is obtained by performing the same operation as in Synthesis Example 4 except that the reaction time is 1 hour in Synthesis Example 4. It was.
Regarding the molecular weight of the resin (A-13) measured by the GPC measurement method, the weight average molecular weight was 12,000 and the number average molecular weight was 8,000. The amine value of the resin (A-13) was 130 mgKOH / g.

  In Table 2, SP-003 (number average molecular weight: 300), SP-012 (number average molecular weight: 1,200), SP-018 (number average molecular weight: 1,800), and SP-200 (number average) (Molecular weight 10,000) is a polyethyleneimine manufactured by Nippon Shokubai Co., Ltd., PAA-001 number average molecular weight is 1000), PAA-003 (number average molecular weight: 3,000) is manufactured by Nitto Boseki Co., Ltd. Polyallylamine.

(Synthesis Example 17) Synthesis of Resin (A-14) 100 g of polyester (i-1) and 10 g of polyethyleneimine (SP-006, manufactured by Nippon Shokubai Co., Ltd.) were heated at 120 ° C. for 3 hours to obtain a resin. The weight average molecular weight of the obtained resin was 10,000, the number average molecular weight was 6,000, and the amine value was 75 mgKOH / g. Thereafter, the obtained resin was allowed to cool to 65 ° C., 200 g of PGMEA containing 7.6 g of succinic anhydride was slowly added, and the mixture was stirred for 2 hours. Thereafter, PGMEA was further added to obtain a 30% by mass PGMEA solution of the resin (A-14) as the specific resin.
The weight average molecular weight of the resin (A-14) was 11,000, the number average molecular weight was 7,000, the acid value was 40 mgKOH / g, and the amine value was 35 mgKOH / g.

(Synthesis Example 18) Synthesis of Resin (A-15) A specific resin (A-15) was synthesized in the same manner as in Synthesis Example 17 except that succinic anhydride was changed to butane sultone in Synthesis Example 17.
The obtained specific resin (A-15) had a weight average molecular weight of 11,000, a number average molecular weight of 7,000, an acid value of 20 mgKOH / g, and an amine value of 15 mgKOH / g.

(Synthesis Example 19) Synthesis of Resin (A-16) In Synthesis Example 17, except that succinic anhydride was changed to diketene, the same operation as in Synthesis Example 17 was performed, and the resin (A-16) as a specific resin was obtained. Synthesized.
The weight average molecular weight of the resin (A-16) was 11,000, the number average molecular weight was 7,000, the acid value was 30 mgKOH / g, and the amine value was 30 mgKOH / g.

(Comparative Synthesis Example 1) Synthesis of Resin (A-17) To 233 g of PEGEA, 15 g (0.17 mol) of methacrylic acid, 85 g of macromonomer (1) having the following structure and 2.0 g (0.0099 mol) of dodecyl mercaptan were added. The mixture was heated to 75 ° C. under a nitrogen stream. Next, 1.48 g (0.0090 mol) of azobisisobutyronitrile was added and heated for 2 hours. Further, 1.48 g (0.0090 mol) of azobisisobutyronitrile was added and heated for 2 hours, then heated to 90 ° C. and heated for 1 hour. The resulting solution was allowed to cool to obtain a 30% by mass PEGEA solution of resin (A-17).
The amine value of the resin (A-17) was 85 mgKOH / g, the weight average molecular weight was 19,000, and the number average molecular weight was 7,000. A synthesis scheme is shown below.

[Examples 1 to 24, Comparative Example 1]
The black curable compositions (B-1) to (B-25) of Examples and Comparative Examples were prepared as follows, and then performance evaluation using these black curable compositions was performed. In addition, the black curable composition (B-23) prepared in Example 22 is a black curable composition of a reference example.

1. Preparation of Titanium Black Dispersion A component having the following composition I was subjected to a high viscosity dispersion treatment with a two roll to obtain a dispersion. In addition, you may knead | mix for 30 minutes with a kneader before a high-viscosity dispersion process.

(Composition I)
-Average primary particle size 75nm titanium black 40 parts (Mitsubishi Materials Corporation "13M-C") (Pigment Black35)
-5 parts of 30 mass% PGMEA solution of each resin (A-1)-(A-17)

  To the obtained dispersion, components shown in the following composition II were added and stirred for 3 hours using a homogenizer under the condition of 3,000 rpm. The obtained mixed solution was subjected to fine dispersion treatment for 4 hours with a disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.3 mm zirconia beads to obtain each titanium black dispersion.

(Composition II)
20 parts of 30% by mass PGMEA solution of resins (A-1) to (A-17) Solvent: 150 parts of PGMEA

2. 2. Preparation of black curable composition 2-1. Preparation of black curable compositions (B-1) to (B-22), (B-25) The components shown in the following composition III were mixed with a stirrer, and the black curable compositions of Examples 1 to 22 and 25 were used. (B-1) to (B-22), (B-25), and the black curable composition (B-17) of Comparative Example 1 were prepared.

(Composition III)
Alkali-soluble resin: Resin D-1 or Resin D-2 shown in Table 2 (structure shown below, composition ratio is mass ratio), both 30 parts by mass of PGMEA solution 10 parts dipentaerythritol hexaacrylate 2.0 Part: Pentaerythritol triacrylate 1.0 part Polymerization initiator listed in Table 2 0.3 part Titanium black dispersion 24 parts Solvent: PEGMEA 10 parts Solvent: ethyl-3-ethoxypropionate 8 parts

2-2. Preparation of black curable composition (B-23) In 200 ml of pure water kept at 60 ° C., 15 g of tin colloid (average particle system: 20 nm, solid content: 20 wt%, manufactured by Sumitomo Osaka Cement Co., Ltd.) and silver colloid (average) (Particulate system: 7 nm, solid content: 20% by weight, manufactured by Sumitomo Osaka Cement Co., Ltd.) 60 g and a solution of 0.75 g of polyvinylpyrrolidone in 100 ml of water were added to obtain a colloidal solution.
Next, this colloidal solution was stirred for 60 minutes while being kept at 60 ° C., and then irradiated with ultrasonic waves for 5 minutes. Next, this colloidal solution was concentrated by centrifugation to obtain a liquid A having a solid content of 25%. The liquid A was dried by a freeze drying method to obtain a powder sample.

A silver tin dispersion was prepared in the same manner as in “1. Preparation of titanium black dispersion” except that the powder sample obtained above was used instead of titanium black and resin (A-1) was used as the resin. Prepared. Further, the black curing of Example 22 (reference example) , which is a silver tin composition, was performed in the same manner as the black curable composition B-1, except that the silver tin dispersion was used instead of the titanium black dispersion. Sex composition (B-23) was prepared.

2-3. Preparation of black curable composition (B-24) (Preparation of red pigment dispersion)
The component shown in the following composition (IV) was finely dispersed for 4 hours with a disperser (trade name: Dispermat GETZMANN) using 0.3 mm zirconia beads to prepare a red pigment dispersion.

(Composition IV)
Organic pigment: C.I. I. Pigment Red 254 30 parts / resin solution (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10, Mw: 10000, resin solid content concentration: 40% PGMEA solution) 10 parts / solvent : PGMEA 200 partsDispersant: 30% PGMEA solution of resin (A-1) 30 parts

(Preparation of curable composition)
Black except that 20 parts of the titanium black pigment dispersion obtained using the resin (A-1) and 4 parts of the red pigment dispersion obtained above were used in “1. Preparation of titanium black dispersion”. In the same manner as in the curable composition B-1, a black curable composition (B-24) of Example 24 was prepared in combination with titanium black and a red pigment.

  Details of the polymerization initiators (I-1) to (I-6) described in Table 2 are shown below.

3. Performance Evaluation of Black Curable Composition Using the obtained black curable compositions of Examples 1 to 24 and Comparative Example 1, residue evaluation on a resin film using a lens material and on a glass substrate Formation and evaluation of a light-shielding film were performed.

3-1. Residue Evaluation on Resin Film Using Lens Material Thermosetting resin films 1 to 4 and photo-curing resin films 5 and 6 (hereinafter simply referred to as “resin films 1 to 6”) Was prepared as shown below.

<Preparation of curable composition for lens formation>
In Table 3, the compound shown in the column of component 2 was added to component 1 in the amount shown in the column of component 2 to prepare curable compositions for lens formation 1-6. Only the component 1 was used for the curable composition for lens formation in which the column of the component 2 was blank.

<Formation of thermosetting resin films 1 to 4>
The obtained lens-forming curable compositions 1 to 4 (2 mL) were applied on a 5 × 5 cm glass substrate (thickness: 1 mm, manufactured by Schott, BK7), and cured by heating at 200 ° C. for 1 minute. Thus, thermosetting resin films 1 to 4 (resin films 1 to 4) were formed.

<Formation of photocurable resin films 5 and 6>
The obtained curable compositions 5 and 6 (2 mL) were applied to a 5 × 5 cm glass substrate (thickness: 1 mm, manufactured by Schott, BK7), and irradiated with 3000 mJ / cm ² of light with a metal halide lamp. Curing was performed to form photocurable resin films 5 and 6 (resin films 5 and 6).

  In Table 3, mass% written together with component 2 is the amount of component 2 added to 100 mass% of component 1.

<Formation and development removal of black curable composition layer>
On the glass substrate provided with any of the resin films 1 to 6, the coating rotation speed of spin coating is adjusted so that the film thickness after coating and heat treatment becomes 2.0 μm, and is described in Table 4. A black curable composition layer was formed by uniformly applying the black curable composition and heat-treating it with a hot plate having a surface temperature of 120 ° C. for 120 seconds.
Next, the black curable composition layer was subjected to paddle development at 23 ° C. for 60 seconds using a 0.3 mass% tetramethylammonium hydroxide aqueous solution, and the black curable composition layer was removed. Thereafter, the glass substrate from which the black curable composition layer was removed was rinsed with a spin shower, further washed with pure water, and dried.

<Evaluation of residue on lens-forming resin film>
Residue evaluation is the maximum transmittance T1 (%) at 400 to 800 nm indicated by the resin films 1 to 6 immediately after being formed, and the resin films 1 to 6 after the formation and development removal of the black curable composition layer indicate The maximum transmittance T2 (%) at 400 to 800 nm is measured, and the transmittance reduction rate (%) of the lens-forming resin film before and after the formation of the black curable composition layer is calculated by the following formula (1). Was done.
Decrease in transmittance of resin film for lens formation (%) = T1 (%) − T2 (%) Formula (1)

  The transmittance in this evaluation is a measured value measured with a spectrophotometer (Shimadzu Corporation UV-3600 model number).

  It means that the residue which originates in a black curable composition remains on the resin film for lens formation, so that the transmittance | permeability reduction degree is large.

The above evaluation results are shown in Table 4 below.
In Table 4, the black curable compositions of Example 1 and Comparative Example 1 that were evaluated by changing the type of the lens-forming resin film were Examples 1-1 to 1-6 and Comparative Example 1. Indicated as -1 to 1-6.

3-2. Formation and evaluation of light shielding film on glass substrate <Formation of patterned light shielding film on glass substrate>
On a glass substrate (thickness: 1 mm, manufactured by Schott, BK7), spin coating was applied so that any of the obtained black curable compositions had a thickness of 2.0 μm after coating and heat treatment. A black curable composition layer was formed by adjusting the number of rotations of the coating and uniformly coating it, followed by heat treatment with a hot plate having a surface temperature of 120 ° C. for 120 seconds.
Then, a black curable composition layer obtained, using a high-pressure mercury lamp, through a photomask having a 50mm hole pattern, to change the exposure amount 100mJ / cm ² 1000mJ / cm up by 50 mJ / cm ^{2 2} exposure did.
The black curable composition layer after exposure was subjected to paddle development at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide to remove the unexposed portion of the black curable composition layer. . Thereafter, rinsing was performed with a spin shower, followed by washing with pure water to obtain a glass substrate having a patterned light-shielding film.

<Evaluation of adhesion between light-shielding film and glass substrate>
About the light shielding film in the obtained glass substrate with a light shielding film, the minimum exposure amount (sensitivity) which did not generate | occur | produce peeling was calculated | required using the optical microscope, and this was made into the parameter | index of adhesiveness. It shows that the adhesiveness of a glass substrate and a light shielding film is so high that the minimum exposure amount is small.

<Evaluation of residue on glass substrate>
Residue evaluation was performed for transmittance T3 (%) at 900 nm indicated by the glass substrate before the formation of the light-shielding film and transmittance T4 at 900 nm indicated by the glass substrate in the portion where the unexposed black curable composition layer was developed and removed. (%) Was measured, and the transmittance reduction degree (%) of the lens-forming resin film before and after the formation of the black curable composition layer was calculated by the following formula (2).
Degree of decrease in transmittance of glass substrate (%) = T3 (%) − T4 (%) Formula (2)
The transmittance was measured in the same manner as the transmittance of the lens-forming resin film.
It means that the residue derived from a black curable composition remains on the glass substrate, so that the transmittance | permeability reduction degree is large.

<Measurement of transmittance of light shielding film>
The transmittance of the obtained light-shielding film was measured in the same manner as the transmittance of the lens-forming resin film.

  The above evaluation results are shown in Table 5 below.

  As shown in Table 4 and Table 5, the black curable compositions of Examples 1 to 24 have a low transmittance reduction degree, which means that the wafer level lens is formed using the black curable composition of Examples. When the light shielding film provided is formed, it means that the generation of residue is reduced outside the light shielding film forming region composed of various lens forming resin films and glass substrates. Therefore, by forming the light shielding film using the black curable composition of the example, a wafer level lens having excellent performance can be provided.

Moreover, as Table 5 shows, the black curable composition of Examples 1-21 containing titanium black as an inorganic pigment is black hardening of Example 22 (reference example) containing inorganic pigments other than titanium black. It can be seen that the curing sensitivity is particularly excellent in comparison with the adhesive composition. Moreover, it turns out that light-shielding property improves more by using together titanium black and a red organic pigment like the black curable composition of Example 23. FIG.

[Example 25]
A curable resin layer is formed on a glass substrate using the lens-forming curable composition 5, the shape is transferred with a quartz mold having a lens shape, and cured with an exposure amount of 3000 mJ / cm ² by a high-pressure mercury lamp. Thus, a lens was formed. Next, the curable composition (B-1) of Example 1 was applied onto the glass substrate on which the lens was formed, and was exposed with a high-pressure mercury lamp through a photomask having a 0.5 mm hole pattern, A non-exposed portion was removed with a 0.3% aqueous solution of tetramethylammonium hydroxide to form a light shielding film on the outside of the lens and the lens peripheral portion, and a wafer level lens array having a plurality of wafer level lenses was produced.

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

  The wafer level lens obtained in Example 25 was free from residue at the lens opening, had good transparency, had high uniformity of the coated surface of the light shielding layer, and had high light shielding properties. .

Claims (11)

(A) titanium black , (B) polyethyleneimine, polyallylamine, or a dispersion resin that is a condensation product of polyvinylamine and polyester, (C) a polymerization initiator, (D) a polymerizable compound, and (E) an alkali-soluble resin. A black curable composition for a wafer level lens.   (A) titanium black, (B) a dispersion product of a primary or secondary amino group-containing compound and a polyester, an amine value of 5 mg KOH / g to 100 mg KOH / g, a dispersion resin, (C) a polymerization initiator, (D A black curable composition for a wafer level lens, comprising: a polymerizable compound; and (E) an alkali-soluble resin.   2. The colored curable composition for a wafer level lens according to claim 1, wherein the amine value of the (B) polyethyleneimine, polyallylamine, or dispersion resin which is a condensate of polyvinylamine and polyester is 5 mgKOH / g to 100 mgKOH / g. object.   The colored curable composition for a wafer level lens according to claim 2, wherein the condensate of the (B) primary or secondary amino group-containing compound and the polyester is a condensate of polyethyleneimine, polyallylamine or polyvinylamine and the polyester. object.   The black curable composition for wafer level lenses according to any one of claims 1 to 4, wherein the amine value of the (B) dispersion resin is 60 mgKOH / g to 78 mgKOH / g.   The colored curable composition for wafer level lenses according to any one of claims 1 to 5, wherein the weight average molecular weight of the (B) dispersion resin (polystyrene equivalent value by GPC method) is 5,000 to 50,000. Composition. Furthermore, (F) The black curable composition for wafer level lenses of any one of Claims 1-6 containing an organic pigment. The wafer level lens according to any one of claims 1 to 7 , wherein the polymerization initiator (C) is at least one polymerization initiator selected from an oxime ester compound and a hexaarylbiimidazole compound. Black curable composition.   The black curable composition for a wafer level lens according to claim 8, wherein the polymerization initiator (C) is an oxime ester compound. The black curable composition for a wafer level lens according to any one of claims 1 to 9 , wherein the (E) alkali-soluble resin is an alkali-soluble resin having a polymerizable double bond in a side chain. A wafer level lens provided with the light shielding film obtained using the black curable composition for wafer level lenses of any one of Claims 1-10 in the peripheral part of the lens which exists on a board | substrate.