JP2008185683A - Composition for solid state imager and method for producing microlens array - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition for a solid state imager excellent in pattern forming property and developability, giving a high refractive index cured product, and capable of easy pattern formation. <P>SOLUTION: The composition for a solid state imager comprises (A) particles in which when the total amount of metal atoms present in a particle surface is considered to be 100 at.%, the percentage of silicon atoms present in the particle surface is ≥20 at.%, (B) a compound having two or more (meth)acryloyl groups, (C) a photopolymerization initiator and (D) an organic solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a composition for a solid-state image sensor, and further relates to a method for manufacturing a microlens array using the composition for a solid-state image sensor.

The micro lens is a means for improving the light condensing power of a liquid crystal panel, a light condensing means for an optical pickup such as a laser disk (registered trademark), a compact disk, or a magneto-optical disk, and a concentrator for coupling an optical fiber with a light emitting element or light receiving element. In order to increase the sensitivity of optical means, solid-state image sensors such as CCDs or one-dimensional image sensors used in facsimiles, condensing means or imaging means for condensing incident light on the photoelectric conversion area, printing on liquid crystal printers and LED printers It is used in combination with various optical elements or optical components in an optical device such as an image forming means for forming an image to be formed on a photosensitive member, a filter for optical information processing.
As a manufacturing method of such a microlens, there are a machining method, a physical vapor deposition method, a registry flow method, etc., in which a mold is engraved with a thin bite and a resin or glass is poured into the mold. The registry flow method is known to be integrated with an optical device, and is used for a small CCD image sensor or the like.

  For example, Patent Documents 1 and 2 disclose positive photosensitive resin compositions in which exposed portions suitable for optical waveguides and lenses for optical elements are dissolved by alkali development. These photosensitive resin compositions contain an aromatic or aliphatic polyamide polymer and inorganic particles. Since these photosensitive resin compositions are positive type, in order to form a pattern, after coating on a silicon wafer, after mask exposure and development, further heating for converting into a heat resistant resin composition film Requires processing.

JP 2005-208465 A JP 2005-344005 A

  SUMMARY OF THE INVENTION An object of the present invention is to provide a negative photosensitive solid-state image sensor composition that is excellent in developability, excellent in pattern formability, and gives a cured product having a high refractive index and that is easy to form a pattern. Furthermore, an object of this invention is to provide the manufacturing method of a micro lens array using this composition for solid-state image sensors.

  In order to achieve the above-mentioned object, the present inventors have conducted intensive research, and as a microlens forming material, a metal oxide particle coated with silicon dioxide, which contains silicon atoms with respect to all metal elements present on the surface of the particle. When a photocurable composition containing metal oxide particles having a ratio of 20 atomic% or more and a polyfunctional (meth) acrylate compound is used, the composition of the uncured portion in the alkali development treatment after pattern formation by exposure The inventors have found that objects can be easily removed and that a highly accurate pattern can be formed, and the present invention has been completed.

［式（１１）中、ＸはＮＨ、Ｏ（酸素原子）又はＳ（イオウ原子）を示し、ＹはＯ又はＳを示す。］
６．前記（Ｂ）の２個以上の（メタ）アクリロイル基を有する化合物が、３個以上の（メタ）アクルロイル基を有する化合物である上記１〜５のいずれかに記載の固体撮像素子用組成物。
７．前記（Ｄ）有機溶剤が、１２０℃以上の沸点を有する有機溶剤である上記１〜６のいずれかに記載の固体撮像素子用組成物。
８．前記（Ｄ）有機溶剤が、乳酸エチル、γ−ブチロラクトン、Ｎ−メチルピロリドンからなる群から選択される１種以上である上記７に記載の固体撮像素子用組成物。
９．さらに、（Ｅ）界面活性剤を含有する上記１〜６のいずれかに記載の固体撮像素子用組成物。
１０．前記（Ｅ）界面活性剤が、フッ素又はシリコン、あるいは両方を含有するノニオン系界面活性剤から選択される上記９に記載の固体撮像素子用組成物。
１１．固体撮像素子の表面レンズ、層内レンズ又は高屈折率層形成用である上記１〜１０のいずれかに記載の固体撮像素子用組成物。
１２．上記１〜１０のいずれかに記載の固体撮像素子用組成物を基材上に塗布し、露光してパターン形成し、アルカリ現像液に浸漬した後、水で洗浄することを含むマイクロレンズアレイの製造方法。
１３．前記アルカリ現像液のアルカリ成分の濃度が、０．０１〜５重量％の範囲内である上記１２に記載のマイクロレンズアレイの製造方法。 The present invention provides the following composition for a solid-state imaging device and a method for producing a microlens array.
1. The following components (A) to (D):
(A) When the total amount of metal atoms present on the particle surface is 100 atomic%, the ratio of silicon atoms present on the particle surface is 20 atomic% or more. (B) Two or more (meth) acryloyl groups A composition for a solid-state imaging device comprising a compound (C) having a photopolymerization initiator (D) and an organic solvent.
2. 2. The composition for a solid-state imaging device as described in 1 above, wherein the particle size of the particle (A) is 3 to 100 nm and the refractive index is 1.70 or more.
3. 3. The composition for a solid-state imaging device according to 1 or 2 above, wherein the particles (A) are particles mainly composed of a metal oxide selected from the group consisting of titania, alumina, and zirconia, and silicon dioxide is present on the surface. object.
4). 4. The composition for a solid-state imaging device as described in any one of 1 to 3 above, wherein the particle (A) is a particle having a polymerizable unsaturated group.
5. 5. The composition for a solid-state imaging device according to 4 above, wherein the polymerizable unsaturated group contained in the particle (A) is a group including a structure represented by the following formula (11).

[In the formula (11), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]
6). The composition for a solid-state imaging device as described in any one of 1 to 5 above, wherein the compound having two or more (meth) acryloyl groups in (B) is a compound having three or more (meth) acryloyl groups.
7). The composition for a solid-state imaging device as described in any one of 1 to 6 above, wherein the (D) organic solvent is an organic solvent having a boiling point of 120 ° C. or higher.
8). 8. The composition for a solid-state imaging device as described in 7 above, wherein the organic solvent (D) is at least one selected from the group consisting of ethyl lactate, γ-butyrolactone, and N-methylpyrrolidone.
9. Furthermore, the composition for solid-state image sensors in any one of said 1-6 containing (E) surfactant.
10. 10. The composition for a solid-state imaging device as described in 9 above, wherein the (E) surfactant is selected from nonionic surfactants containing fluorine, silicon, or both.
11. 11. The composition for a solid-state imaging device as described in any one of 1 to 10 above, which is for forming a surface lens, an in-layer lens or a high refractive index layer of the solid-state imaging device.
12 A microlens array comprising: applying the composition for a solid-state imaging device according to any one of 1 to 10 above onto a substrate; exposing to pattern formation; immersing in an alkali developer; and washing with water. Production method.
13. 13. The method for producing a microlens array as described in 12 above, wherein the concentration of the alkali component in the alkali developer is in the range of 0.01 to 5% by weight.

According to the present invention, a composition for a solid-state imaging device having a high refractive index and excellent alkali developability is provided.
According to the present invention, a microlens array having a high refractive index and a highly accurate pattern can be manufactured.

I. The composition for solid-state image sensors The composition for solid-state image sensors of this invention (henceforth the composition of this invention) may contain the following component (A)-(F). In the present specification, “refractive index” means a refractive index measured at a wavelength of 589 nm and 23 ° C. In the present specification, the “high refractive index material” means a material having a refractive index of 1.68 or more.
Among these, components (A) to (D) are essential components, and (E) to (F) are optional components to be added as necessary.
(A) When the total amount of metal atoms present on the particle surface is 100 atomic%, the ratio of silicon atoms present on the particle surface is 20 atomic% or more. (B) Two or more (meth) acryloyl groups (C) Photopolymerization initiator (D) Organic solvent (E) Surfactant (F) additive Each component constituting the material of the present invention will be described below.

(A) When the total amount of metal atoms present on the particle surface is 100 atomic%, the ratio of silicon atoms present on the particle surface is 20 atomic% or more. When the material is patterned, it is an essential component for obtaining the effect of the present invention that uncured portions are easily removed in the development and washing processes.

Since the composition of the present invention has silicon dioxide (isoelectric point pH = 2) at a high concentration of 20 atomic% or more on the surface of the metal oxide particle, the charge on the particle surface can be controlled, During development, the dispersion is quickly dispersed with an alkaline developer, and the uncured portion can be easily removed when rinsed with water or the like. At this time, the particles are more easily dispersed when the isoelectric point on the particle surface is away from the pH of the developer.
For example, since the isoelectric point of titanium oxide is pH = 7, it is difficult to disperse particles (cannot be developed) even when immersed in an alkaline developer (pH = 10). On the other hand, titanium oxide is coated with silicon dioxide and the isoelectric point is lowered by adjusting the ratio of silicon atoms on the surface of the particles, so that it can be dispersed in an alkali developer and developed.

(1) Particles The particles of the component (A) preferably have a particle diameter of 3 to 100 nm, and more preferably 5 to 20 nm. Further, the refractive index of the particles should be appropriately selected according to the purpose, but when a high refractive index is required, it is preferably 1.70 or more, and more preferably 2.0 or more.
The particles of the component (A) are preferably particles having a metal oxide as a main component (hereinafter referred to as metal oxide particles), and a metal oxide selected from the group consisting of titania, alumina and zirconia as a main component. And particles having a surface coated with silicon dioxide are more preferable, and particles having titania as a main component and the surface coated with silicon dioxide are particularly preferable from the viewpoint of high refractive index. In the present application, “the surface is covered with silicon dioxide” does not require that the particle surface is completely covered with silicon dioxide, but may be any state as long as silicon dioxide is exposed on the particle surface.
The particle | grains of a component (A) may be used individually by 1 type, and may be used in combination of multiple types.

(2) Coating of particles with silicon dioxide As a method of coating metal oxide particles with silicon dioxide, a known method, for example, a method described in JP-A Nos. 2003-112923 and 8-48940 is used. Can do.
Specifically, the metal oxide particles are dispersed in water so as to be 0.1 to 10% by weight. To this dispersion is added a metal hydroxide such as sodium hydroxide or potassium hydroxide, a basic nitrogen compound such as ammonia or quaternary amine, and the pH is adjusted to 9-12. The temperature of the dispersion is adjusted to 50 to 100 ° C., and an alkali metal silicate such as sodium silicate or potassium silicate as a silica source is added continuously or intermittently to the metal oxide particles. It is deposited on the surface to obtain metal oxide particles coated with silicon dioxide. The obtained silicon dioxide-coated metal oxide particles are preferably subjected to heat aging, washing, concentration, and drying as necessary.

  In order to adjust the ratio of silicon atoms on the particle surface, the amount of silicon dioxide to be coated may be adjusted. For example, the amount of alkali metal silicate to be added may be adjusted by the above method.

(3) Ratio of silicon atoms present on the particle surface The ratio of silicon atoms present on the particle surface can be measured as follows. That is, the particle dispersion was diluted with ethyl lactate to 5 to 15% by weight, spin-coated, and the dried coating film was subjected to elemental analysis by X-ray photoelectron spectroscopy (also referred to as XPS or ESCA) (measurement angle: 45). Every time).
When the total amount of metal atoms present on the particle surface is 100 atomic%, the proportion of silicon atoms present on the particle surface is preferably 20 atomic% or more, and more preferably 30 atomic% or more. If the proportion of silicon atoms present on the particle surface is less than 20 atomic%, the dispersibility of the particles in the developer may be reduced.
In addition, the upper limit of the ratio of silicon atoms present on the particle surface is not particularly limited, but when a high refractive index is required, it is naturally determined by the limit amount that can cover the surface of the metal oxide particles with silicon dioxide. Usually, it is about 70 atomic%, preferably about 60 atomic%.

［式（１１）中、ＸはＮＨ、Ｏ（酸素原子）又はＳ（イオウ原子）を示し、ＹはＯ又はＳを示す。］ (4) The particles of the component (A) may be particles having a polymerizable unsaturated group (hereinafter referred to as reactive particles).
The polymerizable unsaturated group contained in the component (A) particles is a compound containing a group that generates a silanol group by hydrolysis and a polymerizable unsaturated group (hereinafter sometimes referred to as “silane coupling agent”). It can be introduced by processing. The silane coupling agent may contain a group represented by the following formula (11).

[In the formula (11), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]

(5) Silane coupling agent The silane coupling agent used in the present invention is a compound containing a polymerizable unsaturated group and a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis. . Commercially available silane coupling agents can be used in the present invention. It can also be obtained by the method described below.

(I) Polymerizable unsaturated group Although there is no restriction | limiting in particular as a polymerizable unsaturated group contained in a silane coupling agent, For example, an acryloyl group, a methacryloyl group, a vinyl group, a propenyl group, a butadienyl group, a styryl group, an ethynyl group A cinnamoyl group, a maleate group and an acrylamide group can be mentioned as preferred examples.
This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

(Ii) A silanol group or a group that generates a silanol group by hydrolysis A silane coupling agent is a compound having a silanol group in the molecule (hereinafter sometimes referred to as “silanol group-containing compound”) or a silanol group by hydrolysis. It is preferably a compound to be generated (hereinafter sometimes referred to as “silanol group-generating compound”). Examples of such a silanol group-forming compound include compounds having an alkoxy group, aryloxy group, acetoxy group, amino group, halogen atom, etc. on the silicon atom, but an alkoxy group or aryloxy group on the silicon atom. In other words, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
The silanol group-generating site of the silanol group or the silanol group-generating compound is a structural unit that binds to the oxide particles by a condensation reaction or a condensation reaction that occurs following hydrolysis.

(Iii) Group represented by Formula (11) The silane coupling agent preferably further includes a group represented by Formula (11) in the molecule. Specific examples of the group [—X—C (═Y) —NH—] represented by the formula (11) include [—O—C (═O) —NH—], [—O—C (═S). ) —NH—], [—S—C (═O) —NH—], [—NH—C (═O) —NH—], [—NH—C (═S) —NH—], and [ -S-C (= S) -NH-]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH— groups.
The group [—X—C (═Y) —NH—] represented by the formula (11) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when cured. It is considered that it gives properties such as adhesion to the material and heat resistance.

(Iv) Preferred Embodiment As a preferred specific example of the silane coupling agent, for example, a compound represented by the following formula (12) can be mentioned.

R ¹⁹ and R ²⁰ may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and a represents a number of 1, 2 or 3.
Examples of R ¹⁹ and R ²⁰ include methyl, ethyl, propyl, butyl, octyl, phenyl, xylyl groups and the like.

Examples of the group represented by [(R ¹⁹ O) _a R ²⁰ _3-a Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, and the like. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

R ²¹ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms and may contain a chain, branched or cyclic structure. Examples of such an organic group include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, and dodecamethylene. Among these, preferred examples are methylene, propylene, cyclohexylene, phenylene and the like.

R ²² is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. For example, chain polyalkylene groups such as hexamethylene, octamethylene, dodecamethylene; alicyclic or polycyclic divalent organic groups such as cyclohexylene and norbornylene; divalent groups such as phenylene, naphthylene, biphenylene and polyphenylene Aromatic group; and these alkyl group-substituted and aryl group-substituted products. Further, these divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and include a polyether bond, a polyester bond, a polyamide bond, a polycarbonate bond, and a group represented by the formula (11). Can also be included.

R ²³ is a (b + 1) -valent organic group, preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.

  Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. For example, acryloyl (oxy) group, methacryloyl (oxy) group, vinyl (oxy) group, propenyl (oxy) group, butadienyl (oxy) group, styryl (oxy) group, ethynyl (oxy) group, cinnamoyl (oxy) group , Maleate group, acrylamide group, methacrylamide group and the like. Among these, an acryloyl (oxy) group and a methacryloyl (oxy) group are preferable. Further, b is preferably a positive integer of 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.

  For the synthesis of the silane coupling agent used in the present invention, for example, a method described in JP-A-9-100111 can be used. That is, (i) it can be carried out by an addition reaction of a mercaptoalkoxysilane, a polyisocyanate compound, and an active hydrogen group-containing polymerizable unsaturated compound. (B) The reaction can be carried out by a direct reaction between a compound having an alkoxysilyl group and an isocyanate group in the molecule and an active hydrogen-containing polymerizable unsaturated compound. Furthermore, (c) it can also be directly synthesized by an addition reaction of a compound having a polymerizable unsaturated group and an isocyanate group in the molecule with mercaptoalkoxysilane or aminosilane.

In order to synthesize the compound represented by the formula (12), (a) is preferably used among these methods. More specifically, for example,
Method (a): First, a mercaptoalkoxysilane and a polyisocyanate compound are reacted to form an intermediate containing an alkoxysilyl group, [—S—C (═O) —NH—] group and an isocyanate group in the molecule. Next, an active hydrogen-containing polymerizable unsaturated compound is reacted with the isocyanate remaining in the intermediate, and this unsaturated compound is bonded via a [—O—C (═O) —NH—] group. How to
Method (b): First, a polyisocyanate compound and an active hydrogen-containing polymerizable unsaturated compound are reacted to form a polymerizable unsaturated group, [—O—C (═O) —NH—] group, and isocyanate in the molecule. Forming an intermediate containing a group, reacting this with a mercaptoalkoxysilane, and bonding the mercaptoalkoxysilane via a [—S—C (═O) —NH—] group,
Etc. Further, among them, the method (a) is preferable in that there is no decrease in polymerizable unsaturated groups due to the Michael addition reaction.

  In the synthesis of the compound represented by the formula (12), examples of alkoxysilane capable of forming a [—S—C (═O) —NH—] group by reaction with an isocyanate group include an alkoxysilyl group and a mercapto group. Mention may be made of compounds each having one or more groups in the molecule. Examples of such mercaptoalkoxysilane include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyldimethoxymethylsilane, mercaptopropylmethoxydimethylsilane, mercaptopropyltriphenoxy silane, mercapto Mention may be made of propyltributoxysilane. Among these, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane are preferable. Moreover, an addition product of an amino-substituted alkoxysilane and an epoxy group-substituted mercaptan and an addition product of an epoxysilane and an α, ω-dimercapto compound can also be used.

  The polyisocyanate compound used for synthesizing the silane coupling agent can be selected from polyisocyanate compounds composed of chain saturated hydrocarbons, cyclic saturated hydrocarbons, and aromatic hydrocarbons.

  Examples of such polyisocyanate compounds include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5- Naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethylphenylene diisocyanate, 4,4′- Biphenylene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanate ester) F) Fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, tetramethylxylylene diisocyanate, 2,5 ( Or 6) -bis (isocyanatomethyl) -bicyclo [2.2.1] heptane and the like. Among these, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanate methyl) cyclohexane, and the like are preferable. These can be used singly or in combination of two or more.

  In the synthesis of a silane coupling agent, as an example of an active hydrogen-containing polymerizable unsaturated compound that can be bonded to the polyisocyanate compound via an [—O—C (═O) —NH—] group by an addition reaction, Mention may be made of compounds having at least one active hydrogen atom capable of forming a [—O—C (═O) —NH—] group by addition reaction with an isocyanate group and at least one polymerizable unsaturated group. .

Examples of these active hydrogen-containing polymerizable unsaturated compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenyloxy. Propyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, Neopentyl glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta ( Data) acrylate, and the like can be mentioned. Moreover, the compound obtained by addition reaction with glycidyl group containing compounds, such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth) acrylate, and (meth) acrylic acid can be used. Among these compounds, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate and the like are preferable.
These compounds can be used individually by 1 type or in mixture of 2 or more types.

(6) Surface treatment method for component (A) particles (hereinafter sometimes simply referred to as particles) The surface treatment method for particles is not particularly limited, but is a hydrolyzable silicon compound or silane coupling agent (hereinafter referred to as surface). It is also possible to produce the mixture by mixing particles with a treating agent) and heating and stirring. The reaction is preferably carried out in the presence of water in order to efficiently combine the silanol group-generating site of the surface treatment agent with the particles. However, when the surface treatment agent has a silanol group, there is no need for water. Therefore, the surface treatment can be performed by a method including an operation of mixing at least the particles and the surface treatment agent.

  The reaction amount of the particles and the surface treatment agent is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, particularly preferably 1% by weight, with the total of the particles and the silane coupling agent being 100% by weight. % Or more. If it is less than 0.01% by weight, the dispersibility of the particles in the composition is not sufficient, and the transparency and scratch resistance of the resulting cured product may not be sufficient.

  The amount of water consumed by hydrolysis of the alkoxysilane compound in the surface treatment agent at the time of the surface treatment may be an amount by which at least one alkoxy group on silicon in one molecule is hydrolyzed. Preferably, the amount of water added or present during hydrolysis is at least one third of the number of moles of all alkoxy groups on the silicon, more preferably one half of the number of moles of all alkoxy groups. It is less than 3 times. The product obtained by mixing the alkoxysilane compound and the particles in a completely moisture-free condition is a product in which the alkoxysilane compound is physically adsorbed on the particle surface, and particles composed of such components are not included. In the hardened | cured material of the composition to contain, the effect of expression of high hardness and abrasion resistance is low.

  At the time of the surface treatment, after subjecting the surface treatment agent to a separate hydrolysis operation, this is mixed with powder particles or solvent dispersion sol of the particles, followed by heating and stirring operation; hydrolysis of the alkoxysilane compound; A method of performing in the presence of particles; or a method of performing surface treatment of particles in the presence of other components such as a polymerization initiator can be selected. In this, the method of hydrolyzing the said alkoxysilane compound in presence of particle | grains is preferable. During the surface treatment, the temperature is preferably 0 ° C. or higher and 150 ° C. or lower, more preferably 20 ° C. or higher and 100 ° C. or lower. The processing time is usually in the range of 5 minutes to 24 hours.

In the case of using a powdery powder during the surface treatment, an organic solvent may be added for the purpose of causing the reaction with the surface treatment agent to be performed smoothly and uniformly. Examples of such organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate and Y-butyrolactone. Esters such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone . Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.
The amount of these solvents added is not particularly limited as long as it meets the purpose of carrying out the reaction smoothly and uniformly.

  When a solvent-dispersed sol is used as the particles, it can be produced by mixing at least a solvent-dispersed sol and a surface treatment agent. Here, an organic solvent which is uniformly compatible with water may be added for the purpose of ensuring the uniformity at the initial stage of the reaction and allowing the reaction to proceed smoothly.

In addition, an acid, a salt or a base may be added as a catalyst to promote the reaction during the surface treatment.
Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, toluenesulfonic acid, phthalic acid, malonic acid, formic acid, acetic acid, and succinic acid; methacrylic acid, acrylic acid, and itacone An unsaturated organic acid such as an acid, as a salt, for example, an ammonium salt such as tetramethylammonium hydrochloride or tetrabutylammonium hydrochloride, and as a base, for example, aqueous ammonia, diethylamine, triethylamine, dibutylamine, Primary, secondary or tertiary aliphatic amines such as cyclohexylamine, aromatic amines such as pyridine, quaternary ammonium hydroxides such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide Etc. can be mentioned.
Among these, preferable examples of the acid include organic acids and unsaturated organic acids, and the base includes tertiary amines or quaternary ammonium hydroxides and aqueous ammonia.

In order to accelerate the reaction, it is also preferable to add a dehydrating agent.
As the dehydrating agent, inorganic compounds such as zeolite, anhydrous silica, and anhydrous alumina, and organic compounds such as methyl orthoformate, ethyl orthoformate, tetraethoxymethane, and tetrabutoxymethane can be used. Of these, organic compounds are preferable, and orthoesters such as methyl orthoformate and ethyl orthoformate are more preferable.
The amount of the alkoxysilane compound bonded to the particles is usually a thermogravimetric analysis from 110 ° C. to 800 ° C. in air as a constant value of weight loss% when the dry powder is completely burned in air. It can ask for.

(7) Compounding amount of component (A) The compounding amount of component (A) in the composition of the present invention is usually 50 to 85% when the total solid content excluding the organic solvent of the composition is 100% by weight. %, Preferably 60 to 75% by weight, more preferably 65 to 75% by weight. If it is less than 50% by weight, the refractive index may be lowered, and if it exceeds 85% by weight, the film forming property may be deteriorated due to a decrease in the resin component serving as a binder.
In addition, when a component (A) is a dispersion liquid, a dispersion medium is not included in the said compounding quantity. Moreover, it is the said compounding quantity regardless of whether particle | grains have a polymerizable unsaturated group.

(B) Compound having two or more (meth) acryloyl groups The component (B) reacts and crosslinks with the decomposition of the initiator by light irradiation, thereby ensuring the strength of the coating film. Specifically, effects such as suppression of swelling of the coating film and outflow of particles during immersion in the developer after exposure, and imparting scratch resistance to the coating film are obtained.

The component (B) is not particularly limited as long as it is a compound having two or more (meth) acryloyl groups, but is preferably a compound having three or more (meth) acryloyl groups.
Examples of such (meth) acrylic esters include tetramethylolmethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (Meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di ( Acrylate), neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanate Nurate di (meth) acrylate, bis ((meth) acryloyloxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane (also referred to as “tricyclodecanediyldimethanol di (meth) acrylate”), and these Poly (meth) acrylates of ethylene oxide or propylene oxide adducts of starting alcohols in the production of the above compounds, oligoesters (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoethers (meta Acrylate , Oligourethane (meth) acrylates, oligoepoxy (meth) acrylates, and the like.

Examples of commercially available components (B) include, for example, dipentaerythritol penta / hexamethacrylate (Aronix TO-1786, manufactured by Toagosei Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.), trimethylolpropane triacrylate (Biscoat # 295, manufactured by Osaka Organic Chemical Industry Co., Ltd.), pentaerythritol triacrylate (Biscoat # 300, manufactured by Osaka Organic Chemical Industry Co., Ltd.), Examples include dipentaerythritol pentaacrylate (SARTOMER SR399E, manufactured by Sakai Kogyo Co., Ltd.), tetramethylol methane triacrylate (NK ester A-TMM-3LM-N, manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.
The compound of a component (B) may be used individually by 1 type, and may be used in combination of multiple types.

(2) Compounding amount of component (B) The compounding amount of component (B) in the composition of the present invention is usually 10 to 50% when the total solid content excluding the organic solvent in the composition is 100% by weight. %, Preferably 20 to 40% by weight, more preferably 20 to 30% by weight. If it is less than 10% by weight, the coating film may swell or collapse when immersed in the developer, or the patterning property may be lowered. If it exceeds 50% by weight, a high refractive index may not be expected.

(C) Photopolymerization initiator By adding the photopolymerization initiator, the component (B) can be efficiently crosslinked. When no photopolymerization initiator is added, the crosslinking reaction does not occur even when irradiated with light, and curing hardly proceeds. Therefore, the strength as a coating film cannot be ensured and patterning becomes impossible.

(1) Type The photopolymerization initiator is a compound that generates active species upon irradiation with active energy rays, and examples thereof include a photo radical generator that generates radicals as active species.
The active energy ray is defined as an energy ray capable of decomposing a compound that generates active species to generate active species. Examples of such active energy rays include optical energy rays such as visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, and γ rays. However, it is preferable to use ultraviolet rays from the viewpoint of having a certain energy level, a high curing speed, and a relatively inexpensive irradiation apparatus, and a small size.

  Examples of the photo radical generator include acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone, 4 , 4′-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1- (4-dodecylphenyl) -2 -Hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenyl Phosphine oxide, 1-H Roxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler ketone, 3-methylacetophenone, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone (BTTB), 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1-butanone, 4-benzoyl -4'-methyldiphenyl sulfide, benzyl, or a combination of BTTB and xanthene, thioxanthene, coumarin, ketocoumarin, and other dye sensitizers.

Among these photopolymerization initiators, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6- Trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2 -Phenylmethyl) -1-butanone and the like are preferable, and 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (Dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl ) -1-butanone, and the like.
These photo radical generators may be used alone or in combination of two or more.

  Examples of commercially available photo radical generators include, for example, hydroxycyclohexyl phenyl ketone (IRGACURE184, manufactured by Ciba Specialty Chemicals), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane. -1-one (IRGACURE907, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 2-hydroxy-2-methylpropiophenone (DAROCURE 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.).

(2) Compounding amount of component (C) The compounding amount of component (C) in the composition of the present invention is usually 1 to 10% when the total solid content excluding the organic solvent in the composition is 100% by weight. %, Preferably 3 to 7% by weight. If the amount is less than 1% by weight, sufficient curing may not be expected. If the amount exceeds 10% by weight, the coating strength may decrease due to an increase in components not involved in crosslinking.

(D) Organic solvent An organic solvent is mix | blended with the composition of this invention. By blending the organic solvent, it becomes possible to provide a leveling property when applying the composition and to obtain a uniform coating film. Moreover, in order to mix uniformly all the components ((A) particle | grains, (B) polyfunctional (meth) acrylate, (C) photoinitiator, (E) surfactant mentioned later), etc.) in a composition. It is preferable to select an organic solvent having a composition that dissolves all the components satisfactorily.

The organic solvent used in the present invention preferably has a boiling point of 120 ° C. or higher at normal pressure. If the boiling point is low, the solvent volatilizes during leveling, and a uniform coating film may not be obtained.
Specific examples of the organic solvent used in the present invention include, for example, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Examples include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, N-methylpyrrolidone, and γ-butyrolactone.
These organic solvents can be used alone or in admixture of two or more, but preferably contain at least one selected from ethyl lactate, γ-butyrolactone, and N-methylpyrrolidone.

  In addition, when the particle | grains of the said component (A) are organic solvent dispersion liquids, you may use the dispersion medium as it is as an organic solvent of a component (D), and may substitute it with another organic solvent.

  The compounding amount of the component (D) in the composition of the present invention is usually 150 to 10,000 parts by weight, preferably 200 to 600 parts by weight, based on 100 parts by weight of the total solid content excluding the organic solvent of the composition. More preferably, it is 300-550 weight part. When the amount is less than 150 parts by weight, there is a risk that the storage stability may be lowered due to a decrease in dispersion stability of the particles, and a uniform coating film may not be obtained due to insufficient leveling. The film thickness may not be obtained, and the light collecting function that the coating film should originally perform may not be exhibited.

(E) Surfactant A surfactant may be added to the composition of the present invention. By adding a surfactant, leveling properties are improved and a more uniform coating film can be obtained.

The surfactant used in the present invention is preferably a nonionic surfactant containing fluorine, silicon, or both. In the case of an anionic or cationic surfactant, if the charge does not match the particle component of the component (A), the particles may aggregate.
Surfactant may be used individually by 1 type and may be used in combination of multiple types.

  The compounding amount of the component (E) in the composition of the present invention is usually 0.01 to 5% by weight, preferably 0.1 to 0.1% when the total solid content excluding the organic solvent of the composition is 100% by weight. 3% by weight, more preferably 0.5 to 2% by weight. If the amount is less than 0.01% by weight, the leveling property may be insufficient and a uniform coating film may not be obtained. If the amount exceeds 5% by weight, the strength of the coating film may be reduced due to an increase in non-crosslinked components. There is a possibility that the affinity with the components is reduced, repellency occurs in the coating film, and a uniform coating film cannot be obtained.

(F) Other additive Various additives can be mix | blended with the composition of this invention in the range which does not impair the effect of this invention. Examples of such additives include developability improvers.
Examples of the developability improver include a polymer or oligomer containing a hydroxyl group and / or a carboxylic acid group or both functional groups. Addition of these is expected to improve developability, and developability may be imparted even if the amount of particles covered with SiO ₂ is small. More specifically, hydroxystyrene etc. are mentioned, for example.

  The composition of this invention is obtained by adding the said component (A)-(D) and the said component (E) and various additives as needed, and stirring uniformly.

  As described above, since the composition of the present invention can easily remove non-exposed portions and has excellent patternability, it is particularly solid-state imaging produced by coating, mask exposure, development, and washing. It is very useful as a material for microlenses for devices. Examples of the solid-state image sensor microlens include a surface lens and an in-layer lens. Furthermore, since the composition of the present invention can provide a cured film having a high refractive index, it is also useful as a material for forming a high refractive index layer of a solid-state imaging device.

II. Manufacturing method of microlens array The manufacturing method of the microlens array of the present invention (hereinafter referred to as the manufacturing method of the present invention) is a method of applying the above-described composition for a solid-state imaging device of the present invention on a substrate and exposing it to pattern formation. And after immersing in an alkali developer, it is washed with water.
The material of the present invention used in the production method of the present invention is a negative photocurable composition in which an exposed portion is cured and an unexposed portion is uncured.
Hereafter, the manufacturing method of this invention is demonstrated for every process.

(1) Application The composition of the present invention is preferably preliminarily filtered with a filter having a pore diameter of about 0.05 to 1 μm, preferably a 0.5 μm filter. The substrate to which the composition of the present invention is applied may be surface-treated with HMDS (hexamethyldisilazane). Examples of the HMDS treatment method include a method of dropping HMDS on a substrate and rotating the substrate with a spin coater to remove excess HMDS, a method of exposing the substrate to an atmosphere containing vaporized HMDS, and the like. Examples of the method for applying the composition of the present invention include spin coating, roll coating, bar coating, large coating, and gravure printing. Spin coating is preferred because it is easy to obtain film thickness uniformity. The coated substrate is preferably further baked with a hot plate or an oven. The baking conditions can be appropriately adjusted depending on the composition. For example, a coating film is prepared by heating on a hot plate at 50 to 120 ° C., preferably 70 to 90 ° C. for 30 to 300 seconds, preferably 60 to 120 seconds. Can do.

(2) Exposure The mask used in the exposure is not particularly limited, and an appropriate mask may be selected according to the purpose.
The coating film produced above is exposed through a mask to form a pattern. For the exposure, a mask aligner, a reduced projection exposure apparatus, or the like can be used. The light source for exposure is not particularly limited as long as it contains light having a wavelength to which the component (C) of the composition of the present invention is sensitive.

(3) Development The exposed film is developed in a subsequent development process. Examples of the developing method include paddle development, dip development, and shower development. Developers include organic solvents such as acetone, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol monomethyl ether acetate, methyl amyl ketone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, sodium hydroxide, potassium hydroxide. An alkaline aqueous solution in which tetramethylammonium hydroxide or the like is dissolved can be used, but an alkaline aqueous solution (alkaline developer) is preferred because high dimensional accuracy is easily obtained.
The concentration of the alkali component in the aqueous alkali solution used here is preferably in the range of 0.01 to 10% by weight, and more preferably in the range of 0.03 to 5% by weight. Since it is possible to obtain better developability when the pH of the developer is far from the isoelectric point (pH = 2) of silicon dioxide on the particle surface, development becomes impossible when the alkali component concentration is less than 0.01% by weight. there is a possibility. On the other hand, if the alkali component concentration exceeds 10% by weight, the exposed portion is dissolved (developed) and may be peeled off from the substrate.

(4) Rinse It is preferable to rinse the developed film with pure water to remove particle components, alkali components, and the like that are not immobilized on the substrate.

In the curable composition conventionally used for forming the microlens, the surface of the metal oxide particle such as titanium oxide does not have a predetermined ratio or more of silicon atoms, that is, the particle surface is made of SiO ₂ with a predetermined amount or more. Since it was not processed, when immersed in an alkali developer after mask exposure, there was a problem that the unexposed portion was not easily dispersed in the developer and a pattern was not formed.

  According to the present invention, since a predetermined amount or more of silicon atoms are present on the particle surface, the unexposed portion is easily dispersed in the developer, and a microlens array excellent in fine patterning property can be easily manufactured.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following, parts and% respectively represent parts by weight and% by weight unless otherwise specified.

Reference Example 1: Measurement of ratio of silicon atoms to all metal atoms present on the surface of silicon dioxide-coated metal oxide particles (1) Preparation method of measurement sample Dispersion liquid of silicon dioxide-coated metal oxide particles shown in Table 1 below ( Particles (1) to (3)) were diluted to 5 to 20% by weight with a dispersion solvent, and spin-coated (300 rpm for 5 seconds and then 2000 rpm for 60 seconds) on a silicon wafer to form a coating film. This was heated on a hot plate at 80 ° C. for 1 hour to obtain a measurement sample.

(2) Elemental composition measurement of particle surface by X-ray photoelectron spectroscopy (XPS) The measurement sample obtained in the above (1) is subjected to an XPS measurement apparatus (AXIS ULTRA, manufactured by Kratos) under the condition of a measurement angle of 45 °. The surface metal element composition was analyzed. The results are shown in Table 1.

The product names in Table 1 are as follows.
Particle (1): manufactured by Catalyst Kasei Kogyo Co., Ltd., silicon dioxide-coated titanium dioxide particles, number average particle diameter 10 nm
Particle (2): manufactured by Teika, silicon dioxide-coated titanium oxide, number average particle diameter major axis 49 nm, minor axis 10 nm
Particle (3): manufactured by Teica, alumina-coated titanium oxide, number average particle diameter major axis 49 nm, minor axis 18 nm
The particle diameter was calculated from an observation image of a TEM (transmission electron microscope).

Reference Example 2: Dispersibility of Particles to Developer Solution Each particle dispersion prepared in Reference Example 1 was spin-coated on a Si wafer (5 seconds at 300 rpm, then 60 seconds at 2000 rpm), and then on a hot plate at 50 ° C. After being heated for 30 seconds, the sample was immersed in developer PD523 (manufactured by JSR, concentration 2.38 wt%) for 1 minute, and whether or not the particles were dispersed in the developer was visually confirmed and evaluated according to the following criteria. The results are shown in Table 2.
○: Dissolved within 30 seconds (good dispersibility)
Δ: Dissolved in about 1 minute (medium dispersibility)
×: Not dissolved even after immersion for 1 minute (poor dispersibility)

Example 1
(1) Manufacture of composition (A) 20.4 parts of tetramethylol and SiO ₂ coated TiO ₂ dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .; the above particles (1)) concentrated to a solid content of 50% Methane triacrylate (Shin Nakamura Chemical) 3.9 parts, photoinitiator IRGACURE907 (Nippon Ciba-Geigy) 0.8 parts, surfactant dimethylpolysiloxane-polyoxyalkylene copolymer (Toray Dow Corning) 0.2 parts, lactic acid 74.8 parts of ethyl was mixed to obtain a composition (A). The obtained composition (A) was filtered through a 0.5 μm filter (grade: DISMIC-25JP, manufactured by PTFE, ADVANTEC).

(2) Production of microlens array Hexamethyldisilazane (HMDS) was dropped onto a silicon wafer and applied using a spin coater (1H-360S, manufactured by Mikasa) at 300 rpm for 5 seconds and then at 2000 rpm for 60 seconds. The substrate was heated on a hot plate for 60 seconds to obtain a HMDS-treated silicon wafer. The composition (A) produced in (1) above was dropped onto this HMDS-treated silicon wafer, and spin coating was applied at 300 rpm for 5 seconds and then at 2000 rpm for 60 seconds. When the coating film of the composition was measured with a stylus film thickness meter, the film thickness was 0.2 to 0.3 μm. This substrate was heated on a hot plate at 80 ° C. for 60 seconds and exposed at 100 mJ / cm ² (high pressure Hg lamp, measurement wavelength 365 nm) using a mask aligner PLA-501F (manufactured by Canon). This was immersed in a 50-fold diluted solution of alkali developer CD200CR (manufactured by JSR Corporation) for 30 seconds, and then washed with pure water.

Example 2
(1) Production of composition (B) 34.0 parts of tetramethylol obtained by concentrating the SiO ₂ coated TiO ₂ dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .; the particles (1)) to a solid concentration of 50%. Methane triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) 6.5 parts, IRGACURE 907 (manufactured by Ciba Geigy Japan, photoinitiator) 1.3 parts, dimethylpolysiloxane-polyoxyalkylene copolymer (manufactured by Toray Dow Corning, silicon) Nonionic surfactant) 0.3 part and ethyl lactate 58.0 parts were mixed to obtain a composition (B). This was filtered through a 0.5 μm filter (grade: DISMIC-25JP, manufactured by PTFE, ADVANTEC) to obtain a composition (B).

(2) Production of microlens array A microlens array was produced in the same manner as in Example 1 except that the composition (B) was used. It was 0.7-0.8 micrometer when the film thickness of the coating film of the composition was measured with the stylus-type film thickness meter.

Production Example 1
(Production of an organic compound having a polymerizable unsaturated group)
To a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air, 222 parts of isophorone diisocyanate was added dropwise over 1 hour at 50 ° C. with stirring, followed by heating and stirring at 70 ° C. for 3 hours. This consists of NK ester A-TMM-3LM-N (60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd. Among them, the one involved in the reaction is pentaerythritol having a hydroxyl group. 549 parts were added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 10 hours to obtain an organic compound (Ab) containing a polymerizable unsaturated group. When the residual isocyanate content in the product was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. Infrared absorption spectrum of the product disappeared absorption peaks characteristic 2260 cm ^-1 to the absorption peak and the raw material isocyanate compounds characteristic 2550 cm ^-1 mercapto group in the raw material, new urethane bond and S (C = O) NH- peaks characteristic 1720 cm ^-1 to a peak and an acryloxy group of characteristic 1660 cm ^-1 based on observed, acryloxy group and -S (C = O as a polymerization unsaturated group) NH-, It was shown that an acryloxy group-modified alkoxysilane having a urethane bond was formed. As a result, 773 parts of the compound represented by the formula (12) was obtained, and 220 parts of pentaerythritol tetraacrylate which was not involved in the reaction were mixed.

Production Example 2: Preparation of Reactive Particle Dispersion 3.9 parts of the composition produced in Production Example 1, SiO ₂ -coated TiO ₂ particle dispersion (particulate solid concentration 27.0 wt%, manufactured by Catalyst Kasei Co., Ltd.) A mixed liquid of 95.5 parts of the particle (1), 0.05 parts of ion exchange water, 0.01 part of sulfuric acid and 0.01 part of p-hydroxyphenyl monomethyl ether was stirred and dissolved. After stirring at 60 ° C. for 4 hours, 0.6 parts of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a dispersion of reactive particles. The solid content concentration of this dispersion was calculated to be 29.5% by weight.

Example 3
(1) Production of composition (C) 25.5 parts of the reactive SiO ₂ -coated TiO ₂ dispersion produced by Production Example 2 (catalyst chemical industry Co., Ltd.) concentrated to 50% solids concentration, Tetramethylol methane triacrylate (1.4 parts made by Shin-Nakamura Chemical Co., Ltd., IRGACURE907 (made by Ciba Geigy Japan, photoinitiator) 0.8 parts, dimethylpolysiloxane-polyoxyalkylene copolymer (made by Toray Dow Corning, silicon) 0.2 part of nonionic surfactant) and 72.3 parts of ethyl lactate were mixed and filtered through a 0.5 μm filter (grade: DISMIC-25JP, manufactured by PTFE, ADVANTEC), and composition (C) was obtained. Obtained.

(2) Production of microlens array A macrolens array was produced in the same manner as in Example 1 except that the composition (C) was used. It was 0.2-0.3 micrometer when the film thickness of the coating film of the composition was measured with the stylus-type film thickness meter.

Example 4
(1) Production of composition (D) 42.5 parts obtained by concentrating the reactive SiO ₂ -coated TiO ₂ dispersion produced in Production Example 2 (catalyst conversion industry Co., Ltd.) to a solid content of 50%, Tetramethylol methane triacrylate (2.3 parts manufactured by Shin-Nakamura Chemical Co., Ltd., IRGACUR907 (manufactured by Nippon Ciba Geigy Co., photoinitiator) 1.3 parts, dimethylpolysiloxane-polyoxyalkylene copolymer (manufactured by Toray Dow Corning Co., Ltd., silicon) 0.3 part of nonionic surfactant) and 53.8 parts of ethyl lactate were mixed and filtered through a 0.5 μm filter (grade: DISMIC-25JP, manufactured by PTFE, ADVANTEC) to obtain the composition (D). Obtained.

(2) Production of microlens array A microlens array was produced in the same manner as in Example 1 except that the composition (D) was used. It was 0.7-0.8 micrometer when the film thickness of the coating film of the composition was measured with the stylus type film thickness meter.

Comparative Examples 1 and 2
Compositions (E) and (F) were produced in the same manner as in Example 1 (1) except that the particles used were changed to particles (2) and (3), respectively. Using these compositions, a coating film was formed in the same manner as in Example 1 (2), exposed, immersed in an alkaline developer, and washed with pure water.

  The following characteristics were evaluated for the compositions (A) to (F) obtained in Examples 1 to 4 and Comparative Examples 1 and 2.

(1) Patternability of composition Each composition was spin-coated on a silicon wafer treated with HMDS (300 rpm for 10 seconds, then 2000 rpm for 60 seconds), heated on a hot plate at 80 ° C., and mask aligner PLA- Using 501F (manufactured by Canon), exposure was performed at 365 nm (the light source was a high-pressure mercury lamp) with an irradiation light amount of 100 mJ / cm ² . It was immersed in a 50-fold diluted solution (alkali component concentration 0.05% by weight) of an alkali developer CD-200CR (manufactured by JSR Corporation) for 30 seconds and rinsed with pure water. Whether or not a desired pattern was formed was confirmed with an optical microscope and evaluated according to the following criteria. The obtained results are shown in Table 3.
○: A pattern of Line / Space = 1/4 (Line = 60 μm, Space = 240 μm) is formed. ×: The unexposed part is not dissolved and the pattern is not formed even after immersion in an alkali developer.

(2) Refractive index Each composition was filtered with a 0.5 μm filter, applied onto a silicon wafer, and cured with an aligner PLA-501F (manufactured by Canon). The obtained coating film was measured at 23 ° C. using an n & k Analyzer (manufactured by n & k Technology, USA) and analyzed to obtain a refractive index. The obtained results are shown in Table 3.

The composition for a solid-state imaging device of the present invention is useful as a material for a member that requires a high refractive index in a solid-state imaging device, particularly as a microlens material.
According to the method for manufacturing a microlens array of the present invention, it is possible to easily manufacture a microlens array with high accuracy.

Claims (13)

The following components (A) to (D):
(A) When the total amount of metal atoms present on the particle surface is 100 atomic%, the ratio of silicon atoms present on the particle surface is 20 atomic% or more. (B) Two or more (meth) acryloyl groups A composition for a solid-state imaging device comprising a compound (C) having a photopolymerization initiator (D) and an organic solvent.   2. The composition for a solid-state imaging device according to claim 1, wherein the particle size of the particle (A) is 3 to 100 nm and the refractive index is 1.70 or more.   3. The solid-state imaging device according to claim 1, wherein the particles of (A) are particles mainly composed of a metal oxide selected from the group consisting of titania, alumina, and zirconia, and silicon dioxide is present on the surface. Composition.   The composition for a solid-state imaging device according to any one of claims 1 to 3, wherein the particles (A) are particles having a polymerizable unsaturated group. The composition for a solid-state imaging device according to claim 4, wherein the polymerizable unsaturated group contained in the particles (A) is a group including a structure represented by the following formula (11).

[In the formula (11), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]   The compound (B) having two or more (meth) acryloyl groups is a compound having three or more (meth) acryloyl groups. 6. Composition.   The said (D) organic solvent is an organic solvent which has a boiling point of 120 degreeC or more, The composition for solid-state image sensors of any one of Claims 1-6.   The composition for a solid-state imaging device according to claim 7, wherein the organic solvent (D) is at least one selected from the group consisting of ethyl lactate, γ-butyrolactone, and N-methylpyrrolidone.   Furthermore, the composition for solid-state image sensors of any one of Claims 1-6 containing (E) surfactant.   The composition for a solid-state imaging device according to claim 9, wherein the surfactant (E) is selected from nonionic surfactants containing fluorine, silicon, or both.   The composition for a solid-state imaging device according to any one of claims 1 to 10, which is used for forming a surface lens, an in-layer lens or a high refractive index layer of a solid-state imaging device.   Applying the composition for solid-state image sensors of any one of Claims 1-10 on a base material, exposing it to pattern formation, immersing it in an alkali developing solution, and then washing with water. A method of manufacturing a lens array. The method for producing a microlens array according to claim 12, wherein the concentration of the alkali component in the alkali developer is in the range of 0.01 to 5% by weight.