WO2016017526A1 - Lens-array member, manufacturing method therefor, lens unit, manufacturing method therefor, camera module, manufacturing method therefor, and manufacturing kit for lens-array member - Google Patents

Abstract

A method for manufacturing a lens-array member, said method having a step in which a hardening accelerator is applied to a bumpy lens-array surface, a step in which a transparent resin is applied to the lens-array surface to which the hardening accelerator has been applied, a step in which the part of the resulting transparent-resin film that contacts the hardening accelerator and the vicinity thereof are cured, and a step in which the transparent resin that was not cured is removed.

Description

Lens array member and manufacturing method thereof, lens unit and manufacturing method thereof, camera module and manufacturing method thereof, lens array member manufacturing kit

The present invention relates to a lens array member and a manufacturing method thereof, a lens unit and a manufacturing method thereof, a camera module and a manufacturing method thereof, and a lens array member manufacturing kit.

Recently, there are a wide variety of optical devices, many of which have an antireflection low refractive index film on the surface of the optical mechanism. The optical mechanism is not limited to a flat surface shape, and examples thereof include a brightness enhancement lens and a diffusion lens of a backlight for liquid crystal, a Fresnel lens, a lenticular lens, and a microlens used for a screen of a video projection television. In such a device, a desired geometrical optical performance is obtained mainly by forming a fine structure with a resin material.
In particular, research and development relating to the material and structure of the microlens unit used in the solid-state imaging device has been energetically advanced (see, for example, Patent Documents 1 to 3). As the background, the miniaturization of the camera module is progressing, and there is a demand for higher performance for realizing efficient light collection. Particularly in recent years, the size of one pixel has become extremely small as the number of pixels increases. In addition, since a larger number of devices are manufactured in one manufacturing process, the size of the wafer used is also increased. Under such circumstances, improvement of manufacturing quality and product quality of the microlens unit is becoming more important.

JP 2006-186295 A JP 2006-98985 A JP 2007-119744 A JP 2013-131613 A

The microlens unit has a structure in which a large number of microlenses are arranged in a planar shape, and irregularities are formed on the surface thereof. When a low refractive index film is applied thereon, if a vapor deposition method or a deposition method is used (see, for example, Patent Document 4), a thin and uniform low refractive index film along the surface irregularities can be formed. On the other hand, when the coating method is used, a liquid pool is formed in the concave portion, and it is difficult to form a thin film along the concave and convex portions of the lens array. That is, it becomes a low refractive index film having a planar surface, and the optical path length to the microlens below is different between the convex part and the concave part of the lens array. When the thickness of the low refractive index film becomes non-uniform as described above, the reflection characteristics become uneven, and flare and ghost cannot be sufficiently reduced. On the other hand, if the vapor deposition method or the deposition method can be switched to the coating method, it is possible to achieve a significant reduction in manufacturing equipment and manufacturing processes, and a technique for realizing this is desired.

An object of the present invention is to provide a method for manufacturing a lens array member, which can form a transparent resin film substantially corresponding to the shape of the surface of an uneven lens array by a coating method. It is another object of the present invention to provide a lens array member, a lens unit and a manufacturing method thereof using the manufacturing method, a camera module and a manufacturing method thereof, and a manufacturing kit of the lens array member used in the manufacturing method.

The above problems have been solved by the following means.
[1] A step of applying a curing accelerator to the lens array surface having irregularities;
A step of applying a transparent resin to the surface of the lens array provided with a curing accelerator;
Curing the portion in contact with the curing accelerator for the transparent resin coating film;
A process for removing an uncured transparent resin.
[2] The method of manufacturing a lens array member according to [1], wherein the surface shape of the cured transparent resin coating film corresponds to the uneven shape of the underlying lens array.
[3] The method for producing a lens array member according to [1] or [2], wherein the curing accelerator is a silane coupling agent.
[4] The method for producing a lens array member according to any one of [1] to [3], wherein the transparent resin contains hollow particles, non-hollow particles, porous particles, or beaded particles.
[5] The method for manufacturing a lens array member according to any one of [1] to [4], wherein the lenses constituting the lens array are made of resin.
[6] The method for producing a lens array member according to [5], wherein the resin constituting the lens is a silicone resin, an acrylic resin, a novolac resin, an epoxy resin, a sulfide resin, or a thiourethane resin.
[7] The lens array according to any one of [1] to [6], wherein the lens array has a structure in which a plurality of convex lenses having a spherical surface are arranged with their protruding directions oriented in the same direction. Manufacturing method of member.
[8] The lens array according to any one of [1] to [7], wherein the unevenness of the lens array is a continuous shape of a spherical convex portion and a V-shaped concave portion formed by a reverse arc. Manufacturing method of member.
[9] The method for manufacturing a lens array member according to any one of [1] to [8], wherein the transparent resin is a siloxane resin or a fluororesin.
[10] Curing of the transparent resin coating film is performed (i) by standing at room temperature, (ii) performed by heating, or (iii) performed by irradiation with light [1] to [9] The manufacturing method of the lens array member as described in any one of these.
[11] The curing accelerator is a silane coupling agent, and the silane coupling agent is an alkoxysilane compound having an amino group, an alkoxysilane compound having a glycidyl group, an alkoxysilane compound having an acryloyl group, or an alkoxy having a thiol group. The method for producing a lens array member according to any one of [3] to [10], which is a silane compound, an alkoxysilane compound having a vinyl group, an alkoxysilane compound having a succinimide group, or an alkoxysilane compound having a maleimide group .
[12] Silane coupling agent is γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyldimethoxy Methylsilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- (meth) acryloxypropyltrialkoxysilane, γ- (meth) acryloxypropylalkyldialkoxysilane, The method for producing a lens array member according to [11], which is γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, or vinyltrialkoxysilane. .
[13] The method for manufacturing a lens array member according to any one of [1] to [12], wherein at least one of an organic solvent and an alkaline liquid is used for removing the uncured transparent resin.
[14] A lens array member having a transparent resin film on an uneven lens array surface, the transparent resin film being composed of a siloxane resin coating cured film, with the silane coupling agent applied to the lens array surface interposed A lens array member in which the siloxane resin is cured.
[15] The lens array member according to [14], wherein the surface shape of the cured transparent resin film corresponds to the uneven shape of the underlying lens array.
[16] The difference between the thickness Tt of the transparent resin film in the convex portion of the lens array and the thickness Tv of the transparent resin film in the concave portion of the lens array is 0.07 μm or less. [14] or [15] Lens array member.
[17] A lens unit manufacturing method for manufacturing a lens unit through the manufacturing method according to any one of [1] to [13].
[18] A method for manufacturing a camera module, in which the lens unit manufactured by the manufacturing method according to [17] is incorporated into a camera module.
[19] A lens unit incorporating the lens array member according to any one of [14] to [16].
[20] A camera module incorporating the lens unit according to [19].
[21] A kit for forming a transparent resin film on the surface of a lens array through the production method according to any one of [1] to [13],
A kit for manufacturing a lens array member, comprising: a curing accelerator for imparting to the lens array surface; and a transparent resin for imparting to the lens array surface to which the curing accelerator is imparted.

According to the production method of the present invention, a transparent resin film corresponding to the shape of the surface can be formed on a concavo-convex lens array by a coating method. Thereby, compared with what uses the precipitation method or a vapor deposition method, manufacturing efficiency can be improved and the burden on manufacturing equipment and manufacturing cost can be reduced. In addition, the lens array member, the lens unit, and the camera module using this manufacturing method can realize high quality and high performance. Moreover, the manufacturing kit of the lens array member of the present invention can be suitably used for the above manufacturing method.

The above and other features and advantages of the present invention will become more apparent from the following description and accompanying drawings.

It is member sectional drawing which shows typically the manufacturing process of the lens array member which concerns on one Embodiment of this invention. It is a microscope image (drawing substitute photograph) of the lens array member produced in the Example. It is member sectional drawing which shows the manufacturing process of a lens array typically.

In the production method of the present invention, a step of applying a curing accelerator to the surface of the lens array having irregularities (step 1) and a step of applying a transparent resin on the lens array to which the curing accelerator has been applied (step 2). And the step (step 3) of curing the portion (and the vicinity thereof) in contact with the curing accelerator with respect to the transparent resin film, and the step of removing the uncured transparent resin (step 4). A member is manufactured. The vicinity thereof means a transparent resin on the side in contact with the curing accelerator in a state where an uncured transparent resin is left. Hereinafter, the present invention will be described in detail focusing on preferred embodiments thereof with reference to the drawings. In the present invention, the steps are not limited to being carried out successively in the order of the above steps 1 to 4, and can be carried out by interposing other steps as appropriate.

<Manufacture of lens array members>
(Process 1)
In this step, a curing accelerator is applied (preferably applied) to the surface of the lens array (FIGS. 1A and 1B). As the lens array 2A, what is usually applied to this type of product can be used as appropriate. For example, a lens obtained by curing a lens forming material (dispersion composition (I) or the like) described later can be suitably used. The lens array 2 </ b> A has a configuration in which the lenses 2, 2, 2... Are arranged on the substrate 1. The lens 2 has a hemispherical shape. All the lenses 2 are arranged with the protruding direction (the apex of the spherical surface) directed in the same direction (upward in the figure). This protruding direction (upward) is the light incident direction when a lens unit or a camera module is formed.
As described above, in the lens array 2A, a large number of lenses 2 protruding in a spherical shape are arranged adjacent to each other. Protruding into a spherical shape also includes a continuous curved surface in which the spherical surface is convex from the base. Therefore, unevenness occurs in the arrangement plane. Specifically, the spherical protrusion 2a at the center of the lens 2 forms a convex portion, and the valley 2b between the lenses forms a concave portion. Since the concave portion is formed at the end of the spherical surface, the concave portion forms a V-shaped space having a reverse arc in the cross section. Since they are arranged on a plane, depending on the direction, the lenses 2 may not be adjacent to each other and may be slightly separated. In such a place, it becomes a reverse arc-shaped wall portion, and a bottom portion becomes a mortar-shaped space constituted by the substrate surface. V-shaped means to include this mortar-shaped form. Details will be described later. That is, it is an advantage of the present invention that a liquid pool of a transparent resin material is not formed in the concave portion, and a cured film having an excessive thickness is not formed in this portion.

In this step, the curing accelerator 3 is further applied (applied) to the surface 2Aa of the lens array 2A (FIG. 1B). Specific materials for the curing accelerator 3 will be described later. The method for applying the curing accelerator 3 is not particularly limited, and examples thereof include a treatment for applying a solution of the curing accelerator 3. It is preferable that the curing accelerator 3 is applied thinly and uniformly. Also at this time, it is preferable not to cause a liquid pool or the like in the concave portion of the lens array 2A. From such a viewpoint, it is preferable to apply a curing accelerator by spin coating or spraying.
The surface of the lens array is preferably subjected to an oxygen ashing treatment or an ultraviolet irradiation treatment as a surface modification pretreatment so that the curing accelerator can be easily applied.

(Process 2)
In this step, the transparent resin 4 is applied on the coating film of the curing accelerator. As the transparent resin 4, a siloxane resin or a fluororesin described later can be suitably used. The method for applying the transparent resin 4 onto the lens array 2A to which the curing accelerator 3 is applied is not particularly limited, and examples thereof include a treatment by coating. In this specification, the application includes treatments such as dropping a solution, flowing down, and spraying. In addition, as an application mode, a spin coating method, a dip coating method, a roller blade method, a spray method, or the like can be applied. In applying the transparent resin 4, it is preferable to apply an excessive amount of resin so that a sufficient film thickness can be realized when a cured film is formed. FIG. 2C schematically shows the form. In the present invention, applying a liquid material to a predetermined location is called coating, and the above-described methods are included in the concept.
It is preferable that the solution of the transparent resin 4 has an appropriate viscosity so that an excessive amount of resin is applied onto the lens array 2A. The application method is not particularly limited, but a spin coating method and a spray method are particularly preferable in order to obtain a sufficient thickness.

(Process 3)
In this step, the portion of the transparent resin 4 that is in contact with the curing accelerator 3 and the vicinity thereof are cured. In this curing step, any treatment may be applied as long as the resin can be cured. For example, (i) standing at room temperature, (ii) heating, (iii) light And so on. The heating temperature in the case of heating should just be set according to restrictions of resin and other members, etc., preferably 50 ° C. or higher, more preferably 65 ° C. or higher, and 70 ° C. or higher. Is particularly preferred. As an upper limit of heating temperature, it is preferable that it is 200 degrees C or less, It is more preferable that it is 150 degrees C or less, It is especially preferable that it is 120 degrees C or less. Although the said hardening time is not specifically limited, It is preferable that it is 0.5 to 60 minutes, and it is more preferable that it is 1 to 10 minutes.
The heating method is not particularly limited, and heating can be performed with a hot plate, an oven, a furnace, or the like.
The atmosphere during heating is not particularly limited, and an inert atmosphere, an oxidizing atmosphere, or the like can be applied. The inert atmosphere can be realized by an inert gas such as nitrogen, helium, or argon. The oxidizing atmosphere can be realized by a mixed gas of these inert gas and oxidizing gas, or air may be used. Examples of the oxidizing gas include oxygen, carbon monoxide, and oxygen dinitride. The heating step can be performed under pressure, normal pressure, reduced pressure, or vacuum.
At this time, in this step, the portion of the imparted transparent resin 4 that is in contact with the curing accelerator and the vicinity thereof are cured. FIGS. 1C and 1D show changes in the shape at this time, and the transparent resin 4 on the lens array 2A has a cured transparent resin film (cured film) 41 and an uncured film after the curing process. A transparent resin film (uncured film) 42 is formed. In other words, in this step, it is preferable that the transparent resin 4 is not cured as a whole. In particular, when a silane coupling agent is used as the curing accelerator 3 and a siloxane resin or a fluororesin is used as the transparent resin 4 in order to bring out the curing by the curing accelerator 3, the above heat treatment is preferable. By setting the temperature and time appropriately within the above range, a cured film having a desired thickness can be obtained.

(Process 4)
In this step, the uncured transparent resin is removed. As described above, the transparent resin 4 provided on the lens array 2A has an uncured portion and a cured portion. The uncured transparent resin film 42 is removed. This removal method may be any method, for example, treating the uncured transparent resin film 42 with a solvent that does not dissolve the cured transparent resin film 41. Specific examples of the solvent that can be suitably used include those listed below as the solvent for dissolving the transparent resin (organic solvent (A)) and alkaline developers.
The substrate from which the uncured resin has been removed in this manner is configured as a lens array member 10 to which the lens array 2A and a transparent resin film 41 cured thereon are applied via the curing accelerator 3. The lens array member 10 is a member having the lens array 2A and the cured transparent resin film 41, and is used in a sense that an arbitrary member such as one formed on the substrate 1 can be included.

As the alkaline developer, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass is suitable. Alkaline compounds include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium Examples thereof include hydroxide, tetrabutylammonium hydroxy, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like. Of these, organic alkali is preferred. In the case where an alkaline aqueous solution is used as a developer, a washing treatment with water is generally performed after development. Among these developers, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide (TMAH) or choline is more preferable.

In the present embodiment, the thickness of the transparent resin film can be made uniform through the above steps. A preferable range of this thickness will be described in detail later.
Note that the attached drawings used in the above description are exaggerated or schematically illustrated members and preparations, and the present invention is not construed as being limited thereto.

<Coating liquid for curing accelerator>
The curing accelerator is not particularly limited as long as it accelerates the curing of the transparent resin, and examples thereof include a silane coupling agent.
As the silane coupling agent, those commonly used can be suitably used. For example, an alkoxysilane compound having an amino group, an alkoxysilane compound having a glycidyl group, an alkoxysilane compound having an acryloyl group, an alkoxysilane compound having a thiol group, an alkoxysilane compound having a vinyl group, an alkoxysilane compound having a succinimide group, Examples thereof include alkoxysilane compounds having a maleimide group. The silane coupling agent preferably has 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and particularly preferably 4 to 12 carbon atoms. The curing accelerator is more preferably represented by the following formula (X).

(R ^x1 ) _a Si (R ^x2 ) _4-a (X)

R ^x1 is a substituent T described later, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms). More preferably 2 to 6 carbon atoms, particularly preferably 2 to 3 carbon atoms), an aryl group (preferably 6 to 24 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably 6 to 10 carbon atoms), An alkoxy group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, particularly preferably having 1 to 3 carbon atoms), an aryloxy group (preferably having 6 to 24 carbon atoms, more preferably having 6 to 14 carbon atoms) An aralkyloxy group (preferably 7 to 25 carbon atoms, more preferably 7 to 15 carbon atoms, particularly preferably 7 to 11 carbon atoms), an acyl group (2 to 12 carbon atoms). Is preferred More preferably 2 to 6 carbon atoms, and particularly preferably 2 to 3 carbon atoms). R ^x1 preferably contains at least one alkoxy group, aryloxy group, or aralkyloxy group, and more preferably contains at least one alkoxy group.
R ^x2 is a functional organic group, and examples thereof include amino group-containing groups, glycidyl group-containing groups, acryloyl group-containing groups, thiol group-containing groups, vinyl group-containing groups, succinimide group-containing groups, and maleimide group-containing groups. The number of carbon atoms in R ^x2 is preferably 0 to 24, more preferably 0 to 12, and particularly preferably 0 to 8.
a is an integer of 1 to 3.
Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, γ -Glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- (meth) acryloxypropyltrialkoxysilane, γ- (meth) acryloxypropylalkyldialkoxysilane, γ-chloropropyl Examples include trialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, and vinyltrialkoxysilane.
A silane coupling agent can be used individually by 1 type or in combination of 2 or more types.
In the present specification, the term “acryl” or “acryloyl” broadly refers to not only an acryloyl group but also a derivative structure thereof, and includes a structure having a specific substituent at the α-position of the acryloyl group. However, in a narrow sense, the case where the α-position is a hydrogen atom may be referred to as acryl or acryloyl. Those having a methyl group at the α-position are referred to as methacryl, which means either acryl (the α-position is a hydrogen atom) or methacryl (the α-position is a methyl group), and is sometimes referred to as (meth) acryl.

・ Organic solvent (A)
The silane coupling agent is preferably used after being dissolved in an organic solvent.
Examples of the organic solvent include aliphatic compounds, halogenated hydrocarbon compounds, alcohol compounds, ether compounds, ester compounds, ketone compounds, nitrile compounds, amide compounds, sulfoxide compounds, and aromatic compounds. These solvents are mixed. May be used. Examples of each are listed below.
・ As aliphatic compounds,
Examples include hexane, heptane, cyclohexane, methylcyclohexane, octane, pentane, and cyclopentane.
・ As halogenated hydrocarbon compounds,
Methylene chloride, chloroform, dichloromethane, ethane dichloride, carbon tetrachloride, trichloroethylene, tetrachloroethylene, epichlorohydrin, monochlorobenzene, orthodichlorobenzene, allyl chloride, hydrochlorofluorocarbon (HCFC), methyl monochloroacetate, ethyl monochloroacetate, monochloroacetic acid Examples include trichloroacetic acid, methyl bromide, methyl iodide, and tri (tetra) chloroethyl.
・ As alcohol compounds,
Methyl alcohol, ethyl alcohol, 1-propyl alcohol, 2-propyl alcohol, 2-butanol, ethylene glycol, propylene glycol, glycerin, 1,6-hexanediol, cyclohexanediol, sorbitol, xylitol, 2-methyl-2,4- Examples include pentanediol, 1,3-butanediol, and 1,4-butanediol.
・ As ether compounds (including hydroxyl group-containing ether compounds)
Dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, cyclohexyl methyl ether, anisole, tetrahydrofuran, alkylene glycol alkyl ether (ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, propylene glycol monomethyl ether) , Diethylene glycol monomethyl ether, triethylene glycol, polyethylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, etc.) And the like.
・ As ester compounds,
Examples include ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate, propylene glycol 1-monomethyl ether 2-acetate and the like.
・ As ketone compounds,
Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, and cyclopentanone.
・ As nitrile compounds,
Examples include acetonitrile.
・ As amide compounds,
N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N-methylformamide, acetamide, N- Examples include methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.
・ As sulfoxide compounds,
Examples thereof include dimethyl sulfoxide.
・ As aromatic compounds,
Examples include benzene and toluene.

Of these, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, and cyclohexanone are preferable.

Although the density | concentration in the coating liquid of a hardening accelerator is not specifically limited, It is preferable that it is 0.01 mass% or more, and it is more preferable that it is 0.1 mass% or more. The upper limit of this concentration is preferably 5% by mass or less, and more preferably 1% by mass or less.
An organic solvent can be used individually by 1 type or in combination of 2 or more types.
In addition, the organic solvent illustrated above is called an organic solvent (A) in this specification.

<Transparent resin coating solution>
The transparent resin coating solution preferably contains a resin exhibiting a predetermined light transmittance when a cured film is formed. In particular, the transparent resin is preferably a siloxane resin or a fluororesin. In addition, the coating liquid of the transparent resin may contain hollow particles or non-hollow particles and a surfactant. Note that developability may be imparted to the transparent resin.

(Siloxane resin)
The siloxane resin can be obtained through a hydrolysis reaction and a condensation reaction using an alkoxysilane compound described later. More specifically, some or all of the alkoxy groups of the alkyltrialkoxysilane are hydrolyzed and converted into silanol groups, and at least some of the generated silanol groups are condensed to form Si—O—Si bonds. Things can be said. The siloxane resin may be a siloxane resin having any silsesquioxane structure such as a cage type, a ladder type, or a random type. The “cage type”, “ladder type”, and “random type” refer to the structure described in, for example, “Chemistry and application development of silsesquioxane materials” (CMC Publishing). it can.
-Silsesquioxane structure It is preferable that the siloxane resin of this embodiment has the silsesquioxane structure represented by following formula (1).
-(R ¹ SiO _3/2 ) _n -Formula (1)
In the above formula (1), R ¹ represents an alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. n is 10 to 10,000, preferably an integer of 20 to 1,000.
The alkyl group represented by R ¹ is not particularly limited as long as the carbon number is within the above range, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Of these, a methyl group and an ethyl group are preferable, and a methyl group is most preferable. R ¹ may have a substituent T, and examples of the optional substituent include a glycidyloxy group and a fluoroalkyl group having a fluorine atom.

In the present invention, unless otherwise specified, a silicon-containing polymer whose main chain is composed of siloxane bonds is called a polysiloxane or a siloxane resin. Since silicon has four bonds, the basic structural unit of polysiloxane is classified according to the number of organic groups typified by methyl and phenyl groups per silicon atom. It can be divided into two. In the following formula, R is an organic group.

In the present invention, silsesquioxane means a general term for polysiloxanes whose basic structural units are T units unless otherwise specified. Since silicon in silsesquioxane is bonded to three oxygens and oxygen is bonded to two silicons, the theoretical composition is RSiO _3/2 (the Latin word for three-half is "Sesquix (SESQUI) "). In the present embodiment, it is preferable that R in the formula of the T unit is the R ¹ and the silsesquioxane structure site is included at the specific content.

The siloxane resin of the present embodiment preferably has 50 to 100% by mass of the silsesquioxane structure. This ratio is preferably 80% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, and most preferably substantially 100% by mass. However, even in the case of 100% by mass, other components such as inevitable impurities may be contained within a range that does not impair the desired effect. In addition, the siloxane resin of this embodiment may contain the specific polysilsesquioxane structure individually by 1 type, or may contain 2 or more types.

-Alkyltrialkoxysilane It is preferable that the siloxane resin of this embodiment is a hydrolysis-condensation product obtained by hydrolytic condensation of alkyltrialkoxysilane. In order to produce the hydrolysis condensate in this embodiment, an alkoxysilane compound containing an alkyltrialkoxysilane can be used as a starting material. In addition, an alkoxysilane compound intends the starting material comprised from alkoxysilane (silicon compound which has an alkoxy group).
An alkyltrialkoxysilane is an organosilicon compound in which one alkyl group and three alkoxy groups are bonded to a silicon atom, and can be represented by the following formula (2).
Formula (2): R ² Si (OR ³ ) ₃
R ² represents an alkyl group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. R ³ represents an alkyl group.
The alkyl group of alkyltrialkoxysilane (R ² in formula (2)) is not particularly limited as long as it has a carbon number of 1 to 3, but is preferably a methyl group or an ethyl group, and most preferably a methyl group. . R ² may have a substituent T, and examples of the optional substituent include a glycidyloxy group and a fluoroalkyl group having a fluorine atom.

The alkoxy group of the alkyltrialkoxysilane is not particularly limited, and examples thereof include a methoxy group and an ethoxy group. More specifically, R ³ in the formula (2) is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. Of these, a carbon number of 1 to 10 is preferable, and a carbon number of 1 to 4 is more preferable. In particular, an ethoxy group in which R ³ in the formula (2) is an ethyl group is preferable because the hydrolysis rate can be easily controlled. R ³ may have a substituent T.

Examples of the alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and γ-glycidoxypropyl. Examples include trimethoxysilane and trifluoropropyltrimethoxysilane. Of these, methyltriethoxysilane and ethyltriethoxysilane are preferably used, and methyltriethoxysilane is most preferably used. In addition, as alkyl trialkoxysilane, only 1 type may be used and 2 or more types may be used together.

65% by mass or more of the alkoxysilane compound is preferably alkyltrialkoxysilane, more preferably 80% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less.

Tetraalkoxysilane In addition to the trialkoxysilane, other alkoxysilanes can be used as the alkoxysilane compound, and tetraalkoxysilane is particularly preferable.
Tetraalkoxysilane is an organosilicon compound in which four alkoxy groups are bonded to a silicon atom, and can be represented by the following formula (3).
Formula (3): Si (OR ⁴ ) ₄
R ⁴ each independently represents an alkyl group.
The alkoxy group of tetraalkoxysilane is not particularly limited, and examples thereof include a methoxy group and an ethoxy group. More specifically, R ⁴ in formula (3) is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. Of these, a carbon number of 1 to 10 is preferable, and a carbon number of 1 to 4 is more preferable. In particular, an ethoxy group in which R ⁴ in the formula (3) is an ethyl group is preferable because the hydrolysis rate can be easily controlled. R ⁴ may have a substituent T.
Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-tert-butoxysilane, and the like. . Of these, tetramethoxysilane and tetraethoxysilane are preferably used.
In addition, as tetraalkoxysilane, only 1 type may be used and 2 or more types may be used together.

The content of tetraalkoxysilane in the alkoxysilane compound is not particularly limited, but is preferably 35% by mass or less, and more preferably 20% by mass or less. There is no particular lower limit, and in order to obtain the effect of adding tetraalkoxysilane, it is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more.

In addition, in this specification, it uses for the meaning containing the salt and its ion other than the said compound itself about the display of a compound (For example, when attaching | subjecting and attaching | subjecting a compound and an end). In addition, it is meant to include derivatives in which a part thereof is changed, such as introduction of a substituent, within a range where a desired effect is exhibited.
In the present specification, a substituent that does not specify substitution / non-substitution (the same applies to a linking group) means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution. Preferred substituents include the following substituent T.
Examples of the substituent T include the following.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl group (Preferably an alkenyl group having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.), cycloalkyl group (Preferably a cycloalkyl group having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms such as phenyl, 1-naphthyl, etc. 4-methoxyphenyl, 2-chlorophenyl, -Methylphenyl, etc.), a heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, preferably a 5- or 6-membered heterocyclic group having at least one oxygen atom, sulfur atom, nitrogen atom, for example 2 -Pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy Etc.), an aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms, such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), an alkoxycarbonyl group (preferably having a carbon number of 2 to 20 alkoxycarbonyl groups such as ethoxycarbonyl, 2-ethyl Xyloxycarbonyl, etc.), aryloxycarbonyl groups (preferably aryloxycarbonyl groups having 6 to 26 carbon atoms, such as phenoxycarbonyl, 1-naphthyloxycarbonyl, 3-methylphenoxycarbonyl, 4-methoxyphenoxycarbonyl, etc.), amino A group (preferably containing an amino group having 0 to 20 carbon atoms, an alkylamino group, an arylamino group, such as amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfamoyl A group (preferably a sulfamoyl group having 0 to 20 carbon atoms such as N, N-dimethylsulfamoyl, N-phenylsulfamoyl etc.), an acyl group (preferably an acyl group having 1 to 20 carbon atoms such as acetyl , Propionyl, butyryl, etc.), aryloyl group ( Preferably an aryloyl group having 7 to 23 carbon atoms, such as benzoyl, an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy), an aryloyloxy group (preferably having 7 to 23 carbon atoms). Aryloyloxy groups such as benzoyloxy, etc., carbamoyl groups (preferably carbamoyl groups having 1 to 20 carbon atoms such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl etc.), acylamino groups (preferably carbon atoms) 1-20 acylamino groups such as acetylamino and benzoylamino), alkylthio groups (preferably alkylthio groups having 1 to 20 carbon atoms such as methylthio, ethylthio, isopropylthio, benzylthio and the like), arylthio groups (preferably carbon An arylthio group of the number 6 to 26, For example, phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio, etc.), alkylsulfonyl groups (preferably alkylsulfonyl groups having 1 to 20 carbon atoms, such as methylsulfonyl, ethylsulfonyl, etc.), arylsulfonyl A group (preferably an arylsulfonyl group having 6 to 22 carbon atoms, such as benzenesulfonyl), an alkylsilyl group (preferably an alkylsilyl group having 1 to 20 carbon atoms, such as monomethylsilyl, dimethylsilyl, trimethylsilyl, triethylsilyl, etc. ), An arylsilyl group (preferably an arylsilyl group having 6 to 42 carbon atoms, such as triphenylsilyl), a phosphoryl group (preferably a phosphate group having 0 to 20 carbon atoms, such as —OP (═O) ( R ^P) _2), a phosphonyl group (preferably charcoal Phosphonyl group having 0-20, for ^{example, -P (= O) (R} P) 2), a phosphinyl group (preferably a phosphinyl group having 0 to 20 carbon atoms, for _{^{example, -P (R P) 2)}} , ( meth ) Acryloyl group, (meth) acryloyloxy group, hydroxyl group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom).
In addition, each of the groups listed as the substituent T may be further substituted with the substituent T described above.
When a compound or a substituent / linking group includes an alkyl group / alkylene group, an alkenyl group / alkenylene group, an alkynyl group / alkynylene group, etc., these may be cyclic or linear, and may be linear or branched These may be substituted as described above or may be unsubstituted.
Each substituent defined in the present specification may be substituted via the following linking group Lx within the range where the effects of the present invention are exhibited. For example, the alkyl group / alkylene group, alkenyl group / alkenylene group and the like may further have the following hetero-linking group interposed in the structure.
Examples of the linking group Lx include a hydrocarbon linking group [an alkylene group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), an alkenylene group having 2 to 10 carbon atoms (more preferably Has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms), an alkynylene group having 2 to 10 carbon atoms (more preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms), 6 to 22 carbon atoms Arylene groups (more preferably 6 to 10 carbon atoms)], hetero-linking groups [carbonyl group (—CO—), thiocarbonyl group (—CS—), ether group (—O—), thioether group (—S—) ), An imino group (—NR ^N —), an imine linking group (R ^N —N═C <, —N═C (R ^N ) —)], or a linking group obtained by combining these. In addition, when condensing and forming a ring, the said hydrocarbon coupling group may form the double bond and the triple bond suitably, and may connect. The ring to be formed is preferably a 5-membered ring or a 6-membered ring. As the five-membered ring, a nitrogen-containing five-membered ring is preferable, and examples of the compound forming the ring include pyrrole, imidazole, pyrazole, indazole, indole, benzimidazole, pyrrolidine, imidazolidine, pyrazolidine, indoline, carbazole, or these And derivatives thereof. Examples of the 6-membered ring include piperidine, morpholine, piperazine, and derivatives thereof. Moreover, when an aryl group, a heterocyclic group, etc. are included, they may be monocyclic or condensed and may be similarly substituted or unsubstituted.
^RN is a hydrogen atom or a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), an alkenyl group (2 carbon atoms). To 24, more preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 to 3, and an alkynyl group (preferably 2 to 24, preferably 2 to 12). More preferably, 2 to 6 carbon atoms are more preferable, and 2 to 3 carbon atoms are particularly preferable), an aralkyl group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, and particularly preferably 7 to 10 carbon atoms). ), An aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 10 carbon atoms).
^RP is a hydrogen atom, a hydroxyl group, or a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), an alkenyl group (2 carbon atoms). To 24, more preferably 2 to 12, more preferably 2 to 6, particularly preferably 2 to 3, and an alkynyl group (preferably 2 to 24, preferably 2 to 12). More preferably, 2 to 6 carbon atoms are more preferable, and 2 to 3 carbon atoms are particularly preferable), an aralkyl group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, and particularly preferably 7 to 10 carbon atoms). ), An aryl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 14 carbon atoms, particularly preferably having 6 to 10 carbon atoms), an alkoxy group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms) More preferably, it has 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms, and an alkenyloxy group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). Preferably 2 to 3 carbon atoms), an alkynyloxy group (preferably 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms, and particularly preferably 2 to 3 carbon atoms). ), An aralkyloxy group (preferably 7 to 22 carbon atoms, more preferably 7 to 14 carbon atoms, particularly preferably 7 to 10 carbon atoms), an aryloxy group (preferably 6 to 22 carbon atoms, 6 to 14 carbon atoms). And more preferably 6 to 10 carbon atoms).
In the present specification, the number of atoms constituting the linking group is preferably from 1 to 36, more preferably from 1 to 24, still more preferably from 1 to 12, and from 1 to 6 Is particularly preferred. The number of linking atoms in the linking group is preferably 10 or less, and more preferably 8 or less. The lower limit is 1 or more. The number of connected atoms refers to the minimum number of atoms that are located in a path connecting predetermined structural portions and are involved in the connection. For example, in the case of —CH ₂ —C (═O) —O—, the number of atoms constituting the linking group is 6, and the number of linking atoms is 3.
Specific examples of combinations of linking groups include the following. Oxycarbonyl group (OCO), carbonate group (OCOO), amide group (CONH), urethane group (NHCOO), urea group (NHCONH), (poly) alkyleneoxy group (-(Lr-O) x-), carbonyl ( Poly) oxyalkylene group (—CO— (O—Lr) x—, carbonyl (poly) alkyleneoxy group (—CO— (Lr—O) x—), carbonyloxy (poly) alkyleneoxy group (—COO— ( Lr-O) x-), (poly) alkyleneimino group (-(Lr-NR ^N ) x), alkylene (poly) iminoalkylene group (-Lr- (NR ^N -Lr) x-), carbonyl (poly) iminoalkylene group ^{(-CO- (NR N -Lr) x-} ), carbonyl (poly) alkyleneimino group ^{(-CO- (Lr-NR N)} x -), ( poly) S. Group (-(CO-O-Lr) x-,-(O-CO-Lr) x-,-(O-Lr-CO) x-,-(Lr-CO-O) x-,-(Lr -O-CO) x-), (poly) amide group (-(CO-NR ^N -Lr) x-,-(NR ^N -CO-Lr) x-,-(NR ^N -Lr-CO) x- ,-(Lr-CO-NR ^N ) x-,-(Lr-NR ^N -CO) x-), etc. x is an integer of 1 or more, preferably 1 to 100, more preferably 1 to 20. .
Lr is preferably an alkylene group, an alkenylene group or an alkynylene group. The carbon number of Lr is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. A plurality of Lr, R ^N , R ^P , x, etc. need not be the same. The direction of the linking group is not limited by the above description, and may be understood as appropriate according to a predetermined chemical formula.

-Manufacture of siloxane resin A siloxane resin can be obtained through a hydrolysis reaction and a condensation reaction using the alkoxysilane compound mentioned above.
As the hydrolysis reaction and the condensation reaction, known methods can be used, and a catalyst such as an acid or a base may be used as necessary. The catalyst is not particularly limited as long as it changes the pH. Specifically, examples of the acid (organic acid, inorganic acid) include nitric acid, oxalic acid, acetic acid, formic acid, hydrochloric acid and the like. Examples of the alkali include ammonia, triethylamine, ethylenediamine, and the like. The amount to be used is not particularly limited when the siloxane resin satisfies a predetermined molecular weight.

If necessary, a solvent may be added to the reaction system for the hydrolysis reaction and the condensation reaction. The solvent is not particularly limited as long as the hydrolysis reaction and the condensation reaction can be performed. For example, water, alcohols such as methanol, ethanol, and propanol, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monopropyl ether. And esters such as methyl acetate, ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate, and ketones such as acetone, methyl ethyl ketone, and methyl isoamyl ketone.

The conditions for the hydrolysis reaction and condensation reaction (temperature, time, amount of solvent) are appropriately selected according to the type of material used.

The weight average molecular weight of the siloxane resin used in the present embodiment is preferably 1,000 or more, more preferably 2,000 or more, further preferably 2,500 or more, and particularly preferably 3,000 or more. The upper limit value is preferably 50,000 or less, more preferably 45,000 or less, and particularly preferably 25,000 or less.
In the present invention, the molecular weight of the polymer means a weight average molecular weight unless otherwise specified, and is measured in terms of standard polystyrene by gel permeation chromatography (GPC). The measuring device and conditions are basically based on the following condition 1, and depending on the solubility of the sample, the condition 2 is allowed. However, depending on the polymer type, an appropriate carrier (eluent) and a column suitable for it may be selected and used.
(Condition 1)
Column: TOSOH TSKgel Super HZM-H,
TOSOH TSKgel Super HZ4000,
TOSOH TSKgel Super HZ2000
Carrier: tetrahydrofuran Measurement temperature: 40 ° C
Carrier flow rate: 1.0 ml / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector (Condition 2)
Column: Two TOSOH TSKgel Super AWM-Hs are connected Carrier: 10 mM LiBr / N-methylpyrrolidone Measurement temperature: 40 ° C.
Carrier flow rate: 1.0 ml / min
Sample concentration: 0.1% by mass
Detector: RI (refractive index) detector

(Fluorine resin)
The transparent resin may be a fluororesin. Examples thereof include fluorine siloxane polymers described in JP-A No. 2004-21036.

A fluororesin is a resin containing fluorine in a substance molecule, specifically, polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkyl. Examples include vinyl ether copolymers, tetrafluoroethylene / ethylene copolymers, hexafluoropropylene / propylene copolymers, polyvinylidene fluoride, vinylidene fluoride / ethylene copolymers, and the like.
Among them, polytetrafluoroethylene and tetrafluoroethylene / ethylene copolymer are preferable, polytetrafluoroethylene is more preferable, and polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer is also preferably used. It is done.
An amorphous fluororesin is also preferably used, and examples of commercially available products include CYTOP (manufactured by Asahi Glass Co., Ltd.). The molecular weight of fluororesin such as polytetrafluoroethylene is preferably in the range of 100,000 to 10,000,000, more preferably in the range of 100,000 to 1,000,000, and is particularly effective for extrusion moldability and flame retardancy. Commercially available products of polytetrafluoroethylene include “Teflon (registered trademark)” 6-J, “Teflon (registered trademark)” 6C-J, and “Teflon (registered trademark)” 62-J manufactured by Mitsui DuPont Fluorochemical Co., Ltd. “Full-on” CD1 and CD076 manufactured by Asahi Glass (formerly Asahi IC Fluoropolymers) are commercially available. A commercial product of polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene particles and an organic polymer is commercially available from Mitsubishi Rayon Co., Ltd. as “Metabrene (registered trademark)” A series. (Registered trademark) “A-3000”, “metabrene (registered trademark)” A-3800, etc. are commercially available.

Further, as the fluororesin, an amorphous fluororesin, a copolymer oligomer containing a perfluoroalkyl group-containing acrylate or methacrylate, a fluorocoating agent, a fluorosurfactant, a fluorocarbon surface treatment containing an electron beam or an ultraviolet curing component A fluorine-based surface treatment agent containing an agent and a thermosetting component is also preferable. As the other copolymerization component of the copolymer oligomer containing a perfluoroalkyl group-containing acrylate or methacrylate, alkyl acrylate or alkyl methacrylate is preferable.

A specific example is shown below. Examples of the amorphous fluororesin include Lumiflon manufactured by Asahi Glass Co., Ltd. and CYTOP. Copolymer oligomers containing perfluoroalkyl group-containing (meth) acrylate and alkyl (meth) acrylate as main components include NOF Modiper F series, Daikin Industries Unidyne, DIC MegaFuck F470 series, Examples thereof include F480 series and F110 series, and the copolymerization is more preferably block copolymerization. Examples of the fluorine-based coating agent include EGC1700 manufactured by 3M Japan. Examples of the fluorosurfactant include Megafac F114, F410 series, 440 series, 450 and 490 series manufactured by DIC. Examples of the fluorine-based surface treating agent containing an electron beam or an ultraviolet curing component include Polyfox PF-3320 manufactured by Omninova Solutions, Cheminox FAMAC-8 manufactured by Unimatec, and EGC1720 manufactured by 3M Japan. Examples of the fluorine-based surface treatment agent containing a thermosetting component include EGC1720 manufactured by 3M Japan, NH-10 and NH-15 manufactured by DIC.

When the transparent resin is used as the coating solution, the solvent is not limited, but examples include the reaction solvent used in the hydrolysis reaction or the organic solvent (A). Among these, alcohol compounds, ether compounds, and ester compounds are preferable, and propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, and ethyl lactate are more preferable. The concentration of the transparent resin in the coating solution is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 3% by mass or more. The upper limit of this concentration is preferably 50% by mass or less, more preferably 25% by mass or less, and particularly preferably 10% by mass or less.

(Surfactant)
In the transparent resin coating solution, it is preferable to use a surfactant from the viewpoint of further improving the coating property, and it is particularly preferable to include a surfactant having a polyoxyalkylene structure. The polyoxyalkylene structure refers to a structure in which an alkylene group and a divalent oxygen atom are present adjacent to each other, and specific examples include an ethylene oxide (EO) structure and a propylene oxide (PO) structure. . As the surfactant having a polyoxyalkylene structure, various surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant as long as the polyoxyalkylene structure is included. Surfactants can be used. Among these, nonionic surfactants, anionic surfactants, and silicone surfactants are preferable, nonionic surfactants and anionic surfactants are more preferable, and anionic surfactants are most preferable.

Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F479, F482, F554, F780, F781 (above, manufactured by DIC), Florard FC430, FC431, FC171 (above, manufactured by 3M Japan), Surflon S-382, S-141, S-145, SC -101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, K393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), Ftop EF301, EF303, EF351, EF352 (Mitsubishi Materials Electronics Kasei (formerly Gemco)), PF 36, PF656, PF6320, PF6520, PF7002 (OMNOVA Inc.) and the like.
Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane ethoxylate and propoxylate (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether (Emulgen 404 manufactured by Kao Corporation), polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, ELEBASE BUB-3 manufactured by Aoki Oil & Fat Co., etc. Is mentioned.
Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), EMULSOGEN COL-020, EMULSOGEN COA-070, EMULSOGEN COL-080, manufactured by Clariant Japan, and Prisurf manufactured by Daiichi Kogyo Seiyaku Co., Ltd. A208B, ETC-3 manufactured by Nikko Chemicals, and the like.
Examples of the silicone-based surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone SH29PA” manufactured by Toray Dow Corning. ”,“ Tole Silicone SH30PA ”,“ Tole Silicone SH8400 ”,“ TSF-4440 ”,“ TSF-4300 ”,“ TSF-4445 ”,“ TSF-4460 ”,“ TSF-4442 ”manufactured by Momentive Performance Materials, Inc. ”,“ KP341 ”,“ KF6001 ”,“ KF6002 ”manufactured by Shin-Etsu Chemical Co., Ltd.,“ BYK307 ”,“ BYK323 ”,“ BYK330 ”manufactured by Big Chemie,“ DBE-224 ”,“ D ”manufactured by GELEST E-621 ", and the like.
Only one type of surfactant may be used, or two or more types may be combined.

Moreover, as a surfactant having a preferred polyoxyalkylene structure of the present embodiment, a surfactant represented by the following formula (4) can be mentioned.
Formula (4): R ⁵ O (R ⁶ O) _m R ⁷
In the above formula, R ⁵ represents an alkyl group having 1 to 20 carbon atoms. R ⁶ represents an alkylene group having 1 to 4 carbon atoms. R ⁷ represents a hydrogen atom, a carboxyl group, or —PO ₃ H ₂ . m represents an integer of 1 to 8.
R ⁵ may be a linear or branched alkyl group. Of these, 5 to 20 carbon atoms are preferable, and 12 to 18 carbon atoms are more preferable.
R ⁶ may be a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and an isobutylene group. Among them, an ethylene group and an isopropylene group (a group that forms an adjacent O atom and an ethylene oxide structure or a propylene oxide structure) are preferable.
R ⁷ is preferably a hydrogen atom or a carboxyl group, and most preferably a carboxyl group.

Other surfactants may be used, and among them, a silicone surfactant is preferably used. Preferable silicone surfactants include polysiloxane type surfactants in which an organic group is introduced into a side chain or a terminal, or a side chain and a terminal. Examples of the side chain group include amino groups, epoxy groups, carbinol groups, mercapto groups, carboxyl groups, hydrogen groups, polyether groups, aralkyl groups, fluoroalkyl groups, and phenyl groups. Examples of the terminal group include an amino group, an epoxy group, a carbinol group, a methacryl group, a polyether group, a mercapto group, a carboxyl group, a phenol group, a silanol group, and a diol group.

Alternatively, it is also preferable to contain an alkylalkoxysilane compound having a specific carbon number (hereinafter referred to as “alkoxysilane compound α”). You may use together 3 types of surfactant of surfactant which has said polyoxyalkylene structure, silicone type surfactant, and alkoxysilane compound (alpha). As the alkoxysilane compound α, an alkoxysilane compound having an alkyl group having 4 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, is preferably used. When this is represented by a general formula, it is preferably a compound represented by the following formula (5).
Formula (5): Si (OR ⁵¹ ) _n-4 (R ⁵² ) _n
Here, R ⁵¹ is the same group as R ⁴ described above. R ⁵² is preferably an alkyl group having 4 to 12 carbon atoms, and more preferably an alkyl group having 6 to 10 carbon atoms. n is an integer of 1 to 3.

The addition amount of the surfactant is not particularly limited, and the lower limit thereof is preferably added in the range of 1 part by mass or more with respect to 100 parts by mass of the transparent resin, and 1.5 parts by mass or more. More preferably, it is most preferably 7.5 parts by mass or more. The upper limit is not particularly limited, and is preferably 30 parts by mass or less, and more preferably 15 parts by mass or less.

(Hollow particles, non-hollow particles, etc.)
The transparent resin coating liquid or the transparent resin film (cured film) obtained by curing the same preferably contains hollow particles or non-hollow particles. As the particles, porous fine particles may be used. The hollow particle has a structure having a cavity inside, and refers to a particle having a cavity surrounded by an outer shell. The porous particle refers to a porous particle having a large number of cavities. Hereinafter, hollow particles or non-hollow particles are appropriately referred to as “specific particles”. The specific particles may be organic particles or inorganic particles.

The porosity of the specific particles is preferably 10% to 80%, more preferably 20% to 60%, and most preferably 30% to 60%. The porosity of the specific particles is preferably in the above range from the viewpoint of reducing the refractive index and maintaining the durability of the particles.
Among the specific particles, hollow particles are more preferable from the viewpoint of easily reducing the refractive index. For example, when the hollow particles are made of silica, the hollow silica particles have air with a low refractive index (refractive index = 1.0), and therefore the refractive index is normal silica (refractive index = 1.6).

As a method for producing hollow particles, for example, the method described in JP-A-2001-233611 can be applied. Further, as a method for producing porous particles, for example, methods described in JP-A 2003-327424, JP-A 2003-335515, JP-A 2003-226516, JP-A 2003-238140, and the like are applied. it can.

The specific particles preferably have an average primary particle diameter of 1 nm or more, and more preferably 10 nm or more. The upper limit of the average primary particle diameter is preferably 200 nm or less, and more preferably 100 nm or less.
The average primary particle diameter of the specific particles here can be determined from the photograph obtained by observing the dispersed particles with a transmission electron microscope. The projected area of the particles is obtained, and the equivalent circle diameter is obtained therefrom, which is the average primary particle diameter. In the present specification, the average primary particle diameter is obtained by measuring the projected area of 300 or more particles, obtaining the equivalent circle diameter, and calculating the number average diameter.
The refractive index of the specific particles is preferably 1.10 to 1.40, more preferably 1.15 to 1.35, and most preferably 1.15 to 1.30.

The specific particles are preferably hollow or porous inorganic particles from the viewpoint of lowering the refractive index. Examples of the inorganic low refractive index particles include magnesium fluoride and silica particles, and silica particles are more preferable from the viewpoint of low refractive index properties, dispersion stability, and cost.
The inorganic particles may be crystalline or amorphous in crystal system, and may be monodispersed particles or aggregated particles as long as a predetermined particle diameter is satisfied. The shape is most preferably spherical, and may be a bead, a shape having a major axis to minor axis ratio of 1 or more, or an indefinite shape.
The specific surface area of the inorganic particles is preferably 10 m ² / g to 2000 m ² / g, more preferably 20 m ² / g to 1800 m ² / g, and 50 m ² / g to 1500 m ² / g. Is most preferred.

Specific examples of specific particles include IPA-ST having a number average particle size of 12 nm using isopropanol as a dispersant, MIBK-ST having a number average particle size of 12 nm using methyl isobutyl ketone as a dispersant, and number average using isopropanol as a dispersant. IPA-ST-L with a particle size of 45 nm, IPA-ST-ZL with a number average particle size of 100 nm using isopropanol as a dispersant, PGM-ST with a number average particle size of 15 nm using propylene glycol monomethyl ether as a dispersant (product names above) Manufactured by Nissan Chemical Industries Ltd.), “Oscar (registered trademark)” 101 having a number average particle diameter of 12 nm using γ-butyrolactone as a dispersant, “Oscar” 105 having a number average particle diameter of 60 nm using γ-butyrolactone as a dispersant, “Oscar” 106 with a number average particle size of 120 nm using diacetone alcohol as a dispersant The number average particle size of 16 nm using “cataloid (registered trademark)”-S (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having a number average particle size of 5 to 80 nm and propylene glycol monomethyl ether as a dispersant. "Quartron (registered trademark)" PL-2L-PGME, "Quatron" PL-1-PGME with a number average particle diameter of 12 nm, "Quatron" PL-2L- with a number average particle diameter of 17 nm using γ-butyrolactone as a dispersant BL, “Quatron” PL-1-BL with a number average particle diameter of 13 nm, “Quatron” PL-2L-DAA with a number average particle diameter of 17 nm using diacetone alcohol as a dispersant, “Quatron” PL with a number average particle diameter of 13 nm -1-DAA, “Quatron” PL-2L, G having a number average particle diameter of 18 nm to 20 nm, in which the dispersion is water -L, “Quartron” PL-1 (trade name, manufactured by Fuso Chemical Industries) with a number average particle diameter of 13 nm to 15 nm, silica (SiO 2) SG-SO100 (trade name, Kyoritsu Material) with a number average particle diameter of 100 nm And “Reolosil (registered trademark)” (manufactured by Tokuyama) having a number average particle diameter of 5 nm to 50 nm. Specific examples of the hollow silica particles include those commercially available, such as those disclosed in Japanese Patent Application Laid-Open No. 2001-233611 and Japanese Patent No. 3272111. Moreover, you may contain 2 or more types of these silica particles and hollow silica particles.

Specific particles used in the present invention include silica fine particles having one or both of porous and hollow inside, and silica fine particles that are not porous inside and have no hollow. Among these silica fine particles, silica fine particles having one or both of porous and hollow are preferable for reducing the refractive index of the coating film. Silica fine particles that are not porous inside and do not have a hollow have a refractive index of 1.45 to 1.5, so that the expected effect of lowering the refractive index is small. On the other hand, silica fine particles having one or both of porous and hollow inside have a large refractive index reducing effect because the refractive index of the particles themselves is 1.2 to 1.4. That is, silica fine particles having one or both of porous and hollow inside are preferably used because they can impart excellent hardness and low refractive index properties.

In this specification, the refractive index of the specific particles can be measured by the following method. A mixed solution sample of a matrix resin and particles having a solid content concentration of 10%, in which the particle content is adjusted to 0% by mass, 20% by mass, 30% by mass, 40% by mass, and 50% by mass is prepared. Each is coated on a silicon wafer by using a spin coater so as to have a thickness of 0.3 μm to 1.0 μm. Subsequently, it is heated and dried on a hot plate at 200 ° C. for 5 minutes to obtain a coating film. Next, for example, the refractive index at a wavelength of 633 nm (25 ° C.) is obtained using an ellipsometer (VUV-base [trade name] manufactured by JA Woollam Co., Ltd.), and the value of 100% by mass of silica fine particles can be extrapolated. .

Introducing silica fine particles having one or both of porous and hollow inside the coating material can not only optimize the refractive index of the film obtained from the coating material, but also increase the hardness of the film. This is preferable.

Silica fine particles that are not porous inside and have no hollow are, for example, IPA-ST in which isopropanol having a particle size of 12 nm is used as a dispersant, MIBK-ST in which methyl isobutyl ketone having a particle size of 12 nm is used as a dispersant, particles IPA-ST-L using isopropanol with a diameter of 45 nm as a dispersant, IPA-STZL using isopropanol with a particle diameter of 100 nm as a dispersant (trade name, manufactured by Nissan Chemical Industries, Ltd.), and γ-butyrolactone having a particle diameter of 12 nm are dispersed. Oscar 101 as a dispersant, Oscar 105 using γ-butyrolactone having a particle diameter of 60 nm as a dispersant, Oscar 106 using a diacetone alcohol having a particle diameter of 120 nm as a dispersant (trade name, manufactured by JGC Catalysts & Chemicals, Inc.) It is done. In addition, the presence or absence of a hollow can be confirmed by a particle cross-sectional image by a TEM (scanning electron microscope) photograph.

Examples of commercially available silica fine particles include organosilica sol “OSCAL” (manufactured by JGC Catalysts & Chemicals), colloidal silica “Snowtex”, organosilica sol (manufactured by Nissan Chemical Industries), high purity colloidal silica, and high purity. Organosol "Quartron" (Fuso Chemical Co., Ltd.)

Inorganic particles are used for physical stabilization such as plasma discharge treatment and corona discharge treatment, surfactants and coupling agents in order to stabilize dispersion, or to increase affinity and binding properties with binder components. Chemical surface treatment by such as may be performed. The use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
That is, when the inorganic particles are silica particles and the coupling agent is a silane compound, the organosilyl group (monoorganosilyl, diorganosilyl, triorganosilyl group) becomes silica particles by the reaction of the silane compound and the silanol group. It binds to the surface. Examples of the organic group on the surface of the surface-treated silica particles include saturated or unsaturated hydrocarbon groups having 1 to 18 carbon atoms and halogenated hydrocarbon groups having 1 to 18 carbon atoms.
The above-mentioned coupling agent may be used as a surface treatment agent for inorganic particles in order to perform surface treatment in advance before the preparation of the coating solution for a low refractive index film, or may be added as an additive at the time of preparing the coating solution.
The inorganic particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

Commercially available particles can be preferably used as the specific particles made of silica.
For example, through rear series manufactured by JGC Catalysts & Chemicals (hollow particles, isopropanol (IPA) dispersion, 4-methyl-2-pentanone (MIBK) dispersion, etc., such as through rear 2320 etc.), OSCAL series, Nissan, etc. Snowtex series (Porous particles, IPA dispersion, ethylene glycol dispersion, methyl ethyl ketone (MEK) dispersion, dimethylacetamide dispersion, MIBK dispersion, propylene glycol monomethyl acetate dispersion, propylene glycol monomethyl ether dispersion, methanol dispersion, ethyl acetate dispersion) Butyl acetate dispersion, xylene-n-butanol dispersion, toluene dispersion, etc. Examples include MIBK-SD-L and MIBK-ST. And PL series (porous particles, IPA dispersion, toluene dispersion, propylene glycol monomethyl ether dispersion, methyl ethyl ketone dispersion, etc., such as PL-1-IPA, PL-2L-PGME, etc.). And silica particles such as EVONIK Aerosil series (including porous particles, propylene glycol acetate dispersion, ethylene glycol dispersion, MIBK dispersion, etc.) can be used.

(Colloidal silica resin)
In the present invention, it is also preferable to use a sol in which beaded colloidal silica particles are dispersed in a liquid medium as specific particles. Generally, as the silica particles contained in the silica sol, in addition to the bead shape, spherical, needle-like or plate-like ones are widely known, and in this embodiment, the silica sol in which the bead-like colloidal silica particles are dispersed is used. It is preferable. This is because the presence of these beaded colloidal silica particles facilitates formation of pores in the formed film, and a film having a very low refractive index can be formed. Further, the particle size is small, and the haze of the film can be reduced.

The beaded colloidal silica particles are preferably those in which a plurality of spherical colloidal silica particles having an average particle diameter of 5 nm to 50 nm are joined by a metal oxide-containing silica. If the average particle diameter is less than the lower limit, the refractive index of the film after formation does not sufficiently decrease. On the other hand, if the average particle diameter exceeds the upper limit, the haze of the film may increase due to irregularities on the film surface. The average particle diameter of the spherical colloidal silica particles is preferably in the range of 5 nm to 30 nm. In addition, the average particle diameter of the said spherical colloidal silica particle means the average particle diameter measured by BET method.

The number average particle diameter measured by the dynamic light scattering method of the spherical colloidal silica particles is defined as D1 (nm). Moreover, let D2 (nm) be the average particle diameter obtained by the formula of D2 = 2720 / S from the specific surface area S (m ² / g) measured by the nitrogen adsorption method of the spherical colloidal silica particles. The beaded colloidal silica particles preferably have a ratio D1 / D2 of D1 and D2 of 3 or more, the D1 is 30 nm to 300 nm, and the spherical colloidal silica particles are connected only in one plane. . If D1 / D2 is less than 3, the haze of the film after formation may increase. D1 / D2 is preferably 3 to 20. If it is less than the lower limit of D1 / D2, the particles tend to aggregate and form a precipitate. On the other hand, if the upper limit of D1 / D2 is exceeded, the haze of the formed film may increase. More preferably, D1 is 35 nm to 150 nm. Moreover, as a metal oxide containing silica which joins a spherical colloidal silica particle, an amorphous silica, an amorphous alumina, etc. are illustrated, for example. Examples of the liquid medium in which the beaded colloidal silica particles are dispersed include methanol, ethanol, IPA, ethylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc., and the silica sol used has a SiO ₂ concentration of 5% by mass to What is 40 mass% is preferable. If the SiO ₂ concentration of the silica sol to be used is too low, the refractive index of the film after formation may not be sufficiently lowered. On the other hand, if it is too high, the SiO ₂ in the silica sol tends to aggregate and the liquid may become unstable. . As a silica sol in which such beaded colloidal silica particles are dispersed, for example, a silica sol described in Japanese Patent No. 4328935 can be used.

The content of the specific particles in the dispersion is preferably 10% by mass to 50% by mass, more preferably 15% by mass to 40% by mass, and further preferably 15% by mass to 30% by mass.

The content of the specific particles with respect to the total solid content in the coating solution of the transparent resin is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, and 20% by mass to 80% by mass. More preferably, it is mass%.
When a transparent resin film is formed, the coating amount of the specific particles is preferably 1 mg / m ² to 100 mg / m ² , more preferably 5 mg / m ² to 80 mg / m ² , still more preferably 10 mg / m ² to 60 mg / m ² . When it is 1 mg / m ² or more, the effect of lowering the refractive index and the effect of improving scratch resistance can be reliably obtained, and when it is 100 mg / m ² or less, the transparent resin film (cured film) It is possible to suppress deterioration of the integrated reflectance due to fine irregularities on the surface.
In the present specification, the total solid content refers to a component that does not volatilize or evaporate when dried at 100 ° C. Typically, it refers to components other than solvents and dispersion media.

(Curing agent)
The transparent resin coating solution may further contain a curing agent. As a hardening | curing agent, the hardening | curing agent which consists of Al, Mg, Mn, Ti, Cu, Co, Zn, Hf, and Zr is preferable, and these can also be used together.

These curing agents can be easily obtained by reacting a metal alkoxide with a chelating agent. Examples of chelating agents that can be used include β-diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane, and β-keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate.

Preferable specific examples of the metal group chelate compound include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetate bis (ethyl acetoacetate), aluminum tris Examples thereof include aluminum chelate compounds such as (acetylacetonate). Moreover, magnesium chelate compounds, such as ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethyl acetoacetate), alkyl acetoacetate magnesium monoisopropylate, magnesium bis (acetylacetonate), etc. are mentioned. Furthermore, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium acetylacetonate bis (ethylacetoacetate), manganese acetylacetonate, cobalt acetylacetonate, copper acetylacetonate, titanium acetylacetonate, titaniumoxyacetylacetate Naruto. Of these, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), magnesium bis (acetylacetonate), magnesium bis (ethylacetoacetate), and zirconium tetraacetylacetonate are preferable. Furthermore, aluminum tris (acetylacetonate) and aluminum tris (ethyl acetoacetate) are particularly preferable in consideration of storage stability and availability.

The total content of the curing agent is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total content of the transparent resin. Particularly preferred is 0.01 to 0.5 parts by mass.

(viscosity)
The viscosity of the transparent resin coating solution is preferably adjusted from the viewpoint of forming a thick and permeable film. The specific viscosity range is not particularly limited, but is preferably 1 mPa · s to 20 mPa · s, more preferably 1.2 mPa · s to 15 mPa · s, and more preferably 1.5 mPa · s to 6 mPa · s. It is particularly preferred that Unless otherwise indicated, the viscosity value in this specification shall be based on the following measuring method.
Measurement method Measured at room temperature (about 25 ° C.) using an E-type viscometer “TV-20 type viscometer / corn plate type TVE-20L” (manufactured by Toki Sangyo Co., Ltd.). Sampling is the average of the values measured for viscosity 5 times every 100 seconds.

<Lens formation material>
The material constituting the lens is not particularly limited, and may be inorganic or organic. In the present invention, it is preferable to apply a resin lens. Resin lenses, such as acrylic lenses, may have high reflectivity, and in such a case, the present invention can exhibit a particularly remarkable effect. When an organic resin is used, for example, a silicone resin, an acrylic resin, a novolac resin, an epoxy resin, a sulfide resin, a thiourethane resin, and the like can be given. Of these, acrylic resins, epoxy resins, and novolac resins are preferable. Specifically, in addition to the dispersion composition of the embodiment described later, a commercially available curable resin can be suitably used. The product names (product numbers) are listed below.
(1) Ultra-high refractive index, high heat-resistant coating material: UR-108, UR-202, UR-501, HR-102 (manufactured by Nissan Chemical Industries)
(2) High refractive index coating material for thick film: UR-108, UR-204, HR-201 (manufactured by Nissan Chemical Industries)
(3) Thioepoxy resin LPH1101 (Mitsubishi Gas Chemical Co., Ltd.)
(4) Episulfide resin MR-174 (Mitsui Chemicals)
(5) Thiourethane resin MR-7 (Mitsui Chemicals)
(6) As the silicone resin lens material, for example, those described in JP2013-080201A can be used. Specifically, polysiloxane is synthesized with phenyltrimethoxysilane, methyltrimethoxysilane, p-tolyltrimethoxysilane, or the like. This includes 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate, quinonediazide compound, tert-butyl dicyclohexylcarbamate (Nt-butoxycarbonyldicyclohexylamine), trioctylamine, propylene A resin composition for a lens can be obtained by blending glycol methyl ether, a fluorosurfactant (trade name “FTX-218”, manufactured by Neos), and the like.
(7) Acrylic positive resin “TMR-P15” (manufactured by Tokyo Ohka Kogyo Co., Ltd.)

In the present invention, the forming material of each lens constituting the lens array is not particularly limited, and is preferably formed of the following dispersion composition (I). The dispersion composition (I) is preferably a dispersion composition containing metal oxide particles, a polymer dispersant, a solvent, a polymerizable compound, and a polymerization initiator.

Metal oxide particles As metal oxide particles, inorganic particles having a high refractive index, titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), zinc (Zn) or magnesium (Mg) These oxide particles are mentioned. Titanium dioxide (TiO ₂ ) particles, zirconium dioxide (ZrO ₂ ) particles, or silicon dioxide (SiO ₂ ) particles are preferable, and among these, titanium dioxide particles (hereinafter sometimes simply referred to as “titanium dioxide”). More preferred.
The colorless or transparent titanium dioxide particles can be represented by the chemical formula TiO ₂ , preferably have a purity of 70% or more, more preferably have a purity of 80% or more, and further have a purity of 85% or more. preferable. The content of low-order titanium oxide, titanium oxynitride or the like represented by the formula Ti _n O _2n-1 (n represents a number of 2 to 4) is preferably 30% by mass or less, and 20% by mass or less. Is more preferable, and it is still more preferable that it is 15 mass% or less.
The metal oxide particles can be appropriately selected from commercially available metal oxide particles, for example. The primary particle diameter of the metal oxide particles is preferably 1 nm to 80 nm, and particularly preferably 1 nm to 50 nm. If the primary particle diameter of the metal oxide particles exceeds the upper limit, the refractive index and the transmittance may be lowered. On the other hand, when the amount is less than the lower limit, the dispersibility and dispersion stability may be reduced due to aggregation.
In the present specification, the primary particle diameter of the metal oxide particles is determined by the method measured in Examples described later.

The refractive index of the metal oxide particles is not particularly limited, and is preferably 1.75 to 2.7, more preferably 1.90 to 2.7 from the viewpoint of obtaining a high refractive index. The method for measuring the refractive index is the same as that for the hollow particles.
The specific surface area of the metal oxide particles is preferably 10 m ² / g to 400 m ² / g, more preferably 20 m ² / g to 200 m ² / g, and 30 m ² / g to 150 m ² / g. Most preferably.

As a metal oxide particle, what is marketed can be used preferably.
Examples of commercially available titanium dioxide particles include TTO series (TTO-51 (A), TTO-51 (C), etc.), TTO-S, and V series (TTO-S-1, TTO-S-) manufactured by Ishihara Sangyo Co., Ltd. 2, TTO-V-3, etc.) and MT series (MT-01, MT-05, etc.) manufactured by Teika.
Commercially available zirconium dioxide particles include, for example, UEP (Daiichi Rare Element Chemical Co., Ltd.), PCS (Nippon Denko Corporation), JS-01, JS-03, JS-04 (Nippon Denko Corporation), UEP -100 (manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.).
Examples of commercially available silicon dioxide particles include OG502-31 manufactured by Clariant Co.
The metal oxide particles may be used alone or in combination of two or more.

The content of the metal oxide particles in the composition is preferably 10% by mass to 90% by mass, more preferably 10% by mass to 50% by mass, and still more preferably 12% in the total solid content. The content is from 40% by weight to 40% by weight, particularly preferably from 15% to 35% by weight. On the other hand, particularly for high-refractive-index microlenses, the total solid content of the dispersion composition is 50% by mass to 90% by mass, more preferably 52% by mass to 85% by mass, and most preferably 55% by mass. % By mass to 80% by mass.

-Polymer dispersing agent It is preferable that the dispersion composition of this embodiment contains a graft copolymer as a polymer dispersing agent (specific dispersion resin). The graft copolymer of this embodiment has a graft chain in which the number of atoms excluding hydrogen atoms is in the range of 40 to 10,000. The graft chain in this case indicates from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain. In the dispersion composition, the specific dispersion resin is a dispersion resin that imparts dispersibility to the metal oxide particles, and has an affinity for the solvent due to the graft chain. Excellent dispersion stability afterwards. Moreover, when it is set as a dispersion composition, it is thought that it is suppressed that the uniformity of the film thickness in a coating film deteriorates because a graft chain and a solvent show favorable interaction.

In the graft copolymer, the number of atoms excluding hydrogen atoms per graft chain is preferably 40 to 10,000, more preferably 100 to 500, and still more preferably 150 to 260. If this number is too small, the graft chain is short, so that the steric repulsion effect is reduced and the dispersibility and dispersion stability may be lowered. On the other hand, if the amount is too large, the graft chain becomes too long, and the adsorptive power to the metal oxide particles is reduced, which may reduce the dispersibility and dispersion stability.
The number of atoms excluding hydrogen atoms per graft chain is included from the base atom bonded to the polymer chain constituting the main chain to the end of the branch polymer branched from the main chain. The number of atoms other than hydrogen atoms. When the graft copolymer contains two or more types of graft chains, it is sufficient that the number of atoms excluding hydrogen atoms of at least one type of graft chain satisfies the above requirements.

As the polymer structure of the graft chain, a poly (meth) acrylic structure, a polyester structure, a polyurethane structure, a polyurea structure, a polyamide structure, a polyether structure, or the like can be used. And in order to improve the interaction between the graft chain and the solvent, thereby increasing the dispersibility and dispersion stability, it is preferably a graft chain having a poly (meth) acrylic structure, a polyester structure, a polyether structure, More preferably, it has a polyester structure or a polyether structure.

Examples of the polymer dispersant include a repeating unit represented by the following formula (I-1) and a repeating unit represented by the formula (I-2), or a repeating unit represented by the formula (I-1) and a formula A dispersion resin containing a repeating unit represented by (I-2a) is preferred.

R ¹ and R ² each independently represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 6 carbon atoms). a independently represents an integer of 1 to 5; * Represents a connecting part between repeating units.
R ⁸ and R ⁹ are the same groups as R ¹ .
L is a single bond or the above linking group Lx. Among the linking groups Lx, an alkylene group (preferably having 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms), a heteroarylene group (having 1 to 6 carbon atoms). 6), an imino group (preferably having a carbon number of 0 to 6), an ether group, a thioether group, a carbonyl group, or a linking group according to a combination thereof is preferable, an alkylene group, an alkenylene group, a carbonyl group, an oxy group Groups based on groups, imino groups and combinations thereof are preferred. The number of linking atoms in the linking group is preferably 1 or more and 10 or less, and more preferably 1 or more and 8 or less.
L ^a is a structural site to form a ring structure together with CR ⁸ CR ⁹ and N, be combined with the carbon atoms of CR ⁸ CR ⁹ is a structural site that form a non-aromatic heterocyclic ring having 3 to 7 carbon atoms preferable. More preferably, it is a structural part that forms a 5- to 7-membered non-aromatic heterocyclic ring by combining the carbon atom and N (nitrogen atom) of CR ⁸ CR ⁹ , and more preferably forms a 5-membered non-aromatic heterocyclic ring It is particularly preferred that it is a structural site that forms pyrrolidine. However, the structural site may further have a substituent such as an alkyl group.
X represents a group having a functional group of pKa (acid dissociation constant) of 14 or less.
Y represents a side chain having 40 to 10,000 atoms.

The specific dispersion resin preferably further has a repeating unit represented by formula (I-3), formula (I-4), or formula (I-5) as a copolymerization component. When the specific dispersion resin contains such a repeating unit, the dispersion performance can be further improved.

R ¹ , R ² , R ⁸ , R ⁹ , L, L ^a , and a are as defined in the formulas (I-1), (I-2), and (I-2a).

Ya represents a side chain having 40 to 10,000 atoms having an anionic group. The repeating unit represented by the formula (I-3) is reacted by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amino group in the main chain. Can be formed. Ya is preferably represented by the following formula (III-2).

・ Partial structure X
The partial structure X in each of the above formulas has a functional group having a pKa of 14 or less at a water temperature of 25 ° C. pKa is one of the indexes for quantitatively expressing the acid strength and is synonymous with the acidity constant. Considering a dissociation reaction in which hydrogen ions are released from an acid, its equilibrium constant Ka is expressed by its negative common logarithm pKa. A smaller pKa indicates a stronger acid. As used herein, “pKa” can refer to the definition described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). Alternatively, for example, a value calculated using ACD / Labs (manufactured by Advanced Chemistry Development) or the like can be used. When evaluation as a compound is necessary, the substituent X may be evaluated as compound XH or X—CH ₃ .
The “functional group of pKa14 or less” is not particularly limited as long as the physical properties satisfy this condition, and examples thereof include those having a pKa satisfying the above range with known functional groups. The following functional groups are preferred, and those having a pKa of 11 or less are particularly preferred. There is no particular lower limit, and it is practical that it is -5 or more. Specific examples of the partial structure X include, for example, a carboxyl group (pKa: about 3 to 5), a sulfonic acid (pKa: about -3 to -2), a -COCH ₂ CO-containing group (pKa: about 8 to 10). , —COCH ₂ CN (pKa: about 8 to 11), —CONHCO— containing group, phenolic hydroxyl group, —R _F CH ₂ OH or — (R _F ) ₂ CHOH (R _F is a perfluoroalkylene group or a perfluoroalkyl group) PKa: about 9 to 11), sulfamoyl group (pKa: about 9 to 11), and the like, particularly carboxyl group (pKa: about 3 to 5), sulfonic acid group (pKa: about -3 to -2) , —COCH ₂ CO— containing group (pKa: about 8 to 10) is preferable.

When the pKa of the functional group of the partial structure X is not more than the above lower limit, the interaction with the highly refractive particles can be effectively achieved. The partial structure X is preferably directly bonded to the basic nitrogen atom in the repeating unit having the basic nitrogen atom. The partial structures X may be linked not only by a covalent bond but also in a form in which a salt is formed by ionic bonding. As the partial structure X, those having a structure represented by the following formula (V-1), formula (V-2) or formula (V-3) are particularly preferable.

U represents a single bond or a divalent linking group.
d and e each independently represents 0 or 1;
Q represents an acyl group or an alkoxycarbonyl group.

Examples of the divalent linking group represented by U include the examples of the linking group Lx. For example, alkylene (more specifically, for _{example, -CH 2 -, - CH 2} CH 2 -, - CH 2 CHMe- (Me is methyl _{group), - (CH 2) 5} -, - CH 2 CH (n —C ₁₀ H ₂₁ ) —, etc.), oxygen-containing alkylene (more specifically, for example, —CH ₂ OCH ₂ —, —CH ₂ CH ₂ OCH ₂ CH ₂ —, etc.), alkenylene groups (vinylene, arylene) Etc.), an arylene group, alkyleneoxy and the like. In particular, an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 30 carbon atoms, or an arylene group having 6 to 20 carbon atoms is preferable, and an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms is most preferable. .
Further, from the viewpoint of productivity, d is preferably 1, and e is preferably 0.

As the acyl group in Q, an acyl group having 1 to 30 carbon atoms is preferable, and acetyl is particularly preferable. The alkoxycarbonyl group in Q preferably has 1 to 30 carbon atoms, and is preferably a methoxycarbonyl group, an ethoxycarbonyl group, or a phenyloxycarbonyl group. Q is particularly preferably an acyl group, and an acetyl group is preferable from the viewpoint of ease of production and availability of ^a raw material (precursor X ^a of X).

The partial structure X is preferably bonded to the basic nitrogen atom in the repeating unit having a basic nitrogen atom. This dramatically improves the dispersibility and dispersion stability of the metal fine particles. The partial structure X is also considered to contribute to dispersion stability by imparting solvent solubility and suppressing resin precipitation over time. Furthermore, since the partial structure X contains a functional group of pKa14 or less, it also functions as an alkali-soluble group. Thereby, it is considered that developability is improved as necessary, and it is possible to achieve both dispersibility, dispersion stability, and developability.

The content of the functional group of pKa14 or less in the partial structure X is not particularly limited, and is preferably 0.01 mmol to 5 mmol, particularly preferably 0.05 mmol to 1 mmol with respect to 1 g of the specific dispersion resin. Further, from the viewpoint of developability, it is preferable that the acid value of the specific dispersion resin is contained in an amount of about 5 mgKOH / g to 50 mgKOH / g from the viewpoint of acid value.
・ Side chain Y
Examples of Y include known polymer chains such as polyester, polyamide, polyimide, and poly (meth) acrylic acid ester that can be connected to the main chain portion of the specific dispersion resin. The binding site with the specific dispersion resin in Y is preferably the terminal of the side chain Y.

Y is at least one selected from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit. It is preferably bonded to the above nitrogen atom of the repeating unit having a nitrogen atom At least one basic selected from a poly (lower alkyleneimine) -based repeating unit, a polyallylamine-based repeating unit, a polydiallylamine-based repeating unit, a metaxylenediamine-epichlorohydrin polycondensate-based repeating unit, and a polyvinylamine-based repeating unit The bonding mode between the main chain portion such as a repeating unit having a nitrogen atom and Y is a covalent bond, an ionic bond, or a mixture of a covalent bond and an ionic bond. The ratio of the binding mode between Y and the main chain is covalent bond: ionic bond = 100: 0 to 0: 100, preferably 95: 5 to 5:95, and particularly preferably 90:10 to 10:90.
Y is preferably ionically bonded as an amide bond or carboxylate with the nitrogen atom of the repeating unit having the basic nitrogen atom.

The number of atoms of the side chain Y is preferably 50 to 5,000, more preferably 60 to 3,000, from the viewpoints of dispersibility, dispersion stability, and developability.
Moreover, the number average molecular weight of Y can be measured by the polystyrene conversion value by GPC method. At this time, it is practical to measure the molecular weight of Y before being incorporated into the resin. The number average molecular weight of Y is particularly preferably 1,000 to 50,000, and most preferably 1,000 to 30,000 from the viewpoints of dispersibility, dispersion stability, and developability. The molecular weight of Y can be specified from the polymer compound used as the raw material for Y, and the measurement method is based on the measurement conditions by GPC.
It is preferable that two or more side chain structures represented by Y are connected to the main chain in one molecule of the resin, and more preferably five or more are connected.

In particular, Y preferably has a structure represented by the formula (III-1).

In the formula (III-1), Z is a polymer or oligomer chain having a polyester chain as a partial structure. It is preferable to represent a residue obtained by removing a carboxyl group from a polyester having a free carboxylic acid represented by HO—CO—Z. When the specific dispersion resin contains repeating units represented by the formulas (I-3) to (I-5), it is preferable that Ya is the formula (III-2).

In formula (III-2), Z has the same meaning as Z in formula (III-1). Polyester having a carboxyl group at one end of the partial structure Y includes polycondensation of carboxylic acid and lactone, polycondensation of hydroxy group-containing carboxylic acid, polycondensation of dihydric alcohol and divalent carboxylic acid (or cyclic acid anhydride). Etc. can be obtained.

Z is preferably-(L ^B ) _nB -Z ^B.
Z ^B represents a hydrogen atom or a monovalent organic group. When Z ^B is an organic group, an alkyl group (preferably having 1 to 30 carbon atoms), an aryl group, a heterocyclic group, or the like is preferable. Z ^B may further have a substituent, and examples of the substituent include an aryl group having 6 to 24 carbon atoms and a heterocyclic group having 3 to 24 carbon atoms.
L ^B is preferably the above-mentioned linking group Lx group having the same meaning as, inter alia an ester chain (- (Lr-O-CO ) -), amide chains ^{(- (Lr-NR N -CO} ) -) is especially preferred . Lr is particularly preferably an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms).
nB is an integer of 5 to 100,000. nB number of L ^B may have a different structure, respectively.

As specific examples of the dispersant composed of the above graft copolymer, the exemplified compounds of [0361] to [0370] of International Publication No. 2013/099945 are cited and incorporated.

In the present embodiment, a polymer dispersant represented by the following formula (1) is suitable.

In the above formula (1), R ¹ represents a (m + n) -valent linking group. R ² represents a single bond or a divalent linking group. A ¹ is an acid group, a urea group, a urethane group, a group having a coordinating oxygen atom, a group having a basic nitrogen atom, a phenol group, an alkyl group, an aryl group, a group having an alkyleneoxy chain, an imide group, a heterocyclic ring Represents a monovalent substituent having at least one group selected from the group consisting of a group, an alkyloxycarbonyl group, an alkylaminocarbonyl group, a carboxylate group, a sulfamoyl group, an alkoxysilyl group, an epoxy group, an isocyanate group and a hydroxyl group . The n A ¹ and R ² may be the same or different. m represents a positive number of 8 or less. n represents 1 to 9. m + n satisfies 3 to 10. P ¹ represents a polymer chain. The m P ¹ may be the same or different.

In the dispersion composition of this embodiment, since the substituent A ¹ can interact with the metal oxide particles, the metal oxide particles have n (1 to 9) substituents A ^1. And can interact strongly. Further, the m polymer chains P ¹ can function as a steric repulsion group, exhibit a good steric repulsion force, and can uniformly disperse metal oxide particles. Further, it is presumed that the molecular structure does not cause adverse effects such as aggregation of particles due to cross-linking between particles, which can occur with a dispersant having a conventional graft random structure.

The molecular weight of the specific dispersion resin is preferably 3,000 to 100,000, and more preferably 5,000 to 55,000 in terms of weight average molecular weight. When the weight average molecular weight is within the above range, the effects of the plurality of adsorption sites introduced at the ends of the polymer are sufficiently exhibited, and performance excellent in adsorptivity to the titanium dioxide particle surfaces can be exhibited. In addition, the molecular weight here shall be calculated | required according to the measuring method by said GPC. Specific dispersion resin can be used individually by 1 type or in combination of 2 or more types.

The content of the specific dispersion resin relative to the total solid content of the dispersion composition is preferably in the range of 10% by mass to 50% by mass, more preferably in the range of 10% by mass to 40% by mass, from the viewpoints of dispersibility and dispersion stability. The range of 10% by mass to 30% by mass is more preferable.
As the polymer compound represented by the above formula (1), refer to the description after paragraph [0039] of JP-A-2007-277514 (corresponding to [0053] of US 2010/0233595 corresponding). The contents of which are incorporated herein by reference. In addition, as a specific example of the polymer compound represented by the above formula (1), paragraph [0266] of JP-A-2007-277514 ([0389] of the corresponding US Patent Application Publication No. 2010/0233595) Reference can be made to the description of the compounds synthesized in the following examples, the contents of which are incorporated herein.

-Solvent The dispersion composition of this embodiment contains a solvent, and the said solvent can be comprised using the said organic solvent (A).
These organic solvents can be used alone or in combination. The concentration of solid content in the dispersion composition is preferably 2% by mass to 60% by mass.

Polymerizable compound The polymerizable compound is preferably an addition polymerizable compound having a polymerizable group such as at least one ethylenically unsaturated double bond, an epoxy group, or an oxetanyl group. Preferably, it is selected from compounds having at least one polymerizable group, more preferably two or more. For example, it has chemical forms such as monomers, prepolymers, ie, dimers, trimers and other oligomers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids, esters thereof, and amides, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, unsaturated carboxylic acids and Amides with aliphatic polyvalent amine compounds are used. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like. Further, an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a nucleophilic substituent such as a hydroxyl group, an amino group, a mercapto group, and a monofunctional or polyfunctional isocyanate or epoxy. A dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, Furthermore, a substitution reaction product of an unsaturated carboxylic acid ester or unsaturated carboxylic acid amide having a leaving substituent such as a halogen group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. It is. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid. As these specific compounds, the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be suitably used in the present invention.

The first preferred form of the polymerizable compound is an embodiment containing a monomer (polymerizable compound) having at least one ethylenically unsaturated double bond or an oligomer having a polymerizable group (polymerizable oligomer). Hereinafter, the polymerizable compound and the polymerizable oligomer may be simply referred to as “polymerizable compound”.

The polymerizable compound is preferably further represented by the following formulas (MO-1) to (MO-6).

In the formula, n is 0 to 14, respectively, and m is 1 to 8, respectively. A plurality of R, T and Z present in one molecule may be the same or different. When T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R. At least one of R is a polymerizable group.

n is preferably 0 to 5, and more preferably 1 to 3.
m is preferably 1 to 5, and more preferably 1 to 3.

Examples of the bisphenol A type epoxy resin include JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), and EPICLON860, EPICLON1050, EPICLON1051 and above. DIC, etc.). Examples of the bisphenol F type epoxy resin include JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin), EPICLON830, EPICLON835 (above, made by DIC), LCE-21, RE-602S (above, Nippon Kayaku Co., Ltd.). Phenol novolac type epoxy resins include JER152, JER154, JER157S70, JER157S65 (above, Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC Corporation) Manufactured) and the like. Cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC), And EOCN-1020 (Nippon Kayaku Co., Ltd.). As the aliphatic epoxy resin, ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA) Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4600 (Above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation) and the like. In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN- 501, EPPN-502 (manufactured by ADEKA), JER1031S (manufactured by Japan Epoxy Resin), and the like.

Specific examples of the polymer having an oxetanyl group in the side chain and the polymerizable compound or oligomer having two or more oxetanyl groups in the molecule include Aronoxetane OXT-121, OXT-221, OX-SQ, PNOX ( As described above, Toagosei Co., Ltd.) can be used.

The details of the use method such as the structure, single use or combined use, and addition amount of these polymerizable compounds can be arbitrarily set in accordance with the final performance design of the dispersion composition.

The content of the polymerizable compound with respect to the total solid content of the dispersion composition is preferably in the range of 1% by mass to 50% by mass, more preferably in the range of 3% by mass to 40% by mass, The range of 5% by mass to 30% by mass is more preferable.
Within this range, the curability is good and preferable without lowering the refractive index.

-Polymerization initiator A polymerization initiator is a compound which starts and accelerates | stimulates superposition | polymerization of a polymeric compound, It is stable to 45 degreeC, and it is preferable that the polymerization initiating ability at the time of high temperature heating is favorable.
The polymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
Moreover, a polymerization initiator can be used individually or in combination of 2 or more types.

Examples of the polymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaarylbiphenyls. Examples include imidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.
As specific examples of these, the description after paragraph [0135] of JP 2010-106268 A (corresponding US Patent Application Publication No. 2011/0124824 [0163]) can be referred to. Incorporated into.

As the polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 whose absorption wavelength is matched with a wavelength light source of 365 nm or 405 nm can also be used.
As the acylphosphine initiator, commercially available products such as IRGACURE-819, Darocur 4265, DAROCUR-TPO (trade names: all manufactured by BASF) can be used.

The oxime compound has a function as a thermal polymerization initiator that is decomposed by heat to start and accelerate polymerization. The oxime compound is less colored by post-heating and has good curability.

The oxime compound preferably has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, more preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and has high absorbance at 365 nm and 455 nm. Particularly preferred.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred. For the molar extinction coefficient of the compound, a known method can be used. Specifically, for example, in an ultraviolet-visible spectrophotometer (Carry-5 spectrophotometer manufactured by Varian), an ethyl acetate solvent is used, and 0.01 g / It is preferable to measure at the concentration of L.
Moreover, as oxime compounds, commercially available products such as IRGACURE OXE01 and IRGACURE OXE02 (both manufactured by BASF) can be suitably used.

As the polymerization initiator, from the viewpoint of curability, trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oximes Compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, 3-aryl substitution Compounds selected from the group consisting of coumarin compounds are preferred.

The content of the polymerization initiator (in the case of 2 or more types, the total content) is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3%, based on the total solid content of the dispersion composition. It is not less than 8% by mass and more preferably not more than 0.5% by mass and not more than 5% by mass. Within this range, good curability can be obtained.

Furthermore, you may contain further the arbitrary components explained in full detail as needed.
-Polymerization inhibitor It is preferable to add a polymerization inhibitor in order to prevent unnecessary polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during production or storage.
Polymerization inhibitors include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, diazonium compounds, and cations Examples include dyes, sulfide group-containing compounds, nitro group-containing compounds, transition metal compounds such as FeCl ₃ and CuCl ₂ . Specific examples of the polymerization inhibitor include those described in paragraphs [0260] to [0280] of JP 2010-106268 A (corresponding to [0284] to [0296] of the corresponding US Patent Application Publication No. 2011/0124824). The description can be referred to and these contents are incorporated herein.

A preferable addition amount of the polymerization inhibitor is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.01 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the polymerization initiator. It is most preferable that it exists in the range of 0.05 mass part or more and 5 mass parts or less.
By setting it as the said range, the curing reaction suppression in a non-image part and the curing reaction acceleration in an image part are fully performed, and image forming property and a sensitivity become favorable.

-Binder polymer It is preferable that the dispersion composition of this embodiment contains a binder polymer further.
It is preferable to use a linear organic polymer as the binder polymer. As such a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such a linear organic polymer include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-sho. There are those described in Japanese Patent Application Laid-Open Nos. 54-25957, 54-92723, 59-53836, and 59-71048. That is, a resin in which a monomer having a carboxyl group is singly or copolymerized, a resin in which an acid anhydride unit is singly or copolymerized, and an acid anhydride unit is hydrolyzed, half-esterified or half-amidated, an epoxy resin And epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene. Examples of the monomer having an acid anhydride include maleic anhydride.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

The weight average molecular weight (polystyrene conversion value measured by GPC method) of the binder polymer is preferably 5,000 or more, more preferably 10,000 to 300,000, and the weight average molecular weight is preferably It is 1,000 or more, More preferably, it is the range of 2,000 or more and 250,000 or less. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 or more and 10 or less.
These binder polymers may be any of random polymers, block polymers, graft polymers and the like.

The content of the binder polymer is preferably 1% by mass or more and 40% by mass or less, more preferably 3% by mass or more and 30% by mass or less, and more preferably 4% by mass with respect to the total solid content of the dispersion composition. More preferably, it is 20 mass% or less.

-Surfactant You may add various surfactant to the dispersion composition of this embodiment. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. In particular, the use of a fluorosurfactant is preferred. Specific examples of the surfactant may be the same as those described for the transparent resin coating solution, and only one type may be used or two or more types may be combined. The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility.
The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the dispersion composition.

-Other additives Furthermore, you may add well-known additives, such as a ultraviolet absorber, a plasticizer, and a sensitizer, with respect to a dispersion composition.
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. When a binder polymer is used, 10% by mass or less of a plasticizer can be added to the total mass of the polymerizable compound and the binder polymer.

<Method of forming lens array>
An example of the lens array forming process will be described with reference to FIG. (0) If necessary, the surface of an uneven element is filled with a transparent resin spin coat and planarized. (1) A lens material is uniformly applied to the flattened surface. (2) A resist is uniformly applied on the lens material. (3) The stepper device irradiates ultraviolet rays using the reticle as a mask, and exposes the space between the lenses. A pattern is formed by disassembling and removing the portion exposed to the developer. (4) Obtained by heating a hemispherical pattern. At this time, the resist melts into a liquid phase, becomes a hemispherical state, and then changes to a solid phase. (5) Thereafter, the lens material layer is etched by dry etching to form a lens array in which hemispherical lenses are arranged.
Another embodiment of the lens array includes a method in which the use of the resist is omitted and the lens material is patterned by exposure. In this embodiment, the patterned lens material is melted as it is to obtain a hemispherical lens.

Regarding the material (dispersion composition) constituting the above-mentioned lens, reference can be made to [0097] to [0373] of International Publication No. 2013/099945, Examples of JP 2013-080201 A, etc. Cited in the invention.

<Lens array member>
As shown in FIG. 1, the lens array member of the present invention preferably has a configuration in which a large number of convex lenses 2 are arranged in parallel. The size of the lens array is not particularly limited, but the size W (FIG. 1A) of one lens is preferably 0.5 μm or more, more preferably 0.8 μm or more, and 1.0 μm. The above is particularly preferable. The upper limit is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 3 μm or less.
The height H of the lens is preferably 0.1 μm or more, more preferably 0.2 μm or more, and particularly preferably 0.3 μm or more. The upper limit is preferably 3 μm or less, more preferably 2 μm or less, and particularly preferably 1 μm or less. The radius of curvature of the lens convex portion is preferably not particularly limited within a range in which a desired effect is achieved.
According to the technology of the present invention, even a micro lens array member as described above can efficiently form a low-refractive index film suitable for the surface, and the effect can be exhibited more remarkably. The
The refractive index of the lens is preferably 1.5 or more, more preferably 1.6 or more, and particularly preferably 1.8 or more. The upper limit value is preferably 2.5 or less, more preferably 2.2 or less, and particularly preferably 2.0 or less.
In the present specification, unless otherwise specified, the refractive index of the film or its material depends on the conditions measured in the examples described later.

<Low refractive index film (transparent resin film)>
The transparent resin film 41 of the present invention is preferably a low refractive index film provided on the surface of the lens array member. The low refractive index film preferably has a refractive index of 1.45 or less, more preferably 1.42 or less, and particularly preferably 1.4 or less from the viewpoint of exhibiting an antireflection effect. The lower limit is preferably 1 or more, particularly preferably 1.2 or more. The difference in refractive index between the high refractive index film (lens) and the low refractive index film is preferably 0.2 or more, and more preferably 0.3 or more. There is no particular upper limit for the difference in refractive index, and it is practical that it is 2 or less, and more practical that it is 1 or less.
The thickness of the low refractive index film (transparent resin film) is not particularly limited, but is preferably 0.05 μm or more, more preferably 0.075 μm or more, and particularly preferably 0.09 μm or more. The upper limit is preferably 0.2 μm or less, more preferably 0.15 μm or less, and particularly preferably 0.12 μm or less. The variation in thickness is preferably small, and the difference (ΔT: Tv−Tt) between the thickness (Tv) of the concave portion and the thickness (Tt) of the convex portion of the lens array is preferably 0.3 μm or less. More preferably, it is 0.15 μm or less, further preferably 0.1 μm or less, and particularly preferably 0.07 μm or less. Usually, the thickness (Tv) of the resin film in the concave portion is larger than the thickness (Tt) in the convex portion. According to the technique of the present invention, this thickness difference (ΔT) has an advantage that it can be realized in spite of a film formed by a coating method.
In the present invention, unless otherwise specified, the thickness of the lens and the transparent resin film is measured by a micrograph taken using an electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation. Specifically, the positions of 50 points in the micrograph are measured and the average value is adopted.

<Antireflection film>
As a suitable usage mode of the low refractive index film (transparent resin film), an antireflection film may be mentioned. In particular, it is suitable as an antireflection film for an optical device using a solid-state imaging device or the like, for example, a microlens for an image sensor, a plasma display panel, a liquid crystal display, or an organic electroluminescence panel. The lower the reflectance when used as an antireflection film, the better. Specifically, the specular average reflectance in the wavelength region of 400 nm to 700 nm is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The reflectance is preferably as small as possible, and most preferably substantially zero.
The haze of the antireflection film is preferably 3% or less, more preferably 1% or less, and most preferably 0.5% or less. The reflectance is preferably as small as possible, and most preferably substantially zero.

<Lens unit>
A lens unit (microlens unit) is mentioned as an example of the utilization form of the lens array member of this invention. The lens unit is a component that is incorporated into the camera module (solid-state imaging device), and includes a lens array member and other necessary members.
The microlens unit according to a preferred embodiment of the present invention preferably has the following configuration. That is, a plurality of convex lenses are applied as the microlenses, and the plurality of convex lenses are arranged with the bulging direction in the same direction (preferably the light incident direction). At this time, the opposite side (surface) 41a of the lens in the transparent resin film corresponds to the unevenness of the surface 2Aa of the lens array member.
In the present specification, “the same direction” means that the directions coincide with each other, but does not have to coincide completely, and there is a certain deviation such as inconsistency in the bulging direction within a range where a desired effect is achieved. The purpose is to allow good. For example, in terms of the deviation in the axial direction of orientation, it is preferably within 30 °, more preferably within 20 °, and particularly preferably within 10 °.
In addition, “corresponding to the unevenness” means that the uneven shape of the lower lens array member and the uneven shape of the surface of the transparent resin film on the upper side are the same or different, It means that the amplitudes are substantially matched and the amplitudes are substantially matched. Here, when the amplitude of the unevenness is specified, the amplitude of the unevenness (F2) on the surface of the transparent resin film 41a is different from the amplitude (F1) of the unevenness on the surface 2Aa of the lens array. It is preferably in the range of 60% to 150%, more preferably in the range of 80% to 120%. In terms of the period as well, it means that there may be an acceptable deviation, and the deviation amount is preferably 40% or less of one period, more preferably 25% or less, and more preferably 10%. It is particularly preferred that

<Camera module>
A camera module according to a preferred embodiment of the present invention has a lens unit on a semiconductor light receiving unit, and is incorporated so that a lens array member and a color filter are adjacent to each other. The light receiving element receives light passing through the transparent resin film, the lens, and the color filter in this order, and functions as an image sensor. Specifically, the transparent resin film functions as an antireflection film, improves the light collection efficiency of the lens, and the light efficiently collected by the lens is detected by the light receiving element via the color filter. Since these function throughout the elements that detect light corresponding to RGB, an extremely clear image can be obtained even when the light receiving elements and the lenses are arranged at high density.

Examples of camera modules to which a lens array is applied include those described in Japanese Patent Application Laid-Open No. 2007-119744. Specifically, a transfer electrode is provided between a CCD region and a photoelectric conversion unit formed on the surface of the semiconductor substrate, and a light shielding film is formed thereon via an interlayer film. On the light shielding film, an interlayer insulating film made of BPSG (Boro-Phospho-Silicate Glass), a passivation film, a transparent planarizing film having a low refractive index made of acrylic resin, and the like are laminated. G. B. Are combined to form a color filter. Further, a large number of microlenses are arranged so as to be positioned above the photoelectric conversion portion which is a light receiving region via a protective film.

<Lens array member manufacturing kit>
A lens array member manufacturing kit according to a preferred embodiment of the present invention is a kit for forming a transparent resin film on the surface of a lens array through the above-described lens array member manufacturing method. That is, it comprises a curing accelerator for imparting to the lens array surface and a transparent resin for imparting to the lens array surface to which this curing accelerator has been imparted.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not construed as being limited by these examples. In this example, “part” and “%” are based on mass unless otherwise specified.

<Transparent resin coating solution>
Hydrolysis / condensation reactions were carried out using the silane compounds shown in Table A below. The solvent used at this time was ethanol, and the catalyst was hydrochloric acid. The obtained hydrolysis condensate had a weight average molecular weight of about 10,000. The weight average molecular weight was confirmed by GPC according to the procedure described above.
Furthermore, an additive having the composition shown in Table A below was added to a solution containing 5 parts of a silane compound in 95 parts of propylene glycol monomethyl ether acetate (PGMEA) to prepare a coating solution of a transparent resin. The viscosities were all 2 mPa · s to 4 mPa · s (25 ° C.).

Table notes MTES: Methyltriethoxysilane TEOS: Tetraethoxysilane γ-GP-TMS: γ-Glycidoxypropyltrimethoxysilane TFP-TMS: Trifluoropropyltrimethoxysilane EMUL-020: Emulsogen COL-020
(Anionic surfactant, Clariant)
ECT-3: Trade name (anionic surfactant, manufactured by Nikko Chemicals)
CYTOP: Product name Asahi Glass Co., Ltd. (fluororesin)
Thruria 2320: Product name JGC Catalysts Chemical Co., Ltd. average particle size 60 nm
PL-1: Product name, average particle diameter of 15 nm, manufactured by Fuso Chemical Industry Co., Ltd.

<Creation of lens array>
<Preparation of dispersion for lens composition>
[Preparation of titanium dioxide dispersion (dispersion composition)]
As a circulation type dispersion device (bead mill) for the mixed solution having the following composition, NPM (Nano Disperser for small diameter beads) manufactured by Shinmaru Enterprises Co., Ltd. is used as a dispersion composition. A titanium dioxide dispersion was obtained.
~ Composition ~
-Titanium dioxide (TTO-51 (C) manufactured by Ishihara Sangyo Co., Ltd.): 150.0 parts-The following dispersion resin 1 (20% PGMEA solution with a solid content) described in International Publication No. 2013/0999945 [0386]: 165.0 Parts / Propylene glycol monomethyl ether acetate: 142.5 parts

The dispersing device was operated under the following conditions.
・ Bead diameter: φ0.05mm
・ Bead filling rate: 60% by volume
・ Peripheral speed: 10m / sec
・ Pump supply amount: 30Kg / hour
・ Cooling water: Tap water ・ Bead mill annular passage volume: 1.0L
・ Amount of liquid mixture to be dispersed: 10kg

After the start of dispersion, the average particle size was measured at 30 minute intervals (one pass time). The average particle diameter decreased with the dispersion time (number of passes), and the amount of change gradually decreased. Dispersion was terminated when the average particle size change when the dispersion time was extended by 30 minutes became 5 nm or less. The average particle size of the titanium dioxide particles in this dispersion was about 40 nm.
The average particle diameter of the metal oxide particles (titanium dioxide, etc.) in this example was obtained by diluting a mixed liquid or dispersion containing the metal oxide particles with propylene glycol monomethyl ether acetate, and the resulting diluted liquid (0.2 (Mass%) means a value obtained by measurement using a dynamic light scattering method. For this measurement, Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd. was used, and the obtained number average particle diameter was adopted.

<Preparation of lens composition>
Using the titanium dioxide dispersion (dispersion composition) obtained above, each component was mixed so as to obtain the following composition to obtain a lower layer coating composition.
-Composition of coating composition for lower layer-
-Titanium dioxide dispersion prepared above (dispersion composition) ... 80 parts-Polymerizable compound: JER157S65 (Copolymer 1)
(Japan Epoxy Resin Co., Ltd.) 3.7 parts

<Synthesis of Copolymer 1>
After the atmosphere in the flask was replaced with nitrogen, 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2′-azobisisobutyronitrile was dissolved was charged. Subsequently, 22.5 g of styrene, 15.0 g of methacrylic acid, 51.5 g of dicyclopentanyl methacrylate, and 90.0 g of glycidyl methacrylate were charged, and then gently stirred. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours, and then heated at 90 ° C. for 1 hour to complete the polymerization. Thereafter, the reaction product solution was dropped into a large amount of water to coagulate the reaction product. The coagulated product was washed with water, redissolved in 200 g of tetrahydrofuran, and coagulated again with a large amount of water. After this re-dissolution / coagulation operation was performed three times in total, the obtained coagulated product was vacuum-dried at 60 ° C. for 48 hours to obtain the desired copolymer 1.
-Polymerization initiator: IRGACURE OXE 01
(BASF) ・ ・ ・ 0.1 part

Polymer: A (benzyl methacrylate /
Methacrylic acid copolymer) ... 1.0 part (copolymerization ratio: 80/20 (mass%), weight average molecular weight: 12,000)
・ Surfactant: Megafac F781 (manufactured by DIC Corporation) 0.20 part ・ Solvent: Propylene glycol monomethyl ether acetate 15 parts

<Formation of lens array>
After the lens composition was applied onto a silicon wafer, pre-baking (100 ° C. for 2 min) and post-baking (230 ° C. for 10 min) were performed to form a coating film having a thickness of 1.1 μm (FIG. 3.1).
Furthermore, HPR-204ESZ-9-5 mPa · s (resist solution manufactured by FUJIFILM Electronics Materials (FFEM)) was applied on this so as to have a dry film thickness of 0.8 μm, and heated at 90 ° C. for 1 minute on a hot plate. Heated (Figure 3.2). This coating film is exposed at 300 mJ / cm ² by an i-line stepper (product name: FPA-3000i5 +, manufactured by Canon Inc.) through a mask having a square lattice pattern having a side of 1.4 μm and a gap between patterns of 0.35 μm. did.
This was subjected to paddle development for 60 seconds at room temperature using an alkaline developer HPRD-429E (manufactured by FUJIFILM Electronics Materials Co., Ltd.), and then rinsed in a spin shower using pure water for 20 seconds. Further, after washing with pure water, the substrate was rotated at high speed and dried to form a resist pattern (FIG. 3.3). The resist was shaped into a lens shape by post-baking with a hot plate at 145 ° C. for 120 seconds, 160 ° C. for 120 seconds and 175 ° C. for 120 seconds (FIG. 3.4).

The substrate obtained as described above was subjected to a dry etching process using a dry etching apparatus (manufactured by Hitachi High-Technologies Corporation: U-621) under the following conditions to form a lens array (FIG. 3.5). ). The height of the lens body was 380 nm.
・ RF power: 800W
・ Antenna bias: 400W
・ Wafer bias: 400W
・ Inner chamber pressure: 2Pa
-Substrate temperature: 50 ° C
Mixed gas type and flow rate: CF ₄ / C ₄ F ₆ / Ar = 350/25/800 ml / min Photoresist etching rate: 140 nm / min

<Creation of curing accelerator coating solution>
The components in Table B below were mixed with a stirrer to prepare each composition for curing accelerator in the table.

・ Table comments PGME: Propylene glycol monomethyl ether

Both are silane coupling agents: Shin-Etsu Chemical Co., Ltd.

<Applying coating liquid for curing accelerator>
The prepared lens array substrate was subjected to oxygen ashing treatment under the following conditions for the purpose of purifying and hydrophilizing the surface. The apparatus used was U-621 manufactured by Hitachi High-Technologies Corporation.
・ RF power: 800W
・ Antenna bias: 400W
・ Wafer bias: 400W
・ Inner chamber pressure: 2Pa
-Substrate temperature: 50 ° C
Mixed gas species and flow rate: O ₂ / Ar = 5/800 ml / min. Then, the composition for curing accelerator was applied on the lens array substrate, baked at 100 ° C. for 2 minutes, and the curing accelerator was applied on the lens array. .

<Application of transparent resin coating solution>
The transparent resin coating solution obtained above was applied to the lens array provided with the curing accelerator as described above, and baked at 100 ° C. for 2 minutes. The substrate was immersed in the removal solution shown in the table below for 1 minute, and then dried at high speed. Further, pre-baking (100 ° C. for 2 min) and post-baking (230 ° C. for 10 min) were performed to form a coating film.

CyHx: cyclohexanone TMAH: 2.38 mass% aqueous solution of tetramethylammonium hydroxide PGMEA: propylene glycol monomethyl ether acetate

<Refractive index>
A transparent resin (sample) was applied to a 4-inch wafer with a spine coater (1H-360S (Mikasa Corp.)) at 700 rpm for 10 seconds and 1100 rpm for 30 seconds. Using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.), it was prebaked at 120 ° C. for 3 minutes to obtain a coating film. This coating film was heated on a hot plate in an air atmosphere at 230 ° C. for 5 minutes to obtain a cured film having a thickness of 0.5 μm.
About the obtained cured film, the refractive index in wavelength 633nm in 25 degreeC room temperature was measured using the ellipsometer (made by Otsuka Electronics Co., Ltd.). At this time, the film thickness was also measured.

[Thickness evaluation]
The thickness (Tv) of the concave portion of the lens array and the thickness (Tt) of the convex portion are measured by cross-sectional observation with an electron microscope. The difference (ΔT: Tv−Tt) was calculated. The results were judged as follows. For c02, the transparent resin baking process (100 ° C. for 2 minutes) was omitted.
4: ΔT <0.07 μm
3: 0.07 μm ≦ ΔT <0.15 μm
2: 0.15 μm ≦ ΔT <0.30 μm
1: 0.30 μm ≦ ΔT
0: There is no film on the uneven part of the lens

From the above results, it can be seen that according to the present invention, a transparent resin film substantially corresponding to the shape of the surface can be formed by a coating method on an uneven lens array. FIG. 2 is a sectional view (drawing substitute photograph) showing a part of the lens array produced in the example.

In place of the epoxy resin of Test 101, lens materials employing silicone resin, acrylic resin, novolac resin, sulfide resin, and thiourethane resin were prepared. As a result of evaluating the film thickness in the same manner as in Table 1, it was confirmed that a thin film having a good low refractive index was obtained on the surface of the lens array.
Moreover, it replaces with the alkoxysilane compound which has the said amino group as a silane coupling agent, The alkoxysilane compound which has a glycidyl group, the alkoxysilane compound which has an acryloyl group, the alkoxysilane compound which has a thiol group, The alkoxysilane compound which has a vinyl group The same experiment was conducted using an alkoxysilane compound having a succinimide group and an alkoxysilane compound having a maleimide group. When the same evaluation as in Table 1 was performed, it was confirmed that a good transparent resin thin film without variations was obtained on the lens array surface.

This application claims priority based on Japanese Patent Application No. 2014-155202 filed in Japan on July 30, 2014, which is hereby incorporated herein by reference. Capture as part.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Lens 2a Convex part 2b Concave part 2A Lens array 2Aa Surface of lens array 3 Curing accelerator 4 Transparent resin (coating film)
10 Lens array member 41 Cured transparent resin film (low refractive index film)
41a Surface of transparent resin film 42 Uncured transparent resin film

Claims (21)

1. Providing a curing accelerator on the surface of the lens array having irregularities;
   Applying a transparent resin to the lens array surface provided with the curing accelerator;
   Curing the portion in contact with the curing accelerator for the transparent resin coating film;
   A process for removing an uncured transparent resin.
2. 2. The method of manufacturing a lens array member according to claim 1, wherein a surface shape of the cured transparent resin coating film corresponds to a concavo-convex shape of the underlying lens array.
3. The method for producing a lens array member according to claim 1 or 2, wherein the curing accelerator is a silane coupling agent.
4. The method for producing a lens array member according to any one of claims 1 to 3, wherein the transparent resin contains hollow particles, non-hollow particles, porous particles, or beaded particles.
5. The method of manufacturing a lens array member according to any one of claims 1 to 4, wherein the lenses constituting the lens array are made of resin.
6. 6. The method of manufacturing a lens array member according to claim 5, wherein the resin constituting the lens is a silicone resin, an acrylic resin, a novolac resin, an epoxy resin, a sulfide resin, or a thiourethane resin.
7. The method for manufacturing a lens array member according to any one of claims 1 to 6, wherein the lens array has a structure in which a plurality of convex lenses having a spherical surface are arranged with their protruding directions oriented in the same direction.
8. The method for manufacturing a lens array member according to any one of claims 1 to 7, wherein the unevenness of the lens array is a continuous shape of a spherical convex portion and a V-shaped concave portion formed by a reverse arc.
9. The method for producing a lens array member according to any one of claims 1 to 8, wherein the transparent resin is a siloxane resin or a fluororesin.
10. 10. The curing of the transparent resin coating film is performed by (i) standing at room temperature, (ii) heating, or (iii) irradiating with light. The manufacturing method of the lens array member of a term.
11. The curing accelerator is a silane coupling agent, and the silane coupling agent is an alkoxysilane compound having an amino group, an alkoxysilane compound having a glycidyl group, an alkoxysilane compound having an acryloyl group, or an alkoxysilane compound having a thiol group. The method for producing a lens array member according to any one of claims 3 to 10, which is an alkoxysilane compound having a vinyl group, an alkoxysilane compound having a succinimide group, or an alkoxysilane compound having a maleimide group.
12. The silane coupling agent is γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane. , Γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ- (meth) acryloxypropyltrialkoxysilane, γ- (meth) acryloxypropylalkyldialkoxysilane, γ- 12. The method for producing a lens array member according to claim 11, wherein the lens array member is chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, or vinyltrialkoxysilane.
13. The method for producing a lens array member according to any one of claims 1 to 12, wherein at least one of an organic solvent and an alkaline liquid is used for removing the uncured transparent resin.
14. A lens array member having a transparent resin film on an uneven lens array surface, wherein the transparent resin film is composed of a siloxane resin coating cured film, with a silane coupling agent applied to the lens array surface interposed therebetween A lens array member in which the siloxane resin is cured.
15. 15. The lens array member according to claim 14, wherein a surface shape of the cured transparent resin film corresponds to a concavo-convex shape of the underlying lens array.
16. The lens array member according to claim 14 or 15, wherein a difference between a thickness Tt of the transparent resin film in the convex portion of the lens array and a thickness Tv of the transparent resin film in the concave portion of the lens array is 0.07 µm or less. .
17. A lens unit manufacturing method for manufacturing a lens unit via the manufacturing method according to any one of claims 1 to 13.
18. A method for manufacturing a camera module, wherein the lens unit manufactured by the manufacturing method according to claim 17 is incorporated into a camera module.
19. A lens unit incorporating the lens array member according to any one of claims 14 to 16.
20. A camera module incorporating the lens unit according to claim 19.
21. A kit for forming a transparent resin film on the surface of a lens array through the production method according to any one of claims 1 to 13,
    A kit for manufacturing a lens array member, comprising: a curing accelerator for imparting to the lens array surface; and a transparent resin for imparting to the lens array surface to which the curing accelerator is imparted.

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