JP2008162191A - Optical element manufacturing method - Google Patents

Abstract

The present invention provides a method for producing an optical element having a molded body made of a transparent curable material having a microlens formed on a surface with good reproducibility and having a heat resistant temperature of 200 ° C. or higher.
(A-1) A reversal structure corresponding to a microlens 14 is formed on the surface, and the surface of the mold containing a fluoropolymer is formed on a solution containing a curable substance or from the curable substance. Supplying a liquid to form a layer of the solution or liquid on the surface of the mold, and (b-1) removing the solvent when the layer contains a solvent below the softening temperature of the fluoropolymer, A step of proceeding the curing reaction until the curable substance becomes a curing precursor, and (d-1) a step of separating the curing precursor layer from the mold having the curing precursor layer to obtain a molded body of the curing precursor. (E-1) The manufacturing method of the optical element 10 which has a process which hardens a hardening precursor and obtains the molded object which consists of the transparent hardening substance 16 in which the microlens 14 was formed in the surface.
[Selection] Figure 1

Description

  The present invention relates to a method for manufacturing an optical element having a microlens.

The following method has been proposed as a method for manufacturing an optical element having a microlens and made of a heat-resistant substance.
(1) A method of processing a lens into a round shape and a hemisphere by using the thermal fluidity of the resin by heat flow (Patent Document 1)
(2) A method of forming a microlens by a dry etching technique (Patent Document 2).
(3) A method of forming a microlens by thermal imprint (Patent Document 3).

  However, the method (1) has a problem that the shape of the microlens is limited. In addition, in a microlens array in which a plurality of microlenses are densely arranged, or in a microlens array in which microlenses are overlapped like a compound eye, there is a problem that the microlenses are fused together by heat flow.

  The method (2) is a method for solving the problem of the method (1). However, the method (2) has many steps. Further, depending on the shape of the microlens, there is a problem that the microlens cannot be formed with good reproducibility.

The method (3) requires high temperature and high pressure conditions, and takes a long time for molding, so that the productivity of the optical element is low. In addition, since the heated heat-resistant substance has a high viscosity, the microlens cannot be formed with good reproducibility, and it is difficult to form a microlens of several hundred μm or less.
JP 60-53073 A JP 2006-41467 A JP 2006-45029 A

  It is an object of the present invention to produce an optical element having a molded product having a microlens formed on its surface with good reproducibility and comprising a transparent cured material having a heat-resistant temperature of 200 ° C. or higher. It is to provide a method.

The method for producing an optical element of the present invention comprises a molded body having a microlens formed on a surface thereof, and a molded body made of a transparent curable material having a heat resistant temperature of 200 ° C. or more obtained by curing a curable material. A method for producing an optical element comprising: (a-1) a reversal structure corresponding to the microlens is formed on a surface, and the surface contains a fluorinated polymer; Supplying a solution containing or a liquid comprising the curable substance to form a layer of the solution or liquid on the surface of the mold, and (b-1) below the softening temperature of the fluoropolymer, When the layer contains a solvent, the solvent is removed, and a step of proceeding a curing reaction until the curable substance becomes a curing precursor; (d-1) from the mold having the layer of the curing precursor, Separating the layers Obtaining a molded article of cured precursor, and having a step of obtaining a molded article comprising a transparent cured material by curing (e-1) wherein the curing precursor.
The curing of the curing precursor in the step (e-1) is preferably performed at a temperature higher than the temperature used in the step (b-1).
In the method for producing an optical element of the present invention, a substrate is placed on the surface of the layer of the cured precursor on the mold (c-1) between the step (b-1) and the step (d-1). You may have the process of bonding.

The method for producing an optical element of the present invention comprises a molded body having a microlens formed on a surface thereof, and a molded body made of a transparent curable material having a heat resistant temperature of 200 ° C. or more obtained by curing a curable material. A method of manufacturing an optical element comprising: (a-2) a reversal structure corresponding to the microlens is formed on the surface, and the surface contains a fluoropolymer; Supplying a solution containing or a liquid comprising the curable material to form a layer of the solution or liquid on the surface of the mold, and (b-2) below the softening temperature of the fluoropolymer, If the layer contains a solvent, removing the solvent to make the curable material a transparent cured product; and (d-2) separating the transparent cured material layer from the mold having the transparent cured material layer. Is this transparent curable substance? Characterized by a step of obtaining a made compact.
In the method for producing an optical element of the present invention, a substrate is placed on the surface of the layer of the transparent curable material on the mold (c-2) between the step (b-2) and the step (d-2). You may have the process of bonding.

The transparent curable substance is preferably a silicon oxide polymer having an organic group bonded to a silicon atom by a carbon-silicon bond or a fluorine-containing aromatic polymer.
The transparent cured material is preferably a cured product of a silicone resin, a cured product of a hydrosilation reaction-curable organosilicone, a fluorine-containing polyarylene ether, or a fluorine-containing polyimide.
The fluorine-containing polymer has an amount of fluorine atoms of 35% by mass or more in the fluorine-containing polymer (100% by mass), and a contact angle with respect to water of the film made of the fluorine-containing polymer is 80 ° or more. preferable.
The diameter of the microlens is preferably 300 μm or less.

  According to the method for producing an optical element of the present invention, an optical element having a molded body having a microlens formed on its surface with good reproducibility and made of a transparent curable material having a heat resistant temperature of 200 ° C. or higher. Can be manufactured with high productivity.

  In the present specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas.

<Optical element>
The optical element in the present invention is a molded body having a microlens formed on the surface thereof, and has a molded body made of a transparent curable material having a heat resistant temperature of 200 ° C. or higher obtained by curing a curable material. . FIG. 1 is a cross-sectional view showing an example of an optical element in the present invention. The optical element 10 includes a base material 12 and a molded body made of a transparent cured material 16 bonded to the base material 12 and having a microlens 14 formed on the surface thereof.

(Base material)
The substrate may be provided as necessary, and is not necessarily provided.
Examples of the base material include quartz, glass, ceramics, plastic, rubber, metal, and an organic-inorganic hybrid material described later. In particular, when used for optical applications, a material that transmits 70% or more of light from 380 nm to 2000 nm is desirable. From the viewpoint, quartz, glass, ceramics, and plastic are preferable.
The difference between the refractive index of the substrate and the refractive index of the microlens is preferably in the range of 0 to 0.15 in the wavelength range of light using the optical element of the present invention. When the refractive index difference is in the range of 0 to 0.15, refraction and scattering at the interface between the substrate and the microlens are suppressed, and good characteristics as an optical element can be obtained. The refractive index difference is more preferably in the range of 0 to 0.10, and further preferably in the range of 0 to 0.05.

Examples of the plastic include fluorine resin, silicone resin, acrylic resin, polyester (polyethylene terephthalate (PET), polyethylene naphthalate (PEN), aliphatic polyester, cellulose, polycarbonate, polyimide, polyvinyl alcohol, polylactic acid, and the like.
Examples of the glass include borosilicate glass.
Examples of ceramics include sapphire.

(Molded body)
The molded body is made of a transparent curable material having a heat resistant temperature of 200 ° C. or more obtained by forming a microlens on the surface and curing the curable material.
The heat resistant temperature of 200 ° C. or higher means that no mass reduction is observed up to at least 200 ° C. in thermal mass spectrometry (TGA curve).
The transparent cured material has a light transmittance of 70% or more at a wavelength of 380 to 2000 nm, preferably 75% or more when a layer of a transparent cured material of about 1 μm is produced on a 1 mm thick quartz substrate. Is more preferable.
The transparent cured material obtained by curing the curable material is preferably a material containing an organic group. By including the organic group, the thickness of the molded body can be 100 nm or more.
Examples of the transparent curable substance include a silicon oxide polymer having an organic group bonded to a silicon atom by a carbon-silicon bond, or a fluorine-containing aromatic polymer. As the silicon oxide polymer having an organic group bonded to a silicon atom by a carbon-silicon bond, a cured product of a silicone resin and a cured product of a hydrosilylation reaction curable organosilicone are preferable. As the fluorine-containing aromatic polymer, fluorine-containing polyarylene ether or fluorine-containing polyimide is preferable.

Examples of the shape of the micro lens include a spherical convex lens, a spherical concave lens, an aspheric convex lens, an aspheric concave lens, a Fresnel lens, a ring prism, and a compound eye structure.
The number of microlenses may be one or plural.

The distance between the microlenses is preferably 0 nm to 500 μm, and more preferably 0 nm to 100 μm, at the narrowest distance.
The diameter of the microlens is preferably 100 nm to 500 μm, and more preferably 300 nm to 300 μm.
The height (or depth) of the microlens is preferably 100 nm to 300 μm, and more preferably 300 nm to 100 μm.

(Optical element)
The thickness of the optical element is preferably 0.01 to 10 mm. If the thickness of the optical element is 0.01 mm or more, the mechanical strength is sufficient, it is difficult to deform, and it is easy to handle. If the thickness of the optical element is 10 mm or less, the optical characteristics are not impaired.
Examples of the optical element include a microlens, a microlens array, a cylindrical lens array, and a Fresnel lens.

<Optical element manufacturing method>
Examples of the method for producing the optical element of the present invention include the following two production methods depending on the type of curable substance, the heating temperature of the curable substance, and the like.
(I) A method in which a curing reaction of a curable substance is advanced to form a curing precursor, and then the curing precursor is cured to form a transparent cured substance.
(II) A method in which a curable substance is cured by a single heating to form a transparent curable substance.

Method (I):
The method (I) has the following steps.
(A-1) An inversion structure corresponding to the microlens is formed on the surface, and the surface contains a fluoropolymer, and the surface of the mold is made of the solution containing the curable substance or the curable substance. Supplying liquid to form the solution or liquid layer on the surface of the mold;
(B-1) A step of proceeding a curing reaction until the temperature is lower than the softening temperature of the fluoropolymer and the layer contains a solvent, and the solvent is removed and the curable substance becomes a curing precursor.
(C-1) The process of bonding a base material to the surface of the layer of the said hardening precursor on a mold as needed.
(D-1) A step of separating the cured precursor layer from the mold having the cured precursor layer to obtain a molded body of the cured precursor.
(E-1) A step of obtaining a molded body made of a transparent cured material by curing the curing precursor.

(A-1) Step:
As shown in FIG. 2 (a-1), a reversal structure 22 corresponding to the microlens 14 is formed on the surface, the surface contains a fluoropolymer, and a solution containing a curable substance on the surface of the mold 20 or A liquid made of a curable material (hereinafter also referred to as “solution or liquid”) is supplied to form the solution or liquid layer 30 on the surface of the mold 20.

  Examples of the method for supplying the solution or liquid to the mold 20 include spin coating, dip coating, casting, slit coating, and spray coating. Depending on the curable substance, temperature control (heating, cooling, etc.), humidity control, and atmosphere selection (air, nitrogen atmosphere, etc.) may be required when supplying the solution or liquid. In order to remove bubbles in the solution or liquid layer 30 after supplying the solution or liquid, it is preferable to perform a reduced pressure treatment to 500 mmHg or less.

(mold)
The surface of the mold 20 contains a fluoropolymer. The solution or liquid supplied to the mold 20 may contain not only neutral components but also weakly acidic, weakly basic, or strongly basic components. The solution may contain an organic solvent. The mold 20 is required to have chemical resistance that does not swell or dissolve in such a solution or liquid. Unlike a mold made of polymethyl methacrylate (PMMA), the mold 20 whose surface contains a fluoropolymer has excellent chemical resistance.
The mold 20 may be one in which a substrate is provided on the back surface of the mold main body containing a fluoropolymer, and may be one in which one or more intermediate layers are provided between the mold main body and the substrate. . The mold 20 is preferably a mold in which 1 to 4 intermediate layers are provided between the mold body and the substrate from the viewpoint of cost and interlayer adhesion. Examples of the intermediate layer include a layer made of a fluoropolymer having a reactive group. Examples of the reactive group include a carboxy group, a sulfonic acid group, a group having an ester bond, a hydroxyl group, an amino group, a cyano group, and an isocyanate group, and a carboxy group is preferable.

  As the substrate, quartz, glass; silicone resin, fluororesin having a glass transition temperature higher than the glass transition temperature of the fluoropolymer by 20 ° C., acrylic resin, PET, PEN, aliphatic polyester resin, cellulose, polycarbonate, Polyimide; sapphire, nickel, iron, stainless steel, copper and the like.

As the fluoropolymer, a thermoplastic fluoropolymer is preferable.
As the fluoropolymer, from the viewpoint of releasability, the amount of fluorine atoms is 35% by mass or more in the fluoropolymer (100% by mass), and the contact angle of the film made of the fluoropolymer with respect to water is small. A fluorine-containing polymer having a temperature of 80 degrees or more is preferred. The contact angle with water is measured using a contact angle meter.
The fluorine-containing polymer is preferably a fluorine-containing chain polymer or a fluorine-containing cyclic polymer.

Examples of the fluorine-containing chain polymer include the following copolymers.
Tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer,
Tetrafluoroethylene / ethylene copolymer (hereinafter referred to as ETFE),
Tetrafluoroethylene / hexafluoropropylene copolymer,
Vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer.

As the fluorine-containing chain polymer, ETFE is preferable from the viewpoint of low releasability and easy processing.
As ETFE, the ratio (TFE / E) of repeating units based on tetrafluoroethylene (hereinafter referred to as TFE) to repeating units based on ethylene (hereinafter referred to as E) is 70/30 to 30/70. (Molar ratio) is preferable, and 65/35 to 40/60 (molar ratio) is more preferable.

ETFE may contain repeat units based on other comonomers. Examples of other comonomers include the following compounds.
Fluoroethylenes (excluding TFE): CF ₂ = CFCl, etc.
Fluoropropylenes: CF ₂ = CFCF ₃ , CF ₂ = CHCF ₃ etc.
Fluoroethylenes having a perfluoroalkyl group having 2 to 12 carbon atoms: CF ₃ CF ₂ CF ₂ CF ₂ CH═CH ₂ , CF ₃ CF ₂ CF ₂ CF ₂ CF═CH _2, etc.
^{_{Perfluorovinylethers: R f (OCFXCF 2) k}} OCF = CF 2 ( provided that, ^{R f} is a perfluoroalkyl group having 1 to 6 carbon atoms, X is a fluorine atom or a trifluoromethyl group, k is 0 An integer of ~ 5), etc.
Olefin (excluding E): C3 olefin (propylene, etc.), C4 olefin (butylene, isobutylene, etc.), etc.

As another comonomer, CF ₃ CF ₂ CF ₂ CF ₂ CH═CH ₂ is particularly preferable.
The proportion of repeating units based on other comonomers is preferably 30 mol% or less, more preferably 0.1 to 15 mol%, more preferably 0.2 to 10 mol, out of all repeating units (100 mol%) constituting ETFE. % Is particularly preferred.

  The fluorinated cyclic polymer is a fluorinated polymer having a fluorinated aliphatic ring in the main chain, and one or more carbon atoms constituting the fluorinated aliphatic ring constitute the main chain of the fluorinated polymer. Is a carbon atom. The monomer having the main chain derived from two carbon atoms of the polymerizable double bond of the monomer constituting the fluoropolymer, or having two polymerizable double bonds In the case of a fluorine-containing polymer obtained by cyclopolymerization of benzene, it is derived from 4 carbon atoms of 2 polymerizable double bonds. The atoms constituting the fluorinated aliphatic ring may contain oxygen atoms, nitrogen atoms, etc. in addition to carbon atoms. The fluorine-containing aliphatic ring is preferably a fluorine-containing aliphatic ring having 1 to 2 oxygen atoms. The number of atoms constituting the fluorine-containing aliphatic ring is preferably 4-7. As the polymerizable double bond, a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group are preferable.

Examples of the fluorinated cyclic polymer include homopolymers or copolymers of cyclic monomers, and homopolymers or copolymers obtained by cyclopolymerizing diene monomers.
The cyclic monomer is a monomer having a polymerizable double bond between the carbon atoms constituting the fluorine-containing aliphatic ring, or the carbon atom constituting the fluorine-containing aliphatic ring and the outside of the fluorine-containing aliphatic ring. It is a monomer having a polymerizable double bond with a carbon atom.
The diene monomer is a monomer having two polymerizable double bonds.

The cyclic monomer and the diene monomer are monomers having a fluorine atom, and the number of fluorine atoms bonded to the carbon atom relative to the total number of hydrogen atoms bonded to the carbon atom and fluorine atoms bonded to the carbon atom. A monomer having a ratio of 80% or more is preferable, and a perfluoromonomer (a monomer having a ratio of 100%) is more preferable.
The cyclic monomer and the diene monomer may be a perhalopolyfluoromonomer in which 1 to 4 fluorine atoms of the perfluoromonomer are substituted with chlorine.
The monomer to be copolymerized with the cyclic monomer and the diene monomer is also preferably a perfluoromonomer or a perhalopolyfluoromonomer.

  As the cyclic monomer, compound (1) or compound (2) is preferable.

However, X < ¹¹ >, X <^12> , R < ¹¹ > and R < ¹² > are respectively a fluorine atom, a C1-C4 perfluoroalkyl group, or a C1-C4 perfluoroalkoxy group. X ¹¹ is preferably a fluorine atom. X ¹² is preferably a fluorine atom, a trifluoromethyl group, or a perfluoroalkoxy group having 1 to 4 carbon atoms.
X ²¹ and X ²² are each a fluorine atom or a C 1-7 perfluoroalkyl group. X ²¹ and X ²² are preferably a fluorine atom or a trifluoromethyl group.

  Specific examples of compound (1) include compounds (1-1) to (1-3).

  Specific examples of compound (2) include compounds (2-1) to (2-2).

The following compounds are mentioned as a monomer copolymerized with a cyclic monomer.
CF ₂ = CF ₂ ,
CF ₂ = CFCl,
CF ₂ = CFOCF ₃ etc.

As the diene monomer, the compound (3) is preferable.
_{CF 2 = CF-Q-CF} = CF 2 ··· (3).
However, Q is a C1-C3 perfluoroalkylene group which may have an etheric oxygen atom. In the case of a perfluoroalkylene group having an etheric oxygen atom, the etheric oxygen atom in the perfluoroalkylene group may be present at one end of the group, and is present at both ends of the group. Or may be present between the carbon atoms of the group. From the viewpoint of cyclopolymerizability, it is preferably present at one end of the group.

  A polymer having repeating units of the following formulas (3-1) to (3-4) is obtained by cyclopolymerization of the compound (3).

Specific examples of the diene monomer include the following compounds.
CF ₂ = CFOCF ₂ CF = CF ₂ ,
CF ₂ = CFOCF (CF ₃ ) CF═CF ₂ ,
CF ₂ = CFOCF ₂ CF ₂ CF = CF ₂ ,
CF ₂ = CFOCF ₂ CF (CF ₃ ) CF═CF ₂ ,
CF ₂ = CFOCF (CF ₃ ) CF ₂ CF = CF ₂ ,
CF ₂ = CFOCF ₂ OCF = CF ₂ ,
_{CF 2 = CFOC (CF 3)} 2 OCF = CF 2,
CF ₂ = CFCF ₂ CF = CF ₂ ,
_{CF 2 = CFCF 2 CF 2 CF} = CF 2 , and the like.

Examples of the monomer copolymerized with the diene monomer include the compound (1), the compound (2), and the following compounds.
CF ₂ = CF ₂ ,
CF ₂ = CFCl,
CF ₂ = CFOCF ₃ etc.

  The fluorinated cyclic polymer preferably contains 20 mol% or more, more preferably 40 mol% or more of the repeating units having a fluorinated aliphatic ring, out of all repeating units (100 mol%), and more preferably contains fluorinated fat. It is particularly preferred that it consists only of repeating units having a group ring. The repeating unit having a fluorinated alicyclic ring is a repeating unit formed by polymerization of a cyclic monomer and a repeating unit formed by cyclopolymerization of a diene monomer.

  As the fluorine-containing polymer, an amorphous or amorphous perfluoropolymer is preferable from the viewpoint of excellent releasability from the curing precursor, and a perfluoropolymer obtained by treating the perfluoropolymer with a fluorine gas is preferable. More preferred.

(Mold manufacturing method)
As a manufacturing method of the mold 20, a nanoimprint method or a casting method using a master mold in which a fine structure corresponding to the reversal structure 22 of the mold 20 (that is, a convex portion or a concave portion having the same shape as the microlens) is formed on the surface. Etc.

Examples of the nanoimprint method include a method having the following steps.
(X-1) A step of thermocompression bonding the surface of the master mold and a film containing a thermoplastic fluoropolymer to form the inversion structure 22 on the film.
(X-2) The process of isolate | separating the film | membrane containing a master mold and a thermoplastic fluoropolymer.

Examples of the casting method include a method having the following steps.
(Y-1) The process of apply | coating the solution of a fluoropolymer to the surface of a master mold.
(Y-2) A step of drying the fluoropolymer solution to form a layer made of the fluoropolymer.
(Y-3) The process of isolate | separating the layer which consists of a master mold and a fluoropolymer.

  Examples of the master mold material include silicon, nickel, copper, titanium, stainless steel, quartz, glass, and polydimethylsiloxane.

(Curable material)
The curable substance is a substance that can be cured by heat or light to form a transparent curable substance.
Examples of the curable substance include a curable substance capable of forming a silicon oxide polymer having an organic group bonded to a silicon atom by a carbon-silicon bond (hereinafter, also simply referred to as a silicon oxide polymer), or a fluorine-containing aromatic. Examples thereof include curable substances capable of forming a group-based polymer.

(Silicon oxide polymer)
The curable substance capable of forming a silicon oxide polymer is at least one selected from the group consisting of organically modified alkoxysilanes, organically modified chlorosilanes, and organically modified silicon-containing polymers, or organically modified alkoxysilanes, organically modified chlorosilanes, and organics. One or more kinds of reactants selected from the group consisting of modified silicon-containing polymers can be mentioned. The reaction product is prepared by adding water, an organic solvent, a pH adjuster, a hydrolysis catalyst, or a polymerization reaction stabilizer to one or more selected from the group consisting of an organic modified alkoxysilane, an organic modified chlorosilane, and an organic modified silicon-containing polymer. It was added and reacted. The reaction is carried out under conditions such as cooling, heating, pressurization, reduced pressure, air, nitrogen atmosphere and the like as necessary.

  Examples of the organically modified alkoxysilane include dimethyldiethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, p-styryltriethoxysilane, methylphenyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-a Nopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyltriethoxysilane, ethoxy groups of these compounds as other alkoxy groups (methoxy groups, etc.) Etc.

  Examples of the organically modified chlorosilane include those in which the alkoxy group of the organically modified alkoxysilane is a chlorine atom.

Organic modified silicon-containing polymers are polysiloxanes, polysilanes, polysilazanes, polycarbosilanes, polyaluminosiloxanes, polytitanosiloxanes, polyborosiloxanes, polyaluminosilazanes, polytitanosilazanes, Polyborosilazanes and copolymers of these silicon-containing polymers.
As the organically modified silicon-containing polymer, polysiloxanes having a reactive functional group are preferable. Examples of the reactive functional group include a hydrosilyl group, a vinyl group, a silanol group, an alkoxysilyl group, a methacryl group, and an epoxy group.

The curable substance that can form the silicon oxide-based polymer may contain inorganic fine particles. By including the inorganic fine particles, the refractive index of the transparent curable material can be controlled, and the strength of the transparent curable material can be improved.
Examples of the inorganic fine particles include oxide fine particles (silica, titania, zirconia, ceria, tin oxide, zinc oxide, etc.).

The primary particle diameter of the inorganic fine particles by electron microscope observation is preferably 100 nm or less. When the primary particle diameter of the inorganic fine particles is 100 nm or less, a decrease in the transmittance of the microlens due to light scattering can be suppressed.
The curable substance that can form the silicon oxide polymer may contain a metal alkoxide, a metal chelate compound, a metal acylate compound, an inorganic metal salt, an inorganic metal complex, and the like.

If necessary, water, an organic solvent, a curing accelerator, a polymerization reaction stabilizer, an additive, and the like may be added to the curable substance that can form the silicon oxide-based polymer.
The organic solvent is selected in consideration of the reactivity of the raw material of the curable substance capable of forming the silicon oxide-based polymer, solubility, stability, and applicability of the solution containing the curable substance.

Examples of the organic solvent include the following organic solvents.
Alcohols: methanol, ethanol, etc.
Ketones: acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
Esters: ethyl acetate, propyl acetate, butyl acetate, etc.
Glycol ethers: ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, etc.
Glycol ether esters: Diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc.
Nitrogen-containing polar solvents: N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc.
Aromatic hydrocarbons: toluene, xylene and the like.

When a curing accelerator is added, the strength of the silicon oxide polymer can be improved even when cured at a low temperature.
Examples of the additive include a leveling agent, an antifoaming agent, a dispersant, and a viscosity modifier.

When the curable substance capable of forming the silicon oxide-based polymer is a liquid, it may be supplied to the surface of the mold 20 as it is, or may be supplied as a solution containing the curable substance.
The solid content concentration of a solution containing a curable substance capable of forming a silicon oxide polymer is preferably 2% by mass or more in terms of silicon oxide polymer. If the solid content concentration of the solution is 2% by mass or more, the coating efficiency is good. The upper limit of the solid content concentration may be 100% by mass as long as the solution can be applied satisfactorily.

  The surface tension of a solution containing a curable substance capable of forming a silicon oxide polymer or a liquid made of the curable substance is preferably 10 to 30 mN / m, more preferably 12 to 27 mN / m, and 14 to 24 mN / m. Particularly preferred. If the surface tension of the solution or liquid is 10 mN / m or more, the solution or liquid layer 30 can be easily obtained. If the surface tension of the solution or liquid is 30 mN / m or less, the mold 20 can be applied uniformly without repelling the solution or liquid. In order to reduce the surface tension of the solution or liquid, a fluorine-based surfactant or a silicone-based surfactant may be added. The surface tension is determined by the ring method.

(Fluorine-containing polyarylene ether)
Examples of the curable substance capable of forming the fluorinated polyarylene ether include a prepolymer obtained by subjecting the following compound (A), compound (B) and compound (C) to a condensation reaction in the presence of a deHF agent.

  The compound (A) is a compound (A-1) having a crosslinkable functional group and a phenolic hydroxyl group and / or a compound (A-2) having a crosslinkable functional group and a fluorine atom-substituted aromatic ring.

  Crosslinkable functional groups include vinyl, allyl, methacryloyl (oxy), acryloyl (oxy), ethynyl, vinyloxy, trifluorovinyl, trifluorovinyloxy, cyano, alkoxysilyl, and diaryl. Hydroxymethyl group, hydroxyfluorenyl group, etc. are mentioned. High reactivity and high crosslink density can be obtained. Ethynyl group, vinyl group, methacryloyl (oxy) group, acryloyl (oxy) group, trifluorovinyloxy Groups are preferred.

Examples of the compound (A-1) include a compound having one phenolic hydroxyl group and a compound having two phenolic hydroxyl groups.
Examples of the compound having one phenolic hydroxyl group include the following compounds.
Phenols having a polymerizable double bond: 4-hydroxystyrene, etc.
Ethynylphenols: 3-ethynylphenol, 4-phenylethynylphenol, 4- (4-fluorophenyl) ethynylphenol and the like.

Examples of the compound having two phenolic hydroxyl groups include the following compounds.
Bis (phenylethynyl) dihydroxybiphenyls: 2,2′-bis (phenylethynyl) -5,5′-dihydroxybiphenyl, 2,2′-bis (phenylethynyl) -4,4′-dihydroxybiphenyl, etc.
Dihydroxydiphenylacetylenes: 4,4′-dihydroxytolane, 3,3′-dihydroxytolane and the like.

Examples of the compound (A-2) include compounds having a perfluoroaromatic ring such as perfluorophenyl and perfluorobiphenyl.
Examples of the compound having a perfluoroaromatic ring include the following compounds.
Fluorine-containing aryls having a polymerizable double bond: pentafluorostyrene, pentafluorobenzyl acrylate, pentafluorobenzyl methacrylate, pentafluorophenyl acrylate, pentafluorophenyl methacrylate, perfluorostyrene, pentafluorophenyl trifluorovinyl ether, 3- ( Pentafluorophenyl) pentafluoropropene-1, etc.
Fluorine-containing aryls having a cyano group: pentafluorobenzonitrile, etc.
Fluorine-containing arylacetylenes: pentafluorophenylacetylene, nonafluorobiphenylacetylene, etc.
Fluorinated diarylacetylenes: phenylethynylpentafluorobenzene, phenylethynylnonafluorobiphenyl, decafluorotolane and the like.

  The compound (B) is a fluorine-containing aromatic compound. A compound (4) is mentioned as a compound (B).

However, i is an integer of 0 to 2, j is an integer of 0 to 3, k is an integer of 0 to 3, and R ^f1 and R ^f2 each contain 1 to 8 carbon atoms. It is a fluorine alkyl group.

Compound (C) is a polyfunctional phenol having 3 or more phenolic hydroxyl groups.
Examples of polyfunctional phenols having 3 or more phenolic hydroxyl groups include trihydroxybenzene, trihydroxybiphenyl, trihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) ethane, and tris (4-hydroxyphenyl) benzene. , Tetrahydroxybenzene, tetrahydroxybiphenyl, tetrahydroxybinaphthyl, and tetrahydroxyspiroindanes.

The solution containing a curable substance capable of forming a fluorinated polyarylene ether is obtained by dissolving the prepolymer in an organic solvent.
Examples of the organic solvent include propylene glycol monomethyl ether acetate, cyclopentanone, cyclohexanone, toluene, xylene, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, dimethylsulftetrahydrofuran, dioxane, Examples include diglyme, ethyl lactate, ethyl benzoate, and butyl benzoate.

(Fluorine-containing polyimides)
Examples of curable substances that can form fluorine-containing polyimides include fluorine-containing polyamic acid. The fluorine-containing polyamic acid is converted into a fluorine-containing polyimide by producing an imide during the curing process.

  The solution containing the fluorine-containing polyamic acid is prepared by mixing and reacting an acid monomer (tetracarboxylic acid, its acid anhydride, acid chloride, esterified product) and a diamine monomer in an organic solvent. However, at least one of the acid anhydride monomer and the diamine monomer is a fluorine-containing compound.

  As the fluorine-containing monomer, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 1-fluoropyromellitic acid, 1,4-difluoropyromellitic acid, 1-trifluoromethylpyromellitic acid, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene, 2,2′-difluoro-3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,2′-bis (trifluoromethyl) -3,3 ′, 4,4′-biphenyltetracarboxylic acid, their acid anhydrides, acid chlorides, esterified compounds, etc. Is mentioned.

  Examples of the fluorine-containing diamine monomer include 2,2-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 3-fluoro-1,2-phenylenediamine, 4-fluoro-1,2-phenylenediamine, 3, 4-difluoro-1,2-phenylenediamine, 3-fluoro-1,3-phenylenediamine, 4-fluoro-1,3-phenylenediamine, 3,4-difluoro-1,3-phenylenediamine, 3-fluoro- 1,4-phenylenediamine, 4-fluoro-1,4-phenylenediamine, 3,4-difluoro-1,4-phenylenediamine, 3-trifluoromethyl-1,2-phenylenediamine, 4-trifluoromethyl- 1,2-phenylenediamine, 3-trifluoromethyl-1,3-phenylenediamine, 4-trifluoro Methyl-1,3-phenylenediamine, 3-trifluoromethyl-1,4-phenylenediamine, 4-trifluoromethyl-1,4-phenylenediamine, 2,2 ′-(bistrifluoromethyl) -4,4 ′ -Diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl and the like.

As the acid anhydride monomer and diamine monomer, a monomer containing no fluorine may be used.
An acid anhydride monomer may be used individually by 1 type, and may be used in combination of 2 or more type.
A diamine monomer may be used individually by 1 type, and may be used in combination of 2 or more type.
It is preferable that the number of moles of the acid anhydride monomer (the total number of moles in the case of two or more) and the number of moles of the diamine monomer (the total number of moles in the case of two or more) are substantially equal.

Examples of the organic solvent for the fluorine-containing polyamic acid solution include polar organic solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamide.
The solid content concentration of the fluorine-containing polyamic acid solution is preferably 5 to 40% by mass, and more preferably 10 to 25% by mass.

(B-1) Step:
As shown in FIG. 2 (b-1), when the solution or liquid layer 30 contains a solvent at a temperature lower than the softening temperature of the fluoropolymer, the solvent is removed, and the curable substance becomes a curing precursor 32. The curing reaction is advanced until it becomes (pre-bake).
The prebaking temperature is preferably lower by 10 ° C. or more than the softening temperature of the fluoropolymer contained in the mold 20. The softening temperature means a glass transition temperature when the fluoropolymer is non-crystalline, and means a melting temperature when the fluoropolymer is crystalline.

  The curing precursor 32 is a state in which part or all of the organic solvent contained in the solution containing the curable substance is volatilized; the state in which the curable substance is semi-cured; or the organic solvent contained in the solution containing the curable substance. A part or all of them are volatilized and the curable substance is semi-cured. The semi-cured state is preferably a finger touch drying of the paint according to JIS standard (a state where the fingertip is not soiled by the paint by touching the center of the painted surface).

During pre-baking, ultraviolet ray irradiation, microwave irradiation, ozone treatment, plasma treatment, or the like may be performed to accelerate curing of the refractory material.
Depending on the heat-resistant material, it may be necessary to control humidity and select an atmosphere (air, nitrogen atmosphere, etc.) during pre-baking.

  The step (a-1) and the step (b-1) may be repeated twice or more to form two or more layers of the curing precursor 32. The two or more layers of the curing precursor 32 may be layers of the same component or may be layers of different components. The layer of the curing precursor 32 may be a porous layer. Further, the porous layer may be impregnated with a solution containing a curable substance or a liquid made of a curable substance.

Step (c-1):
As shown in FIG. 2 (c-1), the base material 12 is bonded to the surface of the layer of the curing precursor 32 on the mold 20.
Step (c-1) may be omitted. For example, if the thickness of the curing precursor 32 is 100 μm or more, the substrate 12 is not necessary.

As a bonding method, a method of heat-pressing the curing precursor 32 and the base material 12; a method of applying the curable substance to the surface of the base material 12 and / or the curing precursor 32, and pressure-bonding at a temperature or room temperature; And a method using an agent.
The temperature at the time of bonding is preferably 10 ° C. or more lower than the softening temperature of the fluoropolymer contained in the mold 20.
The pressure at the time of bonding is preferably 10 MPa or less.

Step (d-1):
As shown in FIG. 2 (d-1), the cured precursor 32 layer is separated from the mold 20 having the cured precursor 32 layer to obtain a molded body of the cured precursor 32.

Step (e-1):
As shown in FIG. 2 (e-1), the curing precursor 32 is completely cured to obtain a molded body made of a transparent cured material 16 having a microlens 14 formed on the surface (firing).
The curing of the curing precursor 32 in the step (e-1) is preferably performed at a temperature higher than the temperature used in the step (b-1).
The firing temperature is preferably 50 to 500 ° C., and particularly preferably 100 to 400 ° C. from the viewpoint of productivity and curability.

At the time of firing, ultraviolet curing, microwave irradiation, ozone treatment, plasma treatment or the like may be performed to accelerate the curing of the curing precursor 32.
During firing, the atmosphere may be changed from the air or nitrogen atmosphere to another atmosphere. As another atmosphere, an atmosphere of oxygen, hydrogen, ammonia, water vapor, or the like can be given.

Method (II):
The method (II) has the following steps.
(A-2) A reversal structure corresponding to the microlens is formed on the surface, and the surface contains a fluoropolymer, and the surface of the mold is made of the solution containing the curable substance or the curable substance. Supplying liquid to form the solution or liquid layer on the surface of the mold;
(B-2) A step of removing the solvent when the layer contains a solvent at a temperature lower than the softening temperature of the fluoropolymer to make the curable substance a transparent cured product.
(C-2) The process of bonding a base material to the surface of the layer of the said transparent hardening substance on a mold as needed.
(D-2) A step of separating the transparent cured material layer from the mold having the transparent cured material layer to obtain a molded body of the transparent cured material.

(A-2) Process:
As shown in FIG. 3 (a-2), a reversal structure 22 corresponding to the microlens 14 is formed on the surface, the surface contains a fluoropolymer, and a solution containing a curable substance on the surface of the mold 20 or A liquid made of a curable material is supplied to form the solution or liquid layer 30 on the surface of the mold 20.
The step (a-2) is performed in the same manner as the step (a-1).

As the mold 20, the same mold as that in the step (a-1) may be used.
As a liquid containing a curable substance or a liquid made of a curable substance, a liquid containing a curable substance that can be completely cured below the softening temperature of the fluoropolymer is used. Examples of the curable substance include a case where the organic component has a high curable substance content among the curable substances capable of forming the silicon oxide polymer. Preferably, a curable material capable of forming a transparent curable material having a carbon atom ratio of 20% by mass or more with respect to all elements constituting the transparent curable material.
When the solution containing a curable substance contains an organic solvent, it is preferable to use an organic solvent having a boiling point lower than the softening temperature of the fluoropolymer.

(B-2) Step:
As shown in FIG. 3 (b-2), when the solution or the liquid layer 30 contains a solvent at a temperature lower than the softening temperature of the fluoropolymer, the solvent is removed, and the curable substance is made into a transparent cured product. A molded body made of the transparent cured material 16 having the microlenses 14 formed thereon is obtained (firing).
The firing temperature is preferably a temperature that is at least 10 ° C. lower than the softening temperature of the fluoropolymer contained in the mold 20.

At the time of baking, ultraviolet ray irradiation, microwave irradiation, ozone treatment, plasma treatment, or the like may be performed to accelerate curing of the heat-resistant material.
Depending on the heat-resistant material, it may be necessary to control humidity and select an atmosphere (air, nitrogen atmosphere, etc.) during firing.

  The step (a-2) and the step (b-2) may be repeated twice or more to form two or more layers of the transparent curable material 16. The two or more layers of the transparent curable material 16 may all be layers of the same component, or may be layers of different components. The layer of transparent curable material 16 may be a porous layer.

Step (c-2):
As shown in FIG. 3 (c-2), the substrate 12 is bonded to the surface of the layer of the transparent curable material 16 on the mold 20.

Step (c-2) may be omitted. For example, if the thickness of the transparent curable material 16 is 100 μm or more, the substrate 12 is not necessary.
Examples of the bonding method include a method using an adhesive.

Step (d-2):
As shown in FIG. 3 (d-2), the layer of the transparent curable material 16 is separated from the mold 20 having the layer of the transparent curable material 16 to obtain a molded body made of the transparent curable material 16.

  In the manufacturing method of the optical element of the present invention described above, since a mold containing a fluorine-containing polymer having excellent durability, dimensional accuracy, chemical resistance and releasability is used on the surface, a microlens is formed on the surface. Can be produced with good productivity, which has a molded body made of a transparent cured material having a heat resistant temperature of 200 ° C. or higher.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
Examples 1 to 5 and 9 are production examples, Examples 6 to 8, 11 and 12 are examples, and Example 10 is a comparative example.

(Intrinsic viscosity)
About the polymer, the intrinsic viscosity in 30 degreeC was measured in perfluoro (2-butyltetrahydrofuran) using the viscometer (the Toki Sangyo company make, TV-20 type | mold).

(Glass-transition temperature)
For the polymer, using a thermogravimetric measuring device (TG-DTA2000, manufactured by Mac Science Co., Ltd.) by differential scanning calorimetry (DSC) from 40 ° C. to 400 ° C. under a nitrogen atmosphere under a temperature rising rate of 10 ° C./min. A scan was performed to measure the glass transition temperature.

(Light transmittance)
The polymer was processed into a film having a thickness of 100 μm, and the light transmittance at a wavelength of 360 to 500 nm was measured using an ultraviolet to near infrared spectrophotometer (manufactured by Shimadzu Corporation, UV-3100).

(Contact angle)
The contact angle with respect to water was measured using a contact angle meter (CA-X150 type, manufactured by Kyowa Interface Science Co., Ltd.) with about 20 μL of water droplets deposited on the surface of the measurement object.

(Inversion structure and microlens dimensions)
About the dimensions (height (depth), width, interval) of the reversal structure (concave part) of the mold and the microlens (convex part) of the optical element, a reversal structure was used using a laser microscope (manufactured by Keyence Corporation, VK-9500). Or the dimension of the microlens was measured.

(chemical resistance)
Two molds were prepared, one mold was immersed in dilute hydrochloric acid (pH 1) for 1 hour, and the other mold was immersed in a 5% aqueous sodium hydroxide solution (pH 14) for 1 hour. Each mold was evaluated according to the following criteria.
○: Corrosion or dissolution is not observed.
X: Corrosion or dissolution is observed.

(Releasability)
The mold releasability when manufacturing the optical element was evaluated according to the following criteria.
○: It is confirmed that the releasability is good and the microlens is formed.
X: Adhering without releasing.

(Heatproof temperature)
About an optical element, the temperature rising rate in the mixed gas (oxygen 21 mass%) atmosphere of oxygen and nitrogen from 40 degreeC to 400 degreeC by thermogravimetric analysis using a thermogravimetric measuring apparatus (the Mac Science company make, TG-DTA2000). Scanning was performed at 10 ° C./min. When the obtained TGA curve does not show a mass reduction to at least 200 ° C., the heat-resistant temperature of the transparent cured material is 200 ° C., and when the mass loss is not found to at least 300 ° C. in the TGA curve, the transparent cure The heat resistance temperature of the compact of the substance was set to 300 ° C.
(transparency)
A layer of transparent cured material (thickness: about 1 μm) is prepared on a quartz substrate (20 mm square, 1 mm thick), and the wavelength is measured using an ultraviolet to near infrared spectrophotometer (manufactured by Shimadzu Corporation, UV-3100). The light transmittance at 380 to 2000 nm was measured.

[Example 1]
Production of polymer (P):
In an autoclave (made of pressure-resistant glass), 100 g of CF ₂ = CFOCF ₂ CF ₂ CF = CF ₂ , 0.5 g of methanol, and 0.7 g of [(CH ₃ ) ₂ CHOCO] ₂ are added, and suspension polymerization is performed. A polymer (P) was obtained.
The polymer (P) is a polymer composed of repeating units represented by the following formula (p). The intrinsic viscosity of the polymer (P) was 0.34 dl / g, and the glass transition temperature was 108 ° C.

[Example 2]
Production of polymer (P1):
The polymer (P) was put into an autoclave (made of nickel, internal volume 1 L), and the inside of the autoclave was replaced with nitrogen gas three times, and then the pressure was reduced to 4.0 kPa (absolute pressure). After introducing fluorine gas diluted to 14 volume% with nitrogen gas into the autoclave up to 101.3 kPa, the internal temperature of the autoclave was maintained at 230 ° C. for 6 hours. The contents of the autoclave were recovered to obtain a polymer (P1) having a fluorinated aliphatic ring in the main chain and having no reactive group.
As a result of measuring the infrared absorption spectrum of the polymer (P1), no peak attributable to the carboxy group was confirmed. The light transmittance of the polymer (P1) is 95% or more, the amount of fluorine atoms is 68% by mass in the polymer (P1) (100% by mass), and the water of the film made of the polymer (P1) The contact angle with respect to was 115 degrees.

Preparation of composition (C1):
A perfluorotributylamine solution containing 9% by mass of the polymer (P1) was prepared, and the solution was filtered through a membrane filter (polytetrafluoroethylene, pore size 0.2 μm) to obtain a composition (C1).

[Example 3]
Production of polymer (P2):
The polymer (P) was heat-treated at 300 ° C. for 1 hour in a hot-air circulating oven under an atmospheric pressure atmosphere. Then, it was immersed in ultra pure water at 110 ° C. for 1 week. The polymer was dried in a vacuum dryer at 100 ° C. for 24 hours to obtain a polymer (P2) having a fluorinated aliphatic ring in the main chain and a reactive group (carboxy group).

  As a result of measuring the infrared absorption spectrum of the polymer (P2), a peak attributable to the carboxy group was confirmed. The light transmittance of the polymer (P2) is 93% or more, the amount of fluorine atoms is 68% by mass in the polymer (P2) (100% by mass), and the water of the film made of the polymer (P2) The contact angle with respect to was 115 degrees.

Preparation of composition (C2):
A perfluorotributylamine solution containing 1% by mass of the polymer (P2) was prepared, and the solution was filtered through a membrane filter (polytetrafluoroethylene, pore size 0.2 μm) to obtain a composition (C2).

[Example 4]
Production of mold 1:
A nickel master mold (length 10 mm × width 10 mm × thickness 5 mm) shown in FIG. 4 was prepared. The master mold has five convex portions (diameter 220 μm, height 30 μm, interval 40 μm) having the same shape as the microlens (spherical convex lens). Moreover, the area | region where the convex part in this master mold was formed is 0.72 mm long and 0.72 mm wide.

  The composition (C1) was applied to the surface of the master mold and held for 5 minutes in a state where the pressure was reduced to 13 kPa. Then, it is heated and dried at 180 ° C. for 1 hour to volatilize perfluorotributylamine in the composition (C1), and a layer (thickness of about 1 μm) made of the polymer (P1) is formed on the surface of the master mold. Formed.

  Next, the composition (C2) is applied to the surface of the layer made of the polymer (P1) with a spin coater, and is heated and dried at 180 ° C. for 1 hour to obtain perfluorotributylamine in the composition (C2). Was volatilized to form a layer (thickness of about 0.05 μm) made of the polymer (P2) on the surface of the layer made of the polymer (P1).

  Subsequently, an ethanol solution containing 0.5% by mass of an amino group-containing silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) and 5% by mass of water is composed of the polymer (P2) with a spin coater. After applying to the surface of the layer and washing with water, the surface treatment was performed by heating and drying at 70 ° C. for 1 hour.

  After 0.5 g of an adhesive (Aron Alpha (registered trademark) manufactured by Toagosei Co., Ltd.) is quickly applied to the surface treated with a silane coupling agent, a glass plate (length 20 mm × width 20 mm × thickness 1.3 mm) ) And the glass plate and the layer made of the polymer (P2) were adhered.

The glass plate and the master mold were separated to obtain a mold 1 in which a reversal structure (concave portion) corresponding to the microlens (convex portion) was formed on the surface of the mold body made of a fluoropolymer on the glass plate.
The dimensions of the inverted structure of the mold 1 were measured to evaluate chemical resistance. The results are shown in Table 1.

[Example 5]
Production of mold 2:
A bank was provided on the periphery of the same master mold as in Example 4 using a work free seal (manufactured by ASONE). The composition (C1) was supplied to the inside of the bank and held for 5 minutes in a state where the pressure was reduced to 13 kPa. Then, it is heated and dried at 180 ° C. for 4 hours to volatilize perfluorotributylamine in the composition (C1), and a layer (thickness of about 250 μm) made of the polymer (P1) is formed on the surface of the master mold. Formed.

The layer made of the polymer (P1) and the master mold were separated to obtain a mold 2 in which a reversal structure (concave portion) corresponding to the microlens (convex portion) was formed on the mold surface made of the fluoropolymer.
The dimensions of the reversal structure of the mold 2 were measured to evaluate chemical resistance. The results are shown in Table 1.

[Example 6]
Production of optical element 1:
On the surface of the mold 1, 2.0 g of liquid glass (composition containing Apollolink, TGA-CP210, organically modified silicon-containing polymer, tetraethoxysilane, dibutyltin diacetate, isopropyl alcohol, and methanol) was applied. With the pressure reduced to 13 kPa, the mold 1 was held at 40 ° C. for 1 hour, and the curing reaction of the liquid glass was advanced to obtain a curing precursor.

Next, the decompression is released, an adhesive (manufactured by Toto Kagaku Kogyo Co., Ltd., Beston) is applied to the surface of the curing precursor, and a glass plate (length 30 mm × width 30 mm × thickness 1.3 mm) is adhered thereon, It was left at room temperature for 9 hours.
Next, the cured precursor and the mold 1 are separated, and the cured precursor is heated at 140 ° C. for 30 minutes to be completely cured, and microlenses (convex parts) are formed on the surface of the molded body made of a transparent cured material. The formed optical element 1 was obtained. The heat resistance temperature of the molded body was 200 ° C.
The releasability of the optical element 1 was evaluated, and the dimensions of the microlens were measured. The results are shown in Table 2.
When the transparency of the transparent curable material forming the optical element 1 was measured, it was 85% or more.

[Example 7]
Production of optical element 2:
A liquid glass (2.0 g of Apollolink: TGA-CP210) was applied to the surface of the mold 2. With the pressure reduced to 13 kPa, the mold 2 was held at 40 ° C. for 1 hour, and the curing reaction of the liquid glass was advanced to obtain a curing precursor.

Next, the decompression is released, an adhesive (manufactured by Toto Kagaku Kogyo Co., Ltd., Beston) is applied to the surface of the curing precursor, and a glass plate (length 30 mm × width 30 mm × thickness 1.3 mm) is adhered thereon, It was left at room temperature for 9 hours.
Next, the curing precursor and the mold 2 are separated, and the curing precursor is heated at 140 ° C. for 30 minutes to be completely cured, and microlenses (convex portions) are formed on the surface of the molded body made of a transparent cured material. The formed optical element 2 was obtained. The heat resistance temperature of the molded body was 200 ° C.
The releasability of the optical element 2 was evaluated, and the dimensions of the microlens were measured. The results are shown in Table 2.
When the transparency of the transparent curable material forming the optical element 2 was measured, it was 85% or more.

[Example 8]
Production of optical element 3:
In a 50 mL two-necked flask equipped with a Dimroth condenser and a stirrer chip, 1.15 g (0.006 mol) of pentafluorophenylacetylene, 0.65 g (0.005 mol) of 1,3,5-trihydroxybenzene, 2.00 g (0.006 mol) of perfluorobiphenyl and 34.22 g of N, N-dimethylacetamide as a solvent were added.
While stirring in the flask, heat to 60 ° C. on an oil bath, and 3.23 g (0.03 mol) of sodium carbonate as a de-HF agent is quickly put into the flask, and the flask is stirred at 60 ° C. Heated for 22 hours.

The reaction solution was cooled to room temperature, and the reaction solution was gradually added to 150 mL of vigorously stirred 0.5N aqueous hydrochloric acid to precipitate a fine brown powder. The fine brown powder was collected by filtration, washed twice with pure water, and then vacuum-dried at 80 ° C. for 12 hours to obtain 2.58 g of a prepolymer (white gray powder).
The prepolymer was dissolved in cyclohexanone to obtain a 20% by mass prepolymer solution. The solution was filtered through a filter (manufactured by polytetrafluoroethylene, pore size 0.5 μm) to obtain Liquid 1.

The liquid material 1 was applied to the surface of the mold 2. With the pressure reduced to 13 kPa, the mold 2 was held at 40 ° C. for 1 hour, and the curing reaction of the liquid glass was advanced to obtain a curing precursor.
Next, the reduced pressure was released, and the mold 2 was placed on a 45 ° C. hot plate for 30 seconds to dry. A glass plate (length 30 mm × width 30 mm × thickness 1.3 mm) was adhered to the surface of the curing precursor, and pressed at room temperature with a pressure of 500 N.

Next, the curing precursor and the mold 2 are separated, and the curing precursor is heated at 350 ° C. for 2 hours in a nitrogen atmosphere to be completely cured, and is made of a transparent curing material (fluorinated polyarylene ether). An optical element 3 having a microlens (convex portion) formed on the surface of the molded body was obtained. The heat resistance temperature of the compact was 300 ° C.
The releasability of the optical element 3 was evaluated, and the dimensions of the microlens were measured. The results are shown in Table 2.
The transparency of the transparent cured material forming the optical element 3 was measured and found to be 75% or more.

[Example 9]
Production of mold 3:
A bank was provided on the periphery of the same master mold as in Example 4 using a work free seal (manufactured by ASONE). Polydimethylsiloxane (manufactured by Dow Corning, SYLGARD 184) was supplied to the inside of the bank, and the pressure was reduced to 13 kPa and held for 5 minutes. Then, it was left overnight at room temperature to form a polydimethylsiloxane layer (thickness of about 3 mm) on the surface of the master mold.

The layer made of polydimethylsiloxane and the master mold were separated to obtain a mold 3 in which an inverted structure (concave portion) corresponding to a microlens (convex portion) was formed on the mold surface made of polydimethylsiloxane.
The dimensions of the inverted structure of the mold 3 were measured to evaluate chemical resistance. The results are shown in Table 1.

[Example 10]
Production of optical element 4:
On the surface of the mold 3, 2.0 g of liquid glass (Apollolink, TGA-CP210) was applied. With the pressure reduced to 13 kPa, the mold 3 was held at 40 ° C. for 1 hour, and the curing reaction of the liquid glass was advanced to obtain a curing precursor.

Next, the decompression is released, an adhesive (manufactured by Toto Kagaku Kogyo Co., Ltd., Beston) is applied to the surface of the curing precursor, and a glass plate (length 30 mm × width 30 mm × thickness 1.3 mm) is adhered thereon, It was left at room temperature for 9 hours.
Next, the curing precursor and the mold 3 are separated, and the curing precursor is heated at 140 ° C. for 30 minutes to be completely cured to form a microlens (convex portion) on the surface of the molded body made of a transparent cured material. Thus obtained optical element 4 was obtained.
The releasability of the optical element 4 was evaluated, and the dimensions of the microlens were measured. The results are shown in Table 2. In addition, since the shape of the microlens was not uniform and distorted due to the rubber elasticity of the mold 3, the dimensions were set to average values.
When the transparency of the transparent curable material forming the optical element 4 was measured, it was 85% or more.

[Example 11]
Production of optical element 5:
On the surface of the mold 1, a thermosetting transparent silicone resin for sealing material (a mixture of KJR-632 manufactured by Shin-Etsu Silicone and C-632 manufactured by Shin-Etsu Silicone, a composition of polysiloxane having a vinyl group and a hydrosilyl group) 0.5 g was applied. It was confirmed that bubbles in the mixture applied by holding for 0.5 hour in the air disappeared, and a glass plate (length 30 mm × width 30 mm × thickness 0.3 mm) was adhered thereon. The silicone resin was cured by holding at 80 ° C. for 40 hours to obtain a curing precursor.
Next, the curing precursor and the mold 1 are separated, and the curing precursor is heated at 150 ° C. for 1 hour to be completely cured to form a microlens (convex portion) on the surface of the molded body made of a transparent cured material. Thus obtained optical element 5 was obtained. The heat resistance temperature of the compact was 300 ° C.
The releasability of the optical element 5 was evaluated, and the dimensions of the microlens were measured. The results are shown in Table 2.
When the transparency of the transparent curable material forming the optical element 5 was measured, it was 90% or more.

[Example 12]
Production of optical element 6:
On the surface of the mold 1, a thermosetting transparent silicone resin for sealing material (a mixture of KJR-632 manufactured by Shin-Etsu Silicone and C-632 manufactured by Shin-Etsu Silicone, a composition of polysiloxane having a vinyl group and a hydrosilyl group) Apply 0.5 g. It is confirmed that bubbles in the mixture applied by holding in the air for 0.5 hours disappear, and held at 80 ° C. for 40 hours to cure the silicone resin to obtain a cured precursor.
Next, the curing precursor and the mold 1 are separated, and the curing precursor is heated at 150 ° C. for 1 hour to be completely cured. An adhesive (GE Toshiba Silicones, TSE3212) is applied to the surface where the microlenses (convex parts) are not formed, and a glass plate (length 30 mm × width 30 mm × thickness 1.3 mm) is adhered thereon. By holding at 150 ° C. for 1 hour, an optical element 6 in which microlenses (convex portions) are formed on the surface of a molded body made of a transparent curable material is obtained. The heat resistance temperature of the molded body is 300 ° C.
The releasability of the optical element 6 is evaluated, and the dimensions of the microlens are measured. The results are shown in Table 2.
When the transparency of the transparent curable material forming the optical element 6 was measured, it was 90% or more.

  The optical element obtained by the production method of the present invention is useful as a micro lens having a very small size, a micro lens array, a cylindrical lens array, a Fresnel lens, or the like.

It is sectional drawing which shows an example of the optical element obtained with the manufacturing method of this invention. It is sectional drawing which shows an example of process (a-1)-(e-1) in the manufacturing method of this invention. It is sectional drawing which shows an example of process (a-2)-(d-2) in the manufacturing method of this invention. It is a front view which shows the master mold used in an Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Optical element 12 Base material 14 Micro lens 16 Transparent hardening substance 20 Mold 22 Inversion structure 30 The liquid layer which consists of a solution containing a hardening agent or a hardening substance 32 A hardening precursor

Claims (9)

A molded body having a microlens formed on the surface, and a molded body made of a transparent cured material having a heat resistance of 200 ° C. or higher obtained by curing a curable material,
(A-1) An inversion structure corresponding to the microlens is formed on the surface, and the surface contains a fluoropolymer, and the surface of the mold is made of the solution containing the curable substance or the curable substance. Supplying a liquid to form a layer of the solution or liquid on the surface of the mold;
(B-1) below the softening temperature of the fluoropolymer, when the layer contains a solvent, removing the solvent and proceeding with a curing reaction until the curable substance becomes a curing precursor;
(D-1) separating the cured precursor layer from the mold having the cured precursor layer to obtain a molded body of the cured precursor;
(E-1) A method for producing an optical element, comprising: curing the curing precursor to obtain a molded body made of a transparent cured material.   The manufacturing method of the optical element of Claim 1 which performs hardening of the hardening precursor in the said (e-1) process at the temperature higher than the temperature used at the said (b-1) process.   2. The method according to claim 1, further comprising: (c-1) attaching a base material to a surface of the layer of the curing precursor on the mold between the step (b-1) and the step (d-1). 2. A method for producing an optical element according to 2. A molded body having a microlens formed on the surface, and a molded body made of a transparent cured material having a heat resistance of 200 ° C. or higher obtained by curing a curable material,
(A-2) A reversal structure corresponding to the microlens is formed on the surface, and the surface contains a fluoropolymer, and the surface of the mold is made of the solution containing the curable substance or the curable substance. Supplying a liquid to form a layer of the solution or liquid on the surface of the mold;
(B-2) a step of removing the solvent when the layer contains a solvent at a temperature lower than the softening temperature of the fluoropolymer, and making the curable substance a transparent cured product;
(D-2) A method for producing an optical element, comprising: separating the transparent cured material layer from the mold having the transparent cured material layer to obtain a molded body made of the transparent cured material.   The method according to claim 4, further comprising: (c-2) attaching a base material to a surface of the layer of the transparent curable material on the mold between the step (b-2) and the step (d-2). The manufacturing method of the optical element of description.   The optical element production according to any one of claims 1 to 5, wherein the transparent curable substance is a silicon oxide polymer having an organic group bonded to a silicon atom by a carbon-silicon bond, or a fluorine-containing aromatic polymer. Method.   The optical element according to claim 1, wherein the transparent cured material is a cured product of a silicone resin, a cured product of a hydrosilation reaction-curable organosilicone, a fluorine-containing polyarylene ether, or a fluorine-containing polyimide. Manufacturing method.   The fluorine-containing polymer has a fluorine atom amount of 35% by mass or more in the fluorine-containing polymer (100% by mass), and a contact angle with respect to water of a film made of the fluorine-containing polymer is 80 ° or more. Item 8. A method for producing an optical element according to any one of Items 1 to 7.   The manufacturing method of the optical element in any one of Claims 1-8 whose diameter of the said micro lens is 300 micrometers or less.

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