WO2009142116A1

WO2009142116A1 - Forming die for precision processing, method of forming molded curable resin, and formed object

Info

Publication number: WO2009142116A1
Application number: PCT/JP2009/058714
Authority: WO
Inventors: 明子原; 大輔渡邉
Original assignee: コニカミノルタオプト株式会社
Priority date: 2008-05-21
Filing date: 2009-05-09
Publication date: 2009-11-26

Abstract

Shape errors and lot-to-lot fluctuations are inhibited from occurring even in precision elements. A forming die for precisely processing a molded curable resin is provided for the inhibition. The die comprises a base and a forming part, and at least the forming part of the die comprises a resin ingredient and an inorganic ingredient dispersed in the resin ingredient.

Description

Mold for precision machining, molding method of curable resin molding, and molding

The present invention relates to a molding die for precision processing, a molding method for a curable resin molding, and a molding.

As a method for manufacturing optical elements such as lenses and diffraction elements used in imaging devices, optical pickup devices, optical communication devices, and precision elements used in semiconductor devices, a photoresist manufacturing method, injection molding using a molding die, or transfer Molding and the like are known. Among them, molding by a molding die is preferably used because a molded product having the same shape can be easily molded repeatedly.

Conventionally, thermoplastic resin is used for applications such as optical elements. When a thermoplastic resin material is molded with a mold, injection is performed by injecting the resin material melted by heat into the mold at high pressure. Molding is used. Therefore, since the metal mold used is required to have high rigidity, a metal metal mold has been used. However, since metal molds have a limited production method for diamond cutting or the like, there is a problem in that manufacturing of a mold having a fine surface shape or a mold for precision elements is costly and laborious. In addition, thermoplastic resins have low heat resistance and are used in a high thermal environment. When processing in a high thermal environment called a reflow process is performed (for example, see Patent Document 1), deformation and coloring due to softening occur. There was a problem.

Therefore, techniques for molding optical elements and precision elements with curable resins are being studied. A curable resin generally has higher heat resistance than a thermoplastic resin, and does not cause problems such as deformation even when used in a high thermal environment. In addition, unlike a thermoplastic resin, the curable resin has a very low viscosity even at room temperature before curing. Therefore, the material of the molding die is not limited, and the molding die made of glass or resin can be used.

JP 2001-24320 A

However, when glass is used as the mold, the melting point is high and molding at high temperature is unavoidable, resulting in an increase in cost. Therefore, a mold made of a resin material can be considered. However, when a precision processing mold is manufactured from a resin material, a new problem has occurred.

For example, when a mold for precision processing is manufactured with a curable resin material, the curable resin material generally shrinks as it cures, so when the mold is cured, it shrinks and cures from the original design value. The shape of the mold may be shifted, and it was necessary to correct it after molding. In addition, when molding a molded product multiple times using the same mold, curing shrinkage occurs due to curing of the uncured portion of the curable resin material that is the material of the mold, resulting in variations among production lots. It has been found.

In addition, when manufacturing precision processing molds with thermoplastic resin materials, it was found that the shape was deformed due to softening, and if the mold was used more than once, there were variations among production lots. .

Accordingly, a main object of the present invention is to provide a molding die and a manufacturing method capable of manufacturing a curable resin molded product by a simple method without causing a shape error or a variation for each manufacturing lot even if it is a precision element. That is.

According to one aspect of the invention,
In a mold for precision processing of a curable resin molding having a base and a molding part,
At least a molding part of the molding die contains a resin component and an inorganic component dispersed in the resin component.

Preferably,
The mold is a mold for precision processing of a photocurable resin molding,
The mold is characterized in that it has transparency to the light used when curing the photocurable resin molding. Note that the light transmittance refers to a light having a transmittance of 20% or more, preferably 50% or more, and more preferably 70% or more, with respect to light having a wavelength to be used.

More preferably,
The inorganic component is inorganic particles having a particle size smaller than the wavelength of light used when the photocurable resin molded product is cured.

Preferably,
The mold is a mold for precision processing of a thermosetting resin composition,
The mold has a softening point higher than a molding temperature when curing the thermosetting resinous molding,
More preferably,
The inorganic component is inorganic particles.

Also preferably,
The base material and the molding part are integrally formed of the same material.

Also preferably,
The base material is formed of a material different from the molded part,
The base material is made of glass.

Also preferably,
The base material is formed of a material different from the molded part,
The base material is made of resin.

Also preferably,
The resin component is a curable resin.

According to another aspect of the invention,
It has a base material and a molded part, and the molded part fills a mold containing a resin component and an inorganic component dispersed in the resin component with a curable resin material, and is cured by light or heat. A method for molding a curable resin molded product is provided.

According to another aspect of the invention,
A molded product obtained by the molding method of the curable resin molded product is provided.

According to the present invention, in a precision processing mold for molding a curable resin molding, at least a molding part including at least a molding surface is made of a material in which an inorganic component is dispersed in a resin component. It is possible to provide a mold capable of producing a curable resin molded product by a simple method without causing variation among lots.

In particular, when used as a mold for precision processing of a photocurable resin molded product, when curing is performed using a point light source, variation in light intensity occurs, so that sufficient hardness cannot be obtained or after molding The molded product may cause a shape error due to curing shrinkage, but since the molded product is uniformly irradiated with light due to scattering by inorganic particles, there is also an effect that more uniform curing is possible. can get.

On the other hand, when used as a mold for precision processing of thermosetting resin moldings, inorganic materials generally have higher thermal conductivity than resin materials, so that the moldings can be cured efficiently and uniformly. Is possible, and precise molding becomes possible.

It is a perspective view which shows schematic structure of a wafer lens. It is a perspective view which shows schematic structure of a master and a submaster. It is drawing for demonstrating the manufacturing method of a wafer lens. It is the schematic which shows typically the mode of the light diffusion of a shaping | molding die.

Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.

As shown in FIG. 1, the wafer lens 1 has a circular glass substrate 3 and a plurality of lens portions 5, and a plurality of lens portions 5 are arranged in an array on the glass substrate 3. ing. The lens unit 5 may be formed on the surface of the glass substrate 3 or may be formed on both front and back surfaces. The lens unit 5 may have a fine structure such as a diffraction groove or a step on the surface of the optical surface.

The lens part 5 is made of resin 5A. A curable resin material is used as the resin 5A. The curable resin material is roughly classified into a photocurable resin and a thermosetting resin, and the resin 5A may be either a photocurable resin or a thermosetting resin.

As the photocurable resin, for example, an acrylic resin or an allyl resin can be used, and these resins can be cured by radical polymerization. As another photocurable resin, for example, an epoxy-based resin can be used, and the resin can be reaction-cured by cationic polymerization.

On the other hand, the thermosetting resin can be cured by addition polymerization such as silicone in addition to the above radical polymerization and cationic polymerization.

In manufacturing the wafer lens 1, a master mold 10 (hereinafter simply referred to as “master 10”) and a sub master mold 20 (hereinafter simply referred to as “submaster 20”) shown in FIG. 2 are used.

The master 10 is a mother die used when the sub master 20 is manufactured, and the sub master 20 is a molding die used when the wafer lens 1 (lens portion 5) is molded. The sub master 20 is used a plurality of times to mass-produce the wafer lens 1, and is different from the master 10 in the purpose of use, frequency of use, and the like. In this embodiment, the master 10 is used as an example of a precision processing mold.
<Master>
As shown in FIG. 2A, the master 10 has a plurality of convex portions 14 formed in an array with respect to a rectangular parallelepiped base portion 12. The convex part 14 is a part corresponding to the lens part 5 of the wafer lens 1 and protrudes in a substantially hemispherical shape. Note that the outer shape of the master 10 may be a quadrangle or a circle as described above. Although the scope of rights of the present invention is not limited by this difference, the following description will be made taking a rectangular shape as an example.

The surface (molded surface) shape of the convex portion 14 is a positive shape corresponding to the optical surface shape (shape of the surface opposite to the glass substrate 3) of the lens unit 5 molded and transferred onto the glass substrate 3.

As the material of the master 10, when an optical surface shape is created by machining such as cutting or grinding, metal or metal glass can be used. The classification includes ferrous materials and other alloys. Examples of the iron system include hot dies, cold dies, plastic dies, high-speed tool steel, general structural rolled steel, carbon steel for mechanical structure, chromium / molybdenum steel, and stainless steel. Among them, plastic molds include pre-hardened steel, quenched and tempered steel, and aging treated steel. Examples of pre-hardened steel include SC, SCM, and SUS. More specifically, the SC system includes PXZ. Examples of the SCM system include HPM2, HPM7, PX5, and IMPAX. Examples of the SUS system include HPM38, HPM77, S-STAR, G-STAR, STAVAX, RAMAX-S, and PSL. Examples of iron-based alloys include Japanese Patent Application Laid-Open Nos. 2005-113161 and 2005-206913. As the non-ferrous alloys, copper alloys, aluminum alloys and zinc alloys are well known. Examples thereof include alloys disclosed in JP-A-10-219373 and JP-A-2000-176970. As the metal glass material, PdCuSi, PdCuSiNi, and the like are suitable because they have high machinability in diamond cutting and less tool wear. Amorphous alloys such as electroless and electrolytic nickel phosphorous plating are also suitable because they have good machinability in diamond cutting. These highly machinable materials may constitute the entire master 10 or may cover only the surface of the optical transfer surface, in particular, by a method such as plating or sputtering.

Further, as the material of the master 10, machining is somewhat difficult, but glass can also be used. If glass is used for the master 10, the merit of allowing light to pass through can also be obtained. If it is the glass generally used, it will not specifically limit.
<Submaster>
As shown in FIG. 2 (b), the sub master 20, which is an example of a precision processing mold, is mainly composed of a molding part 22 and a base material 26. A plurality of recesses 24 are formed in the molding portion 22 in an array. The surface (molding surface) shape of the concave portion 24 is a negative shape corresponding to the lens portion 5 in the wafer lens 1, and is concave in a substantially hemispherical shape in this figure.

In the present embodiment, an example in which the sub master 20 is used for molding the lens portion 5 of the wafer lens 1 is shown. However, the sub master 20 is not limited to this, and the sub master 20 has a fine and precise uneven shape (nano-size) on the surface. It can also be applied to molding of optical elements and precision elements that are required to form scale irregularities). For example, molding of a lens array with a single lens or a plurality of lenses arranged in an array, patterned It can also be applied to media substrate molding and nanohole molding technology in nanoimprint technology.
≪Molding part≫
The molding part 22 is made of an organic / inorganic material 22A. The organic inorganic material 22A is a material mainly composed of a resin component and an inorganic component, and is a material in which an inorganic component is dispersed with respect to the resin component.

Hereinafter, (1) a resin component and (2) an inorganic component will be described separately.
(1) Resin component A thermoplastic resin and a curable resin can be used as the resin component.

However, when the lens portion 5 made of a photocurable resin is molded from the submaster 20 using a photocurable resin as the resin 5A (when the submaster 20 is used as a mold for a photocurable resin molded product). The resin component preferably has transparency to the light used when the photocurable resin molded product (lens portion 5) is cured.

On the other hand, when the lens portion 5 made of a thermosetting resin is molded from the submaster 20 using a thermosetting resin as the resin 5A (when the submaster 20 is used as a mold for a thermosetting resin molded product). The resin component preferably has a softening point higher than the molding temperature when curing the thermosetting resin molding (lens portion 5).

Examples of the thermoplastic resin and curable resin that can be used as the resin component include the following types of resins.
(1.1) Thermoplastic resin As the thermoplastic resin, the following resins can be used.

Cycloolefin resins include dicyclopentadiene, tricyclopentadiene, dichloropentadiene-methylcyclopentadiene co-dimer, 5-ethylidene norbornene, norbornadiene, 5-cyclohexenyl norbornene, 1,4,5,8-dimethano-1,4 , 4a, 5,6,7,8,8a-octahydronaphthalene, 1,4-methano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4 , 5,8-Dimethano-1,4,4a, 5,6,7,8,8a-heptahydro-naphthalene, 6-methyl-1,4,5,8-dimethano-1,4,4a, 5,6 , 7,8,8a-heptahydronaphthalene, 1,4,5,8-dimethano-1,4,4a, 5,8,8a-hexahydronaphthalene, etc. It can be exemplified one or two or more mixtures of cyclic olefins having Ruborunen structure. Moreover, it can also be set as the copolymer of the said cyclic olefin and ethylene.

Examples of the acrylic resin include a homopolymer of an alkyl methacrylate having 1 to 4 alkyl carbon atoms, or a copolymer of 50 mol% or more of the alkyl methacrylate and another copolymerizable monomer. Examples of such an alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and tert-butyl methacrylate. As the copolymerizable monomer, any copolymer can be used as long as it does not impair the transparency of the copolymer obtained by using this, and examples thereof include 2-hydroxylethyl acrylate, 2-hydroxylpropyl acrylate, 3-hydroxyl Hydroxyalkyl acrylate such as butyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, alkyl acrylate such as 2-ethylhexyl acrylate, cyclohexyl acrylate, styrene, vinyl chloride, vinyl acetate, acrylonitrile, methacrylonitrile Acrylic acid, methacrylic acid, and the like. Also, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, tetramethylolmethane tetraacrylate, tetramethylol Methane dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, and the like can also be used.

Examples of the styrene resin include a homopolymer of styrene or a substituted product thereof, or a copolymer of 50 mol% or more of the styrene compound and another copolymerizable monomer. Such styrene compounds include styrene, methylstyrene, chlorostyrene, vinyltoluene and the like. Another copolymerizable monomer is a copolymerizable monomer used in the acrylic resin.

Examples of the vinyl chloride resin include a vinyl chloride homopolymer or a copolymer of 50% or more of the vinyl chloride and other copolymerizable monomers. As another copolymerizable monomer, there is a copolymerizable monomer used in the acrylic resin.

Polycarbonate resins include bisphenol type polycarbonate, octyl benzoic acid, monooctyl phthalate, monooctyl terephthalate and the like.

As the fluorine-based material, homopolymerization such as tetrafluoroethylene, hexafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, or a copolymer of two or more kinds of materials can be used. Cyclic fluorine compounds can also be used.
(1.2) Curable resin The curable resin may be a photocurable resin or a thermosetting resin, and its properties (whether it is photocurable or thermosetting) are: It can be selected depending on the type of initiator.

The following resins can be used as the curable resin.
(1.2.1) Acrylic resin The (meth) acrylate used for the polymerization reaction is not particularly limited, and the following (meth) acrylate produced by a general production method can be used. Ester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, ether (meth) acrylate, alkyl (meth) acrylate, alkylene (meth) acrylate, (meth) acrylate having an aromatic ring, alicyclic structure The (meth) acrylate which has is mentioned. One or more of these can be used.
In particular, (meth) acrylate having an alicyclic structure is preferable, and may be an alicyclic structure containing an oxygen atom or a nitrogen atom. For example, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, cycloheptyl (meth) acrylate, bicycloheptyl (meth) acrylate, tricyclodecyl (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, isoboronyl (meth) ) Acrylate, di (meth) acrylate of hydrogenated bisphenols, and the like. In particular, it preferably has an adamantane skeleton. For example, 2-alkyl-2-adamantyl (meth) acrylate (see Japanese Patent Laid-Open No. 2002-193883), adamantyl di (meth) acrylate (Japanese Patent Laid-Open No. 57-5000785), diallyl adamantyl dicarboxylate (Japanese Patent Laid-Open No. 60-100537). ), Perfluoroadamantyl acrylate (JP 2004-123687), Shin-Nakamura Chemical Co., Ltd. 2-methyl-2-adamantyl methacrylate, 1,3-adamantanediol diacrylate, 1,3,5-adamantane triol triacrylate, Saturated carboxylic acid adamantyl ester (JP 2000-119220 A), 3,3′-dialkoxycarbonyl-1,1 ′ biadamantane (see JP 2001-253835 A), 1,1′-biadamantane compound (US Patent) See No. 3342880 ), Tetraadamantane (see JP-A-2006-169177), 2-alkyl-2-hydroxyadamantane, 2-alkyleneadamantane, 1,3-adamantanedicarboxylate di-tert-butyl, etc. Curable resin (see JP-A-2001-322950), bis (hydroxyphenyl) adamantanes, bis (glycidyloxyphenyl) adamantane (see JP-A-11-35522, JP-A-10-130371), etc. Is mentioned.

It is also possible to contain other reactive monomers.

In the case of (meth) acrylate, for example, methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate Tert-butyl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, and the like.

Examples of the polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) ) Acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol septa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripenta Erythritol penta (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol Such as Li (meth) acrylate.
(1.2.2) Allyl Ester Resin A resin having an allyl group and cured by radical polymerization. Examples thereof include the following, but are not particularly limited to the following.

Bromine-containing (meth) allyl ester not containing an aromatic ring (see JP-A-2003-66201), allyl (meth) acrylate (see JP-A-5-286896), allyl ester resin (JP-A-5-286896) , JP 2003-66201 A), a copolymer of an acrylate ester and an epoxy group-containing unsaturated compound (see JP 2003-128725 A), an acrylate compound (see JP 2003-147072 A), an acrylic And ester compounds (see JP 2005-2064 A).
(1.2.3) Epoxy resin The epoxy resin is not particularly limited as long as it has an epoxy group and is polymerized and cured by light or heat, and an acid anhydride, a cation generator, or the like is used as a curing initiator. Can do.

Examples of the epoxy include novolak phenol type epoxy resin, biphenyl type epoxy resin, and dicyclopentadiene type epoxy resin. Examples include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, 2,2′-bis (4-glycidyloxycyclohexyl) propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, Vinylcyclohexene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1, And 2-cyclopropanedicarboxylic acid bisglycidyl ester.
(1.2.4) Silicone Resin A silicone resin having a siloxane bond with Si—O—Si as the main chain can be used. As the silicone resin, a silicone resin made of a predetermined amount of polyorganosiloxane resin can be used (see, for example, JP-A-6-9937).

The thermosetting polyorganosiloxane resin is not particularly limited as long as it becomes a three-dimensional network structure with a siloxane bond skeleton by a continuous hydrolysis-dehydration condensation reaction by heating. It exhibits curability and has the property of being hard to be re-softened by overheating once cured.

Such a polyorganosiloxane resin includes the following general formula (A) as a structural unit, and the shape thereof may be any of a chain, a ring, and a network.

((R1) (R2) SiO) n (A)
In the general formula (A), “R1” and “R2” represent the same or different substituted or unsubstituted monovalent hydrocarbon groups. Specifically, as “R1” and “R2”, an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, an alkenyl group such as a vinyl group and an allyl group, an allyl group such as a phenyl group and a tolyl group, A cycloalkyl group such as a cyclohexyl group or a cyclooctyl group, or a group in which a hydrogen atom bonded to a carbon atom of these groups is substituted with a halogen atom, a cyano group, an amino group, or the like, such as a chloromethyl group, 3, 3, 3- Examples thereof include a trifluoropropyl group, a cyanomethyl group, a γ-aminopropyl group, and an N- (β-aminoethyl) -γ-aminopropyl group. “R1” and “R2” may be a group selected from a hydroxyl group and an alkoxy group. In the general formula (A), “n” represents an integer of 50 or more.

The polyorganosiloxane resin is usually used after being dissolved in a hydrocarbon solvent such as toluene, xylene or petroleum solvent, or a mixture of these with a polar solvent. Moreover, you may mix | blend and use what differs in a composition in the range which mutually melt | dissolves.

The method for producing the polyorganosiloxane resin is not particularly limited, and any known method can be used. For example, it can be obtained by hydrolysis or alcoholysis of one or a mixture of two or more organohalogenosilanes. Polyorganosiloxane resins generally contain hydrolyzable groups such as silanol groups or alkoxy groups. The group is contained in an amount of 1 to 10% by weight in terms of a silanol group.

These reactions are generally performed in the presence of a solvent capable of melting the organohalogenosilane. It can also be obtained by a method of synthesizing a block copolymer by cohydrolyzing a linear polyorganosiloxane having a hydroxyl group, an alkoxy group or a halogen atom at the molecular chain terminal with an organotrichlorosilane. The polyorganosiloxane resin thus obtained generally contains the remaining HCl, but in the composition of the present embodiment, the storage stability is good, so that the one having 10 ppm or less, preferably 1 ppm or less is used. Is good.
(2) Inorganic component There is no limitation in particular as an inorganic component disperse | distributed in the resin component of the shaping | molding part 22, From a viewpoint of disperse | distributing uniformly with respect to a resin component, it is preferable that an inorganic component is an inorganic particle, for example.

In particular, when the photo-curing resin lens portion 5 is molded from the sub-master 20 using a photo-curing resin as the resin 5A (when the sub-master 20 is used as a mold for a photo-curing resin molding). The inorganic component may be inorganic particles having a particle size smaller than the wavelength of light used when curing the photocurable resin molded product (lens portion 5), and the particle size is preferably 100 nm or less. More preferably, it is 50 nm or less.

The inorganic particles preferably have a particle size of 20 nm or less, more preferably 10 nm or less when used for nanohole molding technology in the nanoimprint technology.

Moreover, in the case of molding the lens portion 5 made of a photocurable resin from the submaster 20 using a photocurable resin as the resin 5A (when the submaster 20 is used as a mold for a photocurable resin molded product), From the viewpoint of transferring and molding the lens part 5 from the molding part 22 predominantly, inorganic particles are uniformly dispersed in the resin component, and light is scattered in the molding part 22 when light is incident on the molding part 22. In order to increase the light transmittance of the molded part 22, it is preferable to reduce the difference in refractive index between the resin component and the inorganic component.

Any inorganic particles having the above properties can be used. Specifically, the following inorganic particles are preferably oxide fine particles, metal salt fine particles, semiconductor fine particles and the like.
(2.1) Oxide fine particles As oxide fine particles, the metal constituting the metal oxide is Li, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co. Ni, Cu, Zn, Rb, Sr, Y, Nb, Zr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Ta, Hf, W, Ir, Tl, Pb, Bi and rare earth A metal oxide that is one or more metals selected from the group consisting of metals can be used. Specifically, for example, silicon oxide, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, hafnium oxide Niobium oxide, tantalum oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, indium oxide, tin oxide, lead oxide, and the complex oxide composed of these oxides Examples thereof include lithium, potassium niobate, lithium tantalate, and aluminum / magnesium oxide (MgAl ₂ O ₄ ). Also, rare earth oxides can be used as oxide fine particles, specifically scandium oxide, yttrium oxide, lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, oxide. Examples also include dysprosium, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, and lutetium oxide.
(2.2) Metal salt fine particles Examples of the metal salt fine particles include carbonates, phosphates, sulfates, and specifically calcium carbonate, aluminum phosphate and the like.
(2.3) Semiconductor fine particles The semiconductor fine particles mean fine particles having a semiconductor crystal composition, and specific examples of the semiconductor crystal composition include those of Group 14 elements of the periodic table such as carbon, silicon, germanium, and tin. Compound consisting of a single element, a group 15 element of the periodic table such as phosphorus (black phosphorus), a group 16 element of the periodic table such as selenium and tellurium, and a group 14 element of a plurality of periodic tables such as silicon carbide (SiC) , Tin oxide (IV) (SnO ₂ ), tin sulfide (II, IV) (Sn (II) Sn (IV) S ₃ ), tin sulfide (IV) (SnS ₂ ), tin sulfide (II) (SnS), Such as tin (II) selenide (SnSe), tin (II) telluride (SnTe), lead (II) sulfide (PbS), lead (II) selenide (PbSe), lead (II) telluride (PbTe) Compound of periodic table group 14 element and periodic table group 16 element, boron nitride (BN), phosphide Boron (BP), boron arsenide (BAs), aluminum nitride (AlN), aluminum phosphide (AlP), aluminum arsenide (AlAs), aluminum antimonide (AlSb), gallium nitride (GaN), gallium phosphide (GaP), Periodic table Group 13 elements such as gallium arsenide (GaAs), gallium antimonide (GaSb), indium nitride (InN), indium phosphide (InP), indium arsenide (InAs), indium antimonide (InSb), etc. Compounds with Group 15 elements (or III-V compound semiconductors), aluminum sulfide (Al ₂ S ₃ ), aluminum selenide (Al ₂ Se ₃ ), gallium sulfide (Ga ₂ S ₃ ), gallium selenide (Ga ₂ Se _3), telluride gallium _(Ga 2 _Te 3), oxide Print Arm _(In _{2 O} 3), indium sulfide _(In _{2 S} 3), indium selenide _(In 2 _Se 3), periodic table Group 13 element and Periodic Table Group 16 such as a telluride, indium _(In 2 Te ₃₎ A compound with an element, thallium chloride (I) (TlCl), thallium bromide (I) (TlBr), thallium iodide (I) (TlI), etc. Compound, zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), cadmium oxide (CdO), cadmium sulfide (CdS), cadmium selenide (CdSe), cadmium telluride (CdTe), mercury sulfide (HgS), mercury selenide (HgSe), mercury telluride (HgTe), etc. There is a II-VI group compound semiconductor), arsenic sulfide _{_{(III) (As 2 S 3}} ), selenium arsenic _{_{(III) (As 2 Se 3}} ), telluride arsenic _{_{(III) (As 2 Te 3}} ), antimony sulfide (III) (Sb ₂ S ₃ ), antimony selenide (III) (Sb ₂ Se ₃ ), antimony telluride (III) (Sb ₂ Te ₃ ), bismuth sulfide (III) (Bi ₂ S ₃ ), selenization Compound of periodic table group 15 element and periodic table group 16 element such as bismuth (III) (Bi ₂ Se ₃ ), bismuth telluride (III) (Bi ₂ Te ₃ ), copper oxide (I) (Cu ₂ O), compounds of Group 11 elements of the periodic table and elements of Group 16 of the periodic table such as copper (I) selenide (Cu ₂ Se), copper chloride (I) (CuCl), copper bromide (I) (CuBr) ), Copper (I) iodide (CuI), silver chloride (AgCl), silver bromide (AgBr) A compound of a periodic table group 11 element and a periodic table group 17 element such as nickel oxide (II) (NiO), a periodic table group 10 element and a periodic table group 16 element, cobalt oxide (II ) (CoO), cobalt sulfide (II) (CoS) and other compounds of Group 9 elements and Group 16 elements of the periodic table, triiron tetroxide (Fe ₃ O ₄ ), iron (II) sulfide (FeS) ), Etc., compounds of Group 8 elements of the Periodic Table, elements of Group 16 of the Periodic Table, compounds of Group 7 elements of the Periodic Table, such as manganese (II) (MnO), and Group 16 elements of the Periodic Table, molybdenum sulfide ( IV) (MoS2), tungsten oxide (IV) (WO ₂ ) and other compounds of Group 6 elements of the periodic table and Group 16 elements of the periodic table, vanadium oxide (II) (VO), vanadium oxide (IV) (VO) _2), tantalum oxide (V) _(Ta 2 _{O 5)} fifth periodic table, such as element and peripheral Table compound of Group 16 element, titanium oxide _{_{_{_{(TiO 2, Ti 2 O 5}}}} , Ti 2 O 3, Ti 5 O 9 , etc.) compounds of the periodic table Group 4 element and Periodic Table Group 16 element such as, Compounds of Group 2 elements of the periodic table and Group 16 elements of the periodic table such as magnesium sulfide (MgS) and magnesium selenide (MgSe), cadmium (II) oxide (Chromium (III) (CdCr ₂ O ₄ ), cadmium selenide (II) chromium _{_{(III) (CdCr 2 Se 4}} ), chalcogen spinels such as copper (II) sulfide chromium _{(III) (CuCr 2 S4)} , mercury selenide (II) chromium _{_{(III) (HgCr 2 Se 4}} ) And barium titanate (BaTiO ₃ ). In addition, G. Schmid et al .; Adv. Mater. 4, 494 (1991) (BN) 75 (BF2) 15F15 and D.C. Fenske et al .; Angew. Chem. Int. Ed. Engl. 29, page 1452 (1990), a semiconductor cluster having a fixed structure such as Cu146Se73 (triethylphosphine) 22 reported in the same manner is also exemplified.

In addition, the shape of the inorganic particles used as an example of the inorganic component is not particularly limited, but spherical inorganic particles are preferably used. Specifically, the minimum diameter of the inorganic particles (the minimum value of the distance between the tangents when drawing two tangents in contact with the outer periphery of the inorganic particles) / the maximum diameter (the two tangents in contact with the outer periphery of the inorganic particles) In this case, the maximum value of the distance between the tangents) is preferably 0.5 to 1.0, and more preferably 0.7 to 1.0.

Further, the particle size distribution is not particularly limited, but in order to achieve the effect of the present invention more efficiently, a particle having a relatively narrow distribution is preferably used rather than a particle having a wide distribution. Used.
≪Base material≫
Even if the base material 26 is inferior in strength only by the molding part 22 of the sub master 20, the strength of the sub master 20 is increased by sticking the base material 26 to the molding part 22, and can be molded many times. It is a backing material.

The base material 26 may be made of a material different from that of the molding part 22 or may be integrally made of the same material as that of the molding part 22. When the base material 26 is made of a material different from that of the molding portion 22, any material having smoothness such as quartz, silicone wafer, metal, glass, resin, etc. may be used. Constructing the base material 26 integrally with the same material as the molding part 22 means that the sub-master 20 is substantially constituted only by the molding part 22.

Next, a method for manufacturing the wafer lens 1 (including a method for forming the lens portion 5) will be described with reference to FIG.

As shown in FIG. 3A, an organic / inorganic material 22A is applied on the master 10, the convex portions 14 of the master 10 are transferred to the organic / inorganic material 22A, the organic / inorganic material 22A is cured, and the organic / inorganic material 22A is cured. A plurality of recesses 24 are formed. Thereby, the shaping | molding part 22 is formed.

When the organic inorganic material 22A (resin component of the molding part 22) and the resin 5A (material of the lens part 5) are curable resins, the optical surface shape (convex part 14) of the master 10 is preferably an organic inorganic material 22A. Is designed in anticipation of curing shrinkage of the resin and curing shrinkage of the resin 5A.

When the organic / inorganic material 22A is applied on the master 10, a technique such as spray coating, spin coating, dropping, or discharging is used. In this case, the organic / inorganic material 22A may be applied while evacuating. If the organic-inorganic material 22A is applied while evacuating, the organic-inorganic material 22A can be cured without introducing bubbles into the organic-inorganic material 22A.

Further, in order to easily peel the cured organic / inorganic material 22A from the master 10, it is preferable to apply a release agent to the surface of the master 10.

When the resin component of the organic inorganic material 22A is a photocurable resin, the light source 50 disposed above the master 10 is turned on and irradiated with light.

Examples of the light source 50 include a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a halogen lamp, a fluorescent lamp, a black light, a G lamp, and an F lamp, and may be a linear light source or a point light source. Good. The high-pressure mercury lamp is a lamp having a narrow spectrum at 365 nm and 436 nm. A metal halide lamp is a kind of mercury lamp, and its output in the ultraviolet region is several times higher than that of a high-pressure mercury lamp. A xenon lamp is a lamp having a spectrum closest to sunlight. Halogen lamps contain a lot of long-wavelength light and are mostly near-infrared light. Fluorescent lamps have uniform illumination intensity for the three primary colors of light. Black light has a peak top at 351 nm and emits near-ultraviolet light of 300 nm to 400 nm.

In the case of irradiating light from the light source 50, a plurality of linear or point light sources 50 may be arranged in a lattice shape so that the light reaches the entire surface of the organic-inorganic material 22A at a time. The point light source 50 may be scanned in parallel to the surface of the organic / inorganic material 22A so that the light sequentially reaches the organic / inorganic material 22A. In this case, preferably, the luminance distribution and the illuminance (intensity) distribution during light irradiation are measured, and the number of irradiations, the irradiation amount, the irradiation time, and the like are controlled based on the measurement results.

After photocuring the organic / inorganic material 22A (after the production of the submaster 20), the submaster 20 may be post-cured (heat treatment). If post-cure is performed, the organic inorganic material 22A (resin component) of the submaster 20 can be completely cured, and the mold life of the submaster 20 can be extended.

When the resin component of the organic / inorganic material 22A is a thermosetting resin, the organic / inorganic material 22A is heated while controlling the heating temperature and the heating time within an optimum range. The organic / inorganic material 22A can also be molded by a technique such as injection molding, press molding, light irradiation and then cooling.

Thereafter, as shown in FIG. 3B, the base material 26 is attached to the back surface (the surface opposite to the concave portion 24) of the molded portion 22 (organic inorganic material 22A), and the molded portion 22 is lined.

The substrate 26 may be quartz or a glass plate, and it is important to have sufficient bending strength and UV transmittance. In order to improve the adhesion between the molded portion 22 and the base material 26, a treatment such as applying a silane coupling agent to the base material 26 may be performed.

When backing the molding part 22 (organic inorganic material 22A) with the base material 26, a conventionally known vacuum chuck device 260 is used, and the base material 26 is sucked and held on the suction surface 260A of the vacuum chuck device 260, while It is preferable that the molded portion 22 is lined with the base material 26 with the suction surface 260A parallel to the molding surface of the convex portion 14 in the master 10. Thereby, the back surface 20A (surface on the base material 26 side) of the sub master 20 is parallel to the molding surface of the convex portion 14 in the master 10, and the molding surface of the recess 24 in the sub master 20 is parallel to the back surface 20A. Therefore, when the lens unit 5 is molded by the submaster 20 as will be described later, the reference surface of the submaster 20, that is, the back surface 20 </ b> A can be made parallel to the molding surface of the recess 24. Or variation in thickness, the shape accuracy of the lens unit 5 can be improved, and the lens performance can be maintained high. Further, since the sub master 20 is sucked and held by the vacuum chuck device 260, the sub master 20 can be attached and detached only by turning on / off the vacuum exhaust. Therefore, the sub master 20 can be easily arranged. Further, the master 10 is also most cautious and careful that the cured sub-master 20 is peeled off from the master 10 when the master 10 is sucked and held by the second vacuum chuck device parallel to the suction surface 260A of the vacuum chuck device 260. Can be easily removed from the molding equipment by turning off the vacuum chuck while the two are cured and in close contact with each other, and a reliable peeling operation can be performed in a wide environment with little equipment restrictions or on another equipment. be able to. Further, when another master and a sub master substrate are attached to the molding apparatus by a vacuum chuck during the operation, the sub master can be continuously molded.

Here, that the back surface 20A is parallel to the molding surface of the recess 24 specifically means that the back surface 20A is perpendicular to the central axis of the molding surface of the recess 24.

Further, the suction surface 260A of the vacuum chuck device 260 is preferably made of a ceramic material. In this case, since the hardness of the suction surface 260A is high and the suction surface 260A is hardly damaged by the attachment / detachment of the submaster 20 (base material 26), the surface accuracy of the suction surface 260A can be maintained high. Moreover, it is preferable to use silicon nitride or sialon as such a ceramic material. In this case, since the linear expansion coefficient is as small as 1.3 ppm, the flatness of the suction surface 260A can be kept high with respect to the temperature change.

In the present embodiment, the following method is used as a method for bringing the suction surface 260A into a parallel state with respect to the molding surface of the convex portion 14 in the master 10.

First, the front and back surfaces of the master 10 are parallelized with high accuracy. Thereby, in the master 10, the shaping | molding surface and back surface of the convex part 14 become parallel.

Further,

reference members

260C and 260D are provided so as to protrude from the support surface 260B that supports the master 10 from the back surface (surface opposite to the convex portion 14) and the suction surface 260A, respectively. Here, the shapes of these

reference members

260C and 260D are such that when the master 10 and the sub master 20 come into contact with each other in a state where the support surface 260B and the suction surface 260A are parallel to each other, there is no backlash.

Thus, by bringing the

reference members

260C and 260D into contact with each other, the support surface 260B of the master 10 and thus the molding surface of the convex portion 14 of the master 10 are parallel to the suction surface 260A.

However, in the above-described method, the reference member may be provided on at least one of the support surface 260B and the suction surface 260A. For example, when the reference member is provided only on the support surface 260B, the shape of the reference member is When the master 10 and the sub master 20 are in contact with each other with the surface 260B and the suction surface 260A being parallel to each other, the shape may be configured to contact the suction surface 260A without backlash. Similarly, when the reference member is provided only on the suction surface 260A, the shape of the reference member is such that when the master 10 and the sub master 20 are in contact with each other with the support surface 260B and the suction surface 260A being parallel to each other, What is necessary is just to make it the shape which contact | abuts with respect to the support surface 260B without backlash. Such parallelism by mechanical contact can realize reproducibility of about a few seconds without having a special alignment device.

Thereafter, as shown in FIG. 3C, the molding part 22 and the base material 26 are released from the master 10 to form the sub-master 20.

When a resin such as PDMS (polydimethylsiloxane) is used as the resin component of the organic inorganic material 22A, the releasability from the master 10 is very good. Is not distorted.

Thereafter, as shown in FIG. 3D, the resin 5A is filled between the sub-master 20 and the glass substrate 3 and cured. More specifically, the resin 5A is filled in the recess 24 of the submaster 20, and the resin 5A is cured while pressing the glass substrate 3 from above.

When filling the resin 5A into the recess 24 of the submaster 20, the resin 5A may be filled while evacuating. If the resin 5A is filled while evacuating, the resin 5A can be cured without introducing bubbles into the resin 5A.

Instead of filling the concave portion 24 of the submaster 20 with the resin 5A, the resin 5A may be applied to the glass substrate 3, and the glass substrate 3 coated with the resin 5A may be pressed against the submaster 20.

When the glass substrate 3 is pressed, the glass substrate 3 is preferably provided with a structure for axial alignment with the submaster 20. When the glass substrate 3 has a circular shape, for example, it is preferable to form a D cut, an I cut, a marking, a notch, or the like. The glass substrate 3 may have a polygonal shape, and in this case, the axis alignment with the submaster 20 is easy. Further, a marker pattern for matching the coaxiality with the front-side molding optical surface at the time of molding the back surface of the glass substrate 3 may be molded and transferred simultaneously with the optical surface at the time of molding the front-surface side.

When the resin 5A is cured, if the resin 5A is a thermosetting resin, it is cured by heating. On the other hand, when the resin 5A is a photocurable resin, the light source 52 disposed below the sub master 20 may be turned on to emit light from the sub master 20 side, or the light source disposed above the glass substrate 3. 54 may be turned on and light may be irradiated from the glass substrate 3 side, or both the

light sources

52 and 54 may be turned on simultaneously and light may be irradiated from both sides of the submaster 20 side and the glass substrate 3 side.

As the

light sources

52 and 54, the same high pressure mercury lamp, metal halide lamp, xenon lamp, halogen lamp, fluorescent lamp, black light, G lamp, and F lamp as the light source 50 described above can be used. It may be a point light source.

When irradiating light from the

light sources

52 and 54, a plurality of linear or point

light sources

52 and 54 may be arranged in a lattice shape so that the light reaches the resin 5A at a time. The point

light sources

52 and 54 may be scanned in parallel to the sub master 20 and the glass substrate 3 so that the light sequentially reaches the resin 5A. In this case, preferably, the luminance distribution and the illuminance (intensity) distribution during light irradiation are measured, and the number of irradiations, the irradiation amount, the irradiation time, and the like are controlled based on the measurement results.

When the resin 5A is cured, the lens portion 5 is formed. Thereafter, the lens unit 5 and the glass substrate 3 are released from the sub-master 20 to manufacture the wafer lens 1 (the wafer lens 1 has the lens unit 5 formed only on the surface of the glass substrate 3). ).

When the wafer lens 1 is released from the sub-master 20, the tension lens 60 is provided in advance between the wafer lens 1 (glass substrate 3) and the sub-master 20, and the tension lens 60 is pulled to remove the wafer lens 1. The mold may be released from the sub master 20.

When the base material 26 of the submaster 20 is an elastic material (resin), it may be bent slightly to release the wafer lens 1 from the submaster 20, or the glass substrate 3 is elastic instead of glass. Even in the case of a material (resin), the wafer lens 1 may be released from the sub master 20 by slightly bending it.

When the wafer lens 1 is slightly separated from the sub master 20 and a gap is formed between both members, air or pure water may be pumped into the gap and the wafer lens 1 may be released from the sub master 20.

In the above description, the method of providing the lens unit 5 on one side of the glass substrate 3 has been described. However, when the lens unit 5 is provided on both sides, first, it corresponds to the optical surface shape of the lens unit 5 on one side of the glass substrate 3. A master (not shown) having a plurality of positive molding surfaces and a master having a plurality of positive molding surfaces corresponding to the optical surface shape of the lens portion 5 on the other surface are prepared, and each of these masters is used. Thus, the

sub masters

20C and 20D (see FIGS. 3E and 3F) are formed. Accordingly, the sub master 20C has a negative molding surface corresponding to the optical surface shape of the lens portion 5 on one surface of the glass substrate 3, and the sub master 20D corresponds to the optical surface shape of the lens portion 5 on the other surface. Will have a negative shaped molding surface. And after filling resin 5A between each submaster 20C and 20D and the glass substrate 3, the resin 5A is hardened simultaneously and the lens part 5 is shape | molded on both surfaces of the glass substrate 3. FIG. According to this, the resin 5A does not cure and shrink on only one side of the glass substrate 3, and the resin 5A cures and shrinks simultaneously on both sides to become the lens parts 5, respectively. In contrast, since the warp of the glass substrate 3 can be prevented, the shape accuracy of the lens portion 5 can be improved. Note that the simultaneous curing of the resin 5A on both surfaces of the glass substrate 3 means that the resin 5A is completely cured in the same curing process, and it is not always necessary to start and end the curing simultaneously. After the resin 5A between the glass substrate 3 is thickened to a predetermined viscosity, the resin 5A and the other resin 5A may be completely cured.

According to the present embodiment described above, in the sub master 20, the constituent material of the molding part 22 including at least the molding surface is the organic inorganic material 22A in which the inorganic component is dispersed in the resin component, whereby the lens part of the wafer lens 1 is obtained. The occurrence of the shape error 5 and the variation of each production lot can be suppressed.

In particular, when the resin 5A of the lens unit 5 is a photocurable resin, when curing is performed using a point light source, variation in light intensity occurs, so that sufficient hardness cannot be obtained or after molding Although the lens unit 5 may cause a shape error due to curing shrinkage, the molded product 22 is irradiated with light uniformly due to scattering by inorganic particles in the molding unit 22 of the sub-master 20, and thus the lens unit 5. Can be cured more uniformly.

On the other hand, when the resin 5A of the lens unit 5 is a thermosetting resin, since the inorganic component generally has higher thermal conductivity than the resin component in the molding unit 22 of the submaster 20, the lens unit 5 is cured. Can be performed efficiently and uniformly, and precise molding becomes possible.

[Example 1]
(1) Durability Evaluation Method of Mold and its Results Six types of molds in which inorganic particles are dispersed in the thermosetting and thermoplastic resins listed in Table 1 (Examples 1 to 3, Comparative Examples 1 to Using 3), a wafer lens was produced.

Specifically, Shotak's Tempax float (thickness 300 μm) was used as the glass substrate of the wafer lens, and a photocurable resin (epoxy resin (Daicel) was used for the molds of Examples 1 to 3 and Comparative Examples 1 to 3. Chemical ceroxide 2021P), UV initiator (UVI-6992 manufactured by Dow Chemical Co., Ltd. added 1 wt%), irradiated with light of about 6000 mJ / cm 2 with a high-pressure mercury lamp, and photocurable on the glass substrate. A plurality of resin-made lens parts were formed in an array (the number of parts of the lens parts was about 2000 parts, and each lens part had a height of about 250 μm and about φ4.0).

Then, the surface shape of the wafer lens (lens part) produced from each mold was measured, and the durability (deterioration degree according to the use frequency) of each mold was evaluated.

Specifically, the PV value of the first lens part surface molded with each mold and the PV value of the deviation from the design value is 100%, and the 10th and 100th lens part surface surfaces molded with each mold PV value was measured. Thereafter, relative deviations of the PV values measured at the 10th and 100th times with respect to the PV value measured at the first time were calculated, and the durability of each mold was evaluated from the calculated values. For the measurement of the PV value, Panasonic UA3P (ultra-high precision three-dimensional measuring device) was used. In the measurement of the PV value, 10 parts were arbitrarily selected from the 2000 lens parts in the wafer lens, and the average value thereof was obtained and used as the PV value.

Table 1 shows the evaluation results of the above evaluation methods. In Table 1, the criteria for “◯”, “Δ”, and “×” are as follows.

○… PV value deviation (vs. 1st) is within ± 5% △… PV value deviation (vs. 1st) is less than ± 20% ×… PV value deviation (vs. 1st) is ± 20% or more

In Table 1, “Silpot 184” is a PDMS (polydimethylsiloxane) -containing silicone resin manufactured by Toray Dow Corning, “APEL” is a cycloolefin polymer manufactured by Mitsui Chemicals, and “Zeonex” is a cycloolefin polymer manufactured by Zeon Corporation. It is. “Silica RX300” is RX300 (particle size: 7 nm) manufactured by Nippon Aerosil Co., Ltd. The amount of silica RX300 added as inorganic particles was 50 wt% with respect to each resin.
(2) Summary As shown in Table 1, when the lens parts were molded using the molds of Examples 1 to 3, the durability of the molds was good, and the deviation of the PV value on the lens part surface was low. It is suppressed. For this reason, it is useful to suppress the shape error of the lens part and the variation of each production lot by forming the mold (molding part) with an organic inorganic material in which inorganic particles are dispersed in the resin component. I understand.
[Example 2]
(1) Production of sample (mold) (1.1) Example 21
Add 50 wt% silica particles (RX300 (Aerosil)) to acrylic curable resin (1: 1 mixture of A-DCP (Shinnakamura Chemical) and A-IB (Shin Nakamura Chemical)) and cure. 1 wt% of perbutyl O (manufactured by Nippon Oil & Fats) was added as an agent, and heated at 150 ° C. for 5 minutes to prepare a mold. Thereafter, the mold was post-cured (heated) at 190 ° C. for 3 hours to obtain a mold of “Example 21”.
(1.2) Comparative Example 21
A mold was produced in the same manner as in Example 21 except that silica particles were not added. Thereafter, the mold was post-cured (heated) at 190 ° C. for 5 hours, and this was used as the mold of “Comparative Example 21”.
(1.3) Example 22
50 wt% of silica particles (RX300) were added to silicone resin SR7010 (manufactured by Toray Dow) and heated at 150 ° C. for 1 hour to produce a mold. Thereafter, the mold was post-cured (heated) at 190 ° C. for 1 hour, and this was used as the mold of “Example 22”.
(1.4) Comparative Example 22
A mold was produced in the same manner as in Example 22 except that silica particles were not added. Thereafter, the mold was post-cured (heated) at 190 ° C. for 3 hours to obtain a mold of “Comparative Example 22”.
(1.5) Example 23
Silica particles (RX300) of 50 wt% was added to Nippon Steel Chemical's Silplus MHD2510, and 365 nm light from a high pressure mercury lamp was irradiated at an intensity of 100 mW / cm 2 for 1 minute to produce a mold. Thereafter, the mold was post-cured (heated) at 190 ° C. for 3 hours to obtain a mold of “Example 23”.
(1.6) Comparative Example 23
A mold was produced in the same manner as in Example 23 except that silica particles were not added. Thereafter, the mold was post-cured (heated) at 190 ° C. for 6 hours to obtain a mold of “Comparative Example 23”.
(2) Method for evaluating durability of mold and results thereof Using molds of Examples 21 to 23 and Comparative Examples 21 to 23, a thermosetting resin (YX8000 manufactured by JER) was used to mold a lens array, The shape of the lens surface was measured to evaluate the durability (deterioration depending on the frequency of use) of each mold. The evaluation results are shown in Table 2.

(3) Summary As shown in Table 2, also in this example, when the lens parts were molded using the molds of Examples 21 to 23, the durability of the molds was good, and the surface of the lens part was good. The deviation of the PV value is kept low. For this reason, it is useful to suppress the shape error of the lens part and the variation of each production lot by forming the mold (molding part) with an organic inorganic material in which inorganic particles are dispersed in the resin component. I understand.
[Example 3]
(1) Evaluation method and result of light diffusibility of molds Six types of molds in which inorganic particles are dispersed in the thermosetting and thermoplastic resins listed in Table 3 (Examples 31 to 33, Comparative Example 31) To 33) were prepared. Each mold is formed with grooves of 200 mm square, 250 μm wide and 250 μm high at intervals of 250 μm. After that, each mold is filled with a photo-curable resin, and the glass plate that has been subjected to the mold release treatment is lined so that the thickness of the molded product becomes 500 μm, and light is irradiated from the mold side to emit light. The curable resin was cured, the glass flat plate was peeled off after curing, and the presence or absence of an uncured portion on the back of the molded product was detected (see FIG. 4). The detection results are shown in Table 3. In Table 3, the criteria for “◯” and “x” were as follows.

○… No uncured part ×… Uncured part

(2) Summary As shown in Table 3, even when any of the molds of Examples 31 to 33 and Comparative Examples 31 to 33 was used, an uncured part was not detected in the thin part on the back of the molded product. When the molds of Examples 31 to 33 were used, no uncured part was detected even in the thick part. This is presumably because the light incident on the mold was uniformly diffused by the presence of the inorganic particles and propagated to the thick part on the back of the molded product as shown in FIG. 4 (see dotted line). For this reason, forming the mold (molded part) with an organic inorganic material in which inorganic particles are dispersed in the resin component improves the light diffusibility of the mold (molded part) and increases the thickness direction of the molded product. It turns out that it is useful for aiming at uniform hardening in.

DESCRIPTION OF SYMBOLS 1 Wafer lens 3 Glass substrate 5 Lens part 5A Resin 10 Master 12 Base part 14 Convex part 16 Concave part 20 Submaster (an example of a precision processing mold)
22 Molding part 22A Organic inorganic material 24 Concave part 26 Base material

Claims

In a mold for precision processing of a curable resin molding having a base and a molding part,
At least a molding part of the molding die contains a resin component and an inorganic component dispersed in the resin component.
The mold is a mold for precision processing of a photocurable resin molding,
2. The mold for precision processing according to claim 1, wherein the mold has transparency to light used when the photocurable resin molded product is cured.
3. The precision processing mold according to claim 2, wherein the inorganic component is an inorganic particle having a particle size smaller than a wavelength of light used when the photocurable resin molded product is cured.
The mold is a mold for precision processing of a thermosetting resin composition,
The mold for precision machining according to claim 1, wherein the mold has a softening point higher than a molding temperature at the time of curing the thermosetting resin molding.
The mold for precision machining according to claim 4, wherein the inorganic component is inorganic particles.
The precision processing mold according to any one of claims 1 to 5, wherein the base material and the molding part are integrally formed of the same material.
The base material is formed of a material different from the molded part,
6. The precision processing mold according to claim 1, wherein the substrate is made of glass.
The base material is formed of a material different from the molded part,
The precision processing mold according to any one of claims 1 to 5, wherein the substrate is made of a resin.
The mold for precision processing according to any one of claims 1 to 8, wherein the resin component is a curable resin.
It has a base material and a molded part, and the molded part fills a mold containing a resin component and an inorganic component dispersed in the resin component with a curable resin material, and is cured by light or heat. A method for forming a curable resin molded product.
A molded product obtained by the method for molding a curable resin molded product according to claim 10.