JP6615249B2 - Optical component and optical device including the same - Google Patents

Description

  The present invention relates to an optical component having a coating layer and an optical device including the same.

  In a camera mounted on a portable electronic device such as a smartphone, a flash lens is installed immediately before the light source in order to diffuse light from the light source. As the flash lens, a Fresnel lens that can cope with a reduction in thickness and size is mainly used.

  The lens may be required to form a black or white portion on the outer edge of the lens for the purpose of imparting light shielding properties or reflectivity, and the lens is painted black or white, or by two-color molding. It is known to cope with the method of forming a lens.

  Here, as a manufacturing method of a lens, for example, a method of injection molding using a thermoplastic resin such as polycarbonate, polymethyl methacrylate, or cycloolefin polymer is known (Patent Documents 1 and 2). However, in injection molding, it has been difficult to manufacture a fine lens for use in a camera mounted on a portable electronic device such as a smartphone. Furthermore, it has been a problem that it is very difficult and costly to paint one by one on a fine lens obtained by injection molding. Further, the method of forming a lens by two-color molding is expensive, and it is difficult to produce lenses in a large amount at a low cost. Furthermore, the lens obtained by using a thermoplastic resin is inferior in heat resistance, and cannot be mounted on a board by reflow soldering (particularly lead-free soldering) together with other parts. .

JP 2013-212593 A JP 2013-224349 A

Accordingly, an object of the present invention is to provide an optical component that is fine and excellent in heat resistance, and that has a coating layer on a part thereof.
Another object of the present invention is to provide a method for producing the optical component simply and efficiently.
Another object of the present invention is to provide an optical device having the optical component.

  As a result of intensive studies to solve the above problems, the present inventors have found that a curable composition containing an epoxy compound has low viscosity and excellent transferability, and a cured product of the curable composition has excellent heat resistance, It was obtained by subjecting the curable composition to casting using a mold having a plurality of optical component mold recesses to form a cured product having the shape of two or more optical components, and then cutting. It has been found that a fine optical component having a coating layer can be easily and efficiently produced by coating the surface of a singulated product of a cured product. The present invention has been completed based on these findings.

  That is, the present invention is an optical component comprising a cured product of a curable composition containing an epoxy compound (A), and at least one coating layer having a thickness of 0.1 mm or less is formed on a part of the surface of the optical component. An optical component having a maximum thickness of 2 mm or less and a maximum width of 10 mm or less in plan view is provided.

［式中、Ｒ¹〜Ｒ¹⁸は同一又は異なって、水素原子、ハロゲン原子、酸素原子若しくはハロゲン原子を含んでいてもよい炭化水素基、又は置換基を有していてもよいアルコキシ基を示す。Ｘは単結合又は連結基を示す］ The present invention also provides the above optical component, wherein the epoxy compound (A) contains a compound represented by the following formula (a).

[Wherein, R ^{1 to} R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent. . X represents a single bond or a linking group]

  The present invention also provides the above optical component, wherein the curable composition contains an epoxy compound (A), an oxetane compound (B), and a cationic polymerization initiator (C).

  The present invention also provides the above-described optical component having a thermal decomposition temperature of 200 ° C. or higher.

  The present invention also provides the above optical component which is a Fresnel lens.

The present invention also provides an optical component manufacturing method for obtaining the optical component through the following steps.
Step 1: Filling a mold having two or more optical component mold recesses with a curable composition containing an epoxy compound (A), and then performing light irradiation and / or heat treatment to produce two or more optical components. A cured product having a shape is obtained. Step 2: A cured product is separated into pieces to obtain a separated product. Step 3: A coating layer is formed on the separated product.

  The present invention also provides a method for producing the above-described optical component in which light irradiation is performed using a UV-LED (wavelength: 350 to 450 nm).

  The present invention also provides an optical device on which the optical component is mounted.

  The present invention also provides an optical device manufacturing method in which an optical component is obtained by the optical component manufacturing method, and the obtained optical component is mounted on a substrate by reflow soldering.

The optical component of the present invention comprises a cured product of a curable composition containing the epoxy compound (A). Therefore, it is excellent in heat resistance, and can be mounted on a substrate by reflow soldering (particularly lead-free soldering) together with other components, and an optical device mounted with the optical components can be manufactured with excellent work efficiency. it can. Moreover, since it has a coating layer, it is excellent in light-shielding property or reflectivity.
Moreover, according to the manufacturing method of this invention, said optical component can be manufactured simply and efficiently. And since the manufacturing method of this invention uses the curable composition excellent in the transferability containing an epoxy compound (A), it is an optical component (for example, Fresnel lens, especially portable electronic devices, such as a smart phone, etc.) which has a fine structure. Even a camera's flash Fresnel lens mounted on equipment can be manufactured with high accuracy.

It is a schematic diagram which shows an example of a Fresnel lens, (a-1) is sectional drawing, (a-2) is the figure seen from right above. It is a schematic diagram which shows an example of the manufacturing method of the optical component of this invention. It is a schematic diagram which shows the shape of the hardened | cured material synthesize | combined by the synthesis example. It is a schematic diagram which shows the shape of the singulated material of the hardened | cured material obtained in the Example, FIG. (4-1) is a top view of an individualized material, (4-2) is a perspective view of an individualized material. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows the apparatus produced in order to evaluate the light-shielding property of the singulated material of the hardened | cured material obtained in the Example, FIG. (5-1) is a perspective view of an apparatus, (5-2) is an apparatus. It is sectional drawing. It is explanatory drawing (schematic diagram of a thermogravimetric analysis result) which shows the evaluation method of the heat resistance of hardened | cured material.

[Curable composition]
(Epoxy compound (A))
The curable composition in the present invention contains an epoxy compound as a curable compound (in particular, a cationic curable compound).

  Examples of the epoxy compound include aromatic glycidyl ether type epoxy compounds (for example, bisphenol A type diglycidyl ether and bisphenol F type diglycidyl ether); alicyclic glycidyl ether type epoxy compounds (for example, hydrogenated bisphenol A type diesters). Glycidyl ether, hydrogenated bisphenol F-type diglycidyl ether, etc.); aliphatic glycidyl ether-based epoxy compounds; glycidyl ester-based epoxy compounds; glycidyl amine-based epoxy compounds; alicyclic epoxy compounds; . An epoxy compound can be used individually by 1 type or in combination of 2 or more types.

  In the present invention, it is particularly preferable that an alicyclic epoxy compound is contained in that a cured product having excellent mechanical strength can be obtained. In addition, in this invention, an alicyclic epoxy compound is a compound which has an alicyclic epoxy group (for example, cyclohexene oxide group etc.) comprised by two adjacent carbon atoms and oxygen atoms which comprise an alicyclic ring. .

As said alicyclic epoxy compound, the compound represented by a following formula (a) can be mentioned, for example.

R ^{1 to} R ¹⁸ in the formula (a) are the same or different and are a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group which may contain a halogen atom, or an alkoxy group which may have a substituent. Indicates. X represents a single bond or a linking group.

As a halogen atom in R < ¹ > -R < ¹⁸ >, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. can be mentioned, for example.

As a hydrocarbon group in R < ¹ > -R < ¹⁸ >, a C1-C20 hydrocarbon group is preferable. The hydrocarbon group includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded.

As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable. For example, C _1- such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, isooctyl, decyl, dodecyl group, etc. ₂₀ alkyl groups (preferably C _1-10 alkyl groups, particularly preferably C _1-4 alkyl groups); vinyl, allyl, methallyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1 A C _2-20 alkenyl group (preferably a C _2-10 alkenyl group, particularly preferably a C _2-4 alkenyl group) such as a pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 5-hexenyl group; A C _2-20 alkynyl group such as a propynyl group (preferably a C _2-10 alkynyl group, particularly preferably a C _2-4 alkynyl group) can be exemplified.

As said alicyclic hydrocarbon group, a C3-C15 alicyclic hydrocarbon group is preferable, for example, _C3-12 cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, a _cyclododecyl group; C _3-12 cycloalkenyl groups such as hexenyl groups; C _4-15 bridged cyclic hydrocarbon groups such as bicycloheptanyl and bicycloheptenyl groups.

The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms, and examples thereof include C _6-14 aryl groups such as phenyl and naphthyl groups (preferably C _6-10 aryl groups). be able to.

In addition, the aliphatic hydrocarbon group and the alicyclic hydrocarbon group in a group in which two or more groups selected from the above-described aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group are bonded to each other. Examples of the bonded group include a C _3-12 cycloalkyl-substituted C _1-20 alkyl group such as a cyclohexylmethyl group; a C _1-20 alkyl-substituted C _3-12 cycloalkyl group such as a methylcyclohexyl group. Can do. Examples of the group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include, for example, a C _7-18 aralkyl group such as a benzyl group or a phenethyl group (particularly a C _7-10 aralkyl group); _6-14 aryl substituted C _2-20 alkenyl group; C _1-20 alkyl substituted C _6-14 aryl group such as tolyl group; C _2-20 alkenyl substituted C _6-14 aryl group such as styryl group, etc. it can.

As the hydrocarbon group optionally containing an oxygen atom or a halogen atom in R ^{1 to} R ^18, at least one hydrogen atom in the above hydrocarbon group is substituted with a group having an oxygen atom or a group having a halogen atom. The group etc. can be mentioned. Examples of the group having an oxygen atom include hydroxyl group; hydroperoxy group; C _1-10 alkoxy group such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, isobutyloxy group; C _2-10 such as allyloxy group. An alkenyloxy group; a C _6-14 aryloxy group optionally having a substituent selected from a C _1-10 alkyl group, a C _2-10 alkenyl group, a halogen atom, and a C _1-10 alkoxy group (for example, C _7-18 aralkyloxy groups such as benzyloxy and phenethyloxy groups; C _1-10 acyloxy groups such as acetyloxy, propionyloxy, (meth) acryloyloxy and benzoyloxy groups; methoxy carbonyl, ethoxycarbonyl, propoxycarbonyl, C _1-10 aralkyl such as a butoxycarbonyl group Alkoxycarbonyl group; C _1-10 alkyl group, C _2-10 alkenyl group, a halogen atom, and C _1-10 may have a substituent group selected from an alkoxy group C _6-14 aryloxycarbonyl group ( For example, phenoxycarbonyl, tolyloxycarbonyl, naphthyloxycarbonyl group, etc.); C _7-18 aralkyloxycarbonyl group such as benzyloxycarbonyl group; epoxy group-containing group such as glycidyloxy group; oxetanyl group such as ethyloxetanyloxy group Groups: C _1-10 acyl groups such as acetyl, propionyl and benzoyl groups; isocyanate groups; sulfo groups; carbamoyl groups; oxo groups; and two or more of these are bonded via a single bond or a C _1-10 alkylene group And the like. Examples of the group having a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkoxy group in R ^{1 to} R ¹⁸ include C _1-10 alkoxy groups such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy, and isobutyloxy groups.

Examples of the substituent that the alkoxy group may have include, for example, a halogen atom, a hydroxyl group, a C _1-10 alkoxy group, a C _2-10 alkenyloxy group, a C _6-14 aryloxy group, a C _1-10 Acyloxy group, mercapto group, C _1-10 alkylthio group, C _2-10 alkenylthio group, C _6-14 arylthio group, C _7-18 aralkylthio group, carboxyl group, C _1-10 alkoxycarbonyl group, C _{6- 14} aryloxycarbonyl group, C _7-18 aralkyloxycarbonyl group, amino group, mono or di C _1-10 alkylamino group, C _1-10 acylamino group, epoxy group-containing group, oxetanyl group-containing group, C _1-10 And an acyl group, an oxo group, and a group in which two or more of these are bonded through a single bond or a C _1-10 alkylene group.

R ^{1 to} R ¹⁸ are preferably hydrogen atoms.

  X in the above formula (a) represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, an amide group, and a plurality of these. The group etc. which were connected individually can be mentioned.

Examples of the divalent hydrocarbon group include linear or branched C _1-18 alkylene groups such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene groups (preferably linear or branched chain). C _1-3 alkylene group); 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, Examples thereof include a C _3-12 cycloalkylene group such as a cyclohexylidene group, and a C _3-12 cycloalkylidene group (preferably a C _3-6 cycloalkylene group and a C _3-6 cycloalkylidene group).

Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include, for example, a vinylene group, a propenylene group, and a 1-butenylene group. , 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group or the like, or a straight chain or branched C _2-8 alkenylene group. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably a C _2-4 alkenylene group in which all of the carbon-carbon double bonds are epoxidized. It is.

  Representative examples of the compound represented by the above formula (a) include 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, (3,4,3 ′, 4′-diepoxy) biphenyl. Cyclohexyl, bis (3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 2,2-bis (3,4-epoxy) And cyclohexane-1-yl) propane and 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane. These can be used alone or in combination of two or more. These are preferable in that the shrinkage rate or expansion rate during curing is small.

  The epoxy compound (A) may contain other epoxy compounds in addition to the alicyclic epoxy compound, and the glycidyl ether type epoxy compound (especially aromatic glycidyl ether) in that the refractive index can be adjusted. It is preferable to contain an epoxy-based epoxy compound and / or an alicyclic glycidyl ether-based epoxy compound).

  The content of the epoxy compound (A) in the total amount (100% by weight) of the curable compound contained in the curable composition (the total amount when containing two or more types) is, for example, 30 to 90% by weight, preferably 50 to 90%. % By weight, particularly preferably 60 to 85% by weight. When content of a component (A) is less than the said range, there exists a tendency for the intensity | strength of hardened | cured material to fall. On the other hand, when content of a component (A) exceeds the said range, there exists a tendency for the sclerosis | hardenability of hardened | cured material to fall.

  Further, the content of the alicyclic epoxy compound in the total amount (100% by weight) of the curable composition contained in the curable composition (the total amount when containing two or more types) is, for example, 30 to 80% by weight, preferably 30%. It is -70 weight%, Most preferably, it is 40-60 weight%. When content of an alicyclic epoxy compound is less than the said range, there exists a tendency for sclerosis | hardenability to fall. On the other hand, when the content of the alicyclic epoxy compound exceeds the above range, the cured product tends to be brittle.

(Oxetane compound (B))
The curable composition in the present invention may contain other curable compounds (particularly cationic curable compounds) in addition to the epoxy compound (A), and the curable composition may contain an oxetane compound. It is preferable at the point which can improve sclerosis | hardenability.

（式中、Ｒ^aは１価の有機基を示し、Ｒ^bは水素原子又はエチル基を示す。ｍは０以上の整数を示す） The oxetane compound is represented, for example, by the following formula (b).

(In the formula, R ^a represents a monovalent organic group, R ^b represents a hydrogen atom or an ethyl group, and m represents an integer of 0 or more.)

The monovalent organic group in Ra includes ^a monovalent hydrocarbon group, a monovalent heterocyclic group, a substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, cycloalkyloxycarbonyl group). Etc.), substituted carbamoyl groups (N-alkylcarbamoyl groups, N-arylcarbamoyl groups, etc.), acyl groups (aliphatic acyl groups such as acetyl groups; aromatic acyl groups such as benzoyl groups), and two or more of these A monovalent group bonded through a single bond or a linking group is included.

Examples of the monovalent hydrocarbon group include the same examples as R ^{1 to} R ¹⁸ in the above formula (a).

  The monovalent hydrocarbon group includes various substituents [eg, halogen atom, oxo group, hydroxyl group, substituted oxy group (eg, alkoxy group, aryloxy group, aralkyloxy group, acyloxy group, etc.), carboxyl group, Substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group, etc.] You may have. The hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis.

As the heterocyclic ring constituting the heterocyclic group, a 3- to 10-membered ring having a carbon atom and at least one hetero atom (for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.) in the atoms constituting the ring (preferably Includes 4 to 6-membered rings) and condensed rings thereof. Specifically, a heterocycle containing an oxygen atom as a heteroatom (for example, a 4-membered ring such as an oxetane ring; a 5-membered ring such as a furan ring, a tetrahydrofuran ring, an oxazole ring, an isoxazole ring, or a γ-butyrolactone ring; 6-membered rings such as oxo-4H-pyran ring, tetrahydropyran ring and morpholine ring; condensed rings such as benzofuran ring, isobenzofuran ring, 4-oxo-4H-chromene ring, chroman ring and isochroman ring; 3-oxatricyclo [4.3.1.1 ^4,8 ] undecan-2-one ring, bridged ring such as 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one ring), heteroatom A heterocycle containing a sulfur atom as (for example, a 5-membered ring such as a thiophene ring, a thiazole ring, an isothiazole ring or a thiadiazole ring; a 6-membered ring such as a 4-oxo-4H-thiopyran ring; A condensed ring such as a thiophene ring), a heterocyclic ring containing a nitrogen atom as a hetero atom (for example, a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, a triazole ring, etc .; a pyridine ring, a pyridazine ring, a pyrimidine ring, 6-membered rings such as pyrazine ring, piperidine ring, piperazine ring; condensed rings such as indole ring, indoline ring, quinoline ring, acridine ring, naphthyridine ring, quinazoline ring, and purine ring). Examples of the monovalent heterocyclic group include groups in which one hydrogen atom has been removed from the above structural formula of the heterocyclic ring.

The heterocyclic group may have a substituent. As the substituent, in addition to the substituent that the hydrocarbon group may have, an alkyl group (for example, a C group such as a methyl group or an ethyl group). _1-4 alkyl group), cycloalkyl group (for example, C _3-12 cycloalkyl group), aryl group (for example, C _6-14 aryl group such as phenyl group, naphthyl group) and the like.

  Examples of the linking group include a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond (—CONH—), and a carbonate bond. (-OCOO-), a silyl bond (-Si-), and a group in which a plurality of these are linked.

  Examples of the compound represented by the formula (b) include 3-methoxyoxetane, 3-ethoxyoxetane, 3-propoxyoxetane, 3-isopropoxyoxetane, 3- (n-butoxy) oxetane, and 3-isobutoxyoxetane. 3- (s-butoxy) oxetane, 3- (t-butoxy) oxetane, 3-pentyloxyoxetane, 3-hexyloxyoxetane, 3-heptyloxyoxetane, 3-octyloxyoxetane, 3- (1-propenyloxy ) Oxetane, 3-cyclohexyloxyoxetane, 3- (4-methylcyclohexyloxy) oxetane, 3-[(2-perfluorobutyl) ethoxy] oxetane, 3-phenoxyoxetane, 3- (4-methylphenoxy) oxetane, 3 -(3-Chloro-1-pro Xyl) oxetane, 3- (3-bromo-1-propoxy) oxetane, 3- (4-fluorophenoxy) oxetane, and compounds represented by the following formulas (b-1) to (b-15) Can do.

  Examples of the oxetane compound include “Aron oxetane OXT-101”, “Aron oxetane OXT-121”, “Aron oxetane OXT-212”, “Aron oxetane OXT-211”, “Aron oxetane OXT-213”, “Aron oxetane”. Commercial products such as “OXT-221” and “Aron oxetane OXT-610” (manufactured by Toagosei Co., Ltd.) can be used.

  The content of the oxetane compound in the total amount (100% by weight) of the curable compound contained in the curable composition (the total amount when containing two or more types) is, for example, 5 to 40% by weight, preferably 5 to 30% by weight, Particularly preferred is 10 to 30% by weight. When the oxetane compound is contained in the above range, it is preferable in that the effect of improving the curability can be obtained while ensuring the strength of the cured product.

(Other curable compounds)
Although the curable composition in this invention may contain other curable compounds besides the said epoxy compound (A) and oxetane compound (B), content (2 or more types) of other curable compounds The total amount when contained) is, for example, 30% by weight or less, preferably 20% by weight or less, particularly preferably 10% by weight or less, most preferably, of the total amount (100% by weight) of the curable compound contained in the curable composition. 5% by weight or less. If the content of the other curable compound exceeds the above range, the effect of the present invention tends to be difficult to obtain.

(Cationic polymerization initiator (C))
The curable composition in the present invention preferably contains a cationic polymerization initiator. The cationic polymerization initiator includes a photocationic polymerization initiator and a thermal cationic polymerization initiator.

  The cationic photopolymerization initiator is a compound that generates an acid upon irradiation with light and initiates a curing reaction of the cationic curable compound contained in the curable composition, and includes a cation moiety that absorbs light and a source of acid generation. It consists of the anion part. A photocationic polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

  Examples of the photocationic polymerization initiator of the present invention include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salts. And the like, and the like.

  In the present invention, it is particularly preferable to use a sulfonium salt compound in that a cured product having excellent curability can be formed. Examples of the cation moiety of the sulfonium salt compound include (4-hydroxyphenyl) methylbenzylsulfonium ion, triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, and 4- (4-biphenylylthio) phenyl. Examples thereof include arylsulfonium ions (particularly, triarylsulfonium ions) such as -4-biphenylylphenylsulfonium ion and tri-p-tolylsulfonium ion.

As an anion part of the photocationic polymerization initiator, for example, [(Y) _k B (Phf) _4-k ] ⁻ (wherein Y represents a phenyl group or a biphenylyl group. Phf represents at least one hydrogen atom, A phenyl group substituted with at least one selected from a perfluoroalkyl group, a perfluoroalkoxy group, and a halogen atom (k is an integer of 0 to 3), BF ₄ ⁻ , PF ₆ ⁻ , [( Rf) _t PF _6-t ] ⁻ (Rf: an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, t: an integer of 1 to 5), AsF ₆ ⁻ , SbF ₆ ⁻ , SbF ₅ OH ^{− and the} like Can be mentioned. In the present invention, among them, the cationic photopolymerization initiator having an anion moiety of SbF ₆ ⁻ has high activity as an initiator, has high curability, and can obtain a cured product having excellent heat resistance. Is preferable.

  Examples of the photocationic polymerization initiator of the present invention include (4-hydroxyphenyl) methylbenzylsulfonium tetrakis (pentafluorophenyl) borate, 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (penta Fluorophenyl) borate, 4- (phenylthio) phenyldiphenylsulfonium phenyltris (pentafluorophenyl) borate, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate, Diphenyl [4- (phenylthio) phenylsulfonium] hexafluoroantimonate, diphenyl [4- (phenylthio) phenyl] sulfonium tris (pentafluoroethyl) Lifluorophosphate, diphenyl [4- (phenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, 4- (4-biphenylylthio) phenyl-4-biphenyl Rilphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide phenyltris (pentafluorophenyl) borate, [4- (2-thioxanthonylthio) phenyl] phenyl-2 -Thioxanthonylsulfonium phenyltris (pentafluorophenyl) borate, trade names "Syracure UVI-6970", "Syracure UVI-6974", "Syrah "Ure UVI-6990", "Syracure UVI-950" (manufactured by Union Carbide, USA), "Irgacure 250", "Irgacure 261", "Irgacure 264", "CG-24-61" (above, manufactured by BASF), “CG-24-61” (manufactured by Ciba Geigy), “Optomer SP-150”, “Optomer SP-151”, “Optomer SP-170”, “Optomer SP-171” (above, manufactured by ADEKA Corporation), “DAICAT II” (manufactured by Daicel Corporation), “UVAC1590”, “UVAC1591” (manufactured by Daicel-Cytec Inc.), “CI-2064”, “CI-2638”, “CI-2624”, “ CI-2481 "," CI-2734 "," CI-2855 "," CI-2823 " CI-2758 ”,“ CIT-1682 ”(manufactured by Nippon Soda Co., Ltd.),“ PI-2074 ”(manufactured by Rhodia, tetrakis (pentafluorophenyl) borate toluylcumyliodonium salt),“ FFC509 ”(3M Manufactured by the same company), “BBI-102”, “BBI-101”, “BBI-103”, “MPI-103”, “TPS-103”, “MDS-103”, “DTS-103”, “NAT-103” ", NDS-103" (above, manufactured by Midori Chemical Co., Ltd.), "CD-1010", "CD-1011", "CD-1012" (above, manufactured by Sartomer, USA), "CPI-100P" Commercial products such as “CPI-101A” (manufactured by San Apro Co., Ltd.) can be used.

  The thermal cationic polymerization initiator is a compound that generates an acid by heat treatment and initiates a curing reaction of the cationic curable compound contained in the curable composition, and generates a cation moiety that absorbs heat and an acid. It consists of the anion part which becomes the source. A thermal cationic polymerization initiator can be used individually by 1 type or in combination of 2 or more types.

  Examples of the thermal cationic polymerization initiator of the present invention include iodonium salt compounds and sulfonium salt compounds.

  Examples of the cationic part of the thermal cationic polymerization initiator include 4-hydroxyphenyl-methyl-benzylsulfonium, 4-hydroxyphenyl-methyl- (2-methylbenzyl) sulfonium, 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium. , P-methoxycarbonyloxyphenyl-benzyl-methylsulfonium (particularly monoarylsulfonium ion) and the like.

  As an anion part of a thermal cationic polymerization initiator, the same example as the anion part of the said photocationic polymerization initiator can be given.

  Examples of the thermal cationic polymerization initiator include 4-hydroxyphenyl-methyl-benzylsulfonium phenyltris (pentafluorophenyl) borate and 4-hydroxyphenyl-methyl- (2-methylbenzyl) sulfonium phenyltris (pentafluorophenyl) borate. 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium phenyltris (pentafluorophenyl) borate, p-methoxycarbonyloxyphenyl-benzyl-methylsulfonium phenyltris (pentafluorophenyl) borate, and the like.

  As a curable composition in this invention, it is preferable to contain a photocationic polymerization initiator especially at the point which is excellent in storage stability.

  As content of a cationic polymerization initiator, it is 0.1-10 with respect to 100 weight part of sclerosing | hardenable compounds (especially cationic curable compound, when it contains 2 or more types) contained in a curable composition, for example. 0.0 parts by weight, preferably 0.1 to 5.0 parts by weight, particularly preferably 0.2 to 3.0 parts by weight, and most preferably 0.2 to 1.0 parts by weight. When content of a cationic polymerization initiator is less than the said range, there exists a tendency for sclerosis | hardenability to fall. On the other hand, when the content of the cationic polymerization initiator exceeds the above range, the cured product tends to be easily colored.

(Other ingredients)
The curable composition in the present invention may contain other components in addition to the epoxy compound (A), the oxetane compound (B), and the polymerization initiator (C) as long as the effects of the present invention are not impaired. Good. Examples of other components include an antioxidant, a photosensitizer, an antifoaming agent, a surface modifier, a coupling agent, a surfactant, a flame retardant, and an ultraviolet absorber. These can be used alone or in combination of two or more.

  Examples of the surface modifier include silicone-based, acrylic-based, and fluorine-based surfactants. By adding a surface modifier to the curable composition, the wettability to the mold can be improved, and the effect of reducing foaming at the time of filling the curable composition into the mold can be obtained. In the present invention, a silicone-based surfactant is particularly preferable because it is particularly excellent in the effect of reducing foaming.

  Examples of the silicone surfactant include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane having an acrylic group, and polyester-modified polydimethylsiloxane having an acrylic group. In the present invention, for example, trade names “BYK-333”, “BYK-345”, “BYK-UV3510”, “BYK-UV3500”, “BYK-UV3530”, “BYK-UV3570” (above, Big Chemie Japan) Commercially available products such as those manufactured by KK can be suitably used.

  The content of the surface modifier (the total amount when two or more are included) is, for example, 0.01 to 3 parts by weight relative to the total amount of the curable compound (100 parts by weight) contained in the curable composition. The amount is preferably 0.03 to 2 parts by weight, particularly preferably 0.1 to 1 part by weight.

  Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, thioester antioxidants, amine antioxidants, and the like. In the present invention, it is preferable to use a phenol-based antioxidant and / or a phosphorus-based antioxidant because the heat resistance of the resulting cured product can be further improved.

  Examples of phenolic antioxidants include pentaerythritol tetrakis [3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-di-t-butyl). -4-hydroxyphenyl) propionate], octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propanoate, N, N'-hexamethylenebis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionamide], octyl 3- (4-hydroxy-3,5-diisopropylphenyl) propionate, 1,3,5-tris (4-hydroxy-3,5-di-t-) Butylbenzyl) -2,4,6-trimethylbenzene, 2,4-bis (dodecylthiomethyl) -6-methylphenol, calcium bi [3,5-di (t-butyl) -4-hydroxybenzyl (ethoxy) phosphinate], and the like. In the present invention, for example, trade names “Irganox 1010”, “Irganox 1035”, “Irganox 1076”, “Irganox 1098”, “Irganox 1135”, “Irganox 1330”, “Irganox 1726”, “Irganox 1726”, “Irganox 1726” Commercial products such as BASF) may be used.

  Examples of phosphorus antioxidants include 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (2 , 6-Di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 2,2'-methylenebis (4,6-di-) t-butylphenyl) -2-ethylhexyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, and the like. In the present invention, for example, trade names “PEP-8”, “PEP-8W”, “PEP-36 / 36A”, “HP-10”, “2112”, “2112RG”, “1178” ) Commercial products such as ADEKA) can be used.

  The content of the antioxidant (when 2 or more types are contained, the total amount) is 100 parts by weight of the curable compound contained in the curable composition (particularly the cationic curable compound, when 2 or more types are contained). For example, 0.1 to 10.0 parts by weight, preferably 0.5 to 5.0 parts by weight, and particularly preferably 0.5 to 3.0 parts by weight.

  The curable composition in the present invention can be prepared, for example, by stirring and mixing the above components at a predetermined ratio and defoaming under vacuum as necessary.

  The viscosity (at 25 ° C., shear rate 20 (1 / s)) of the curable composition in the present invention is, for example, 100 to 1000 mPa · s, and the upper limit of the viscosity is preferably 500 mPa · s, particularly preferably 400 mPa · s. s, most preferably 350 mPa · s, particularly preferably 250 mPa · s. Therefore, it is excellent in the filling property to a mold, can reduce foaming, and can manufacture a highly accurate optical component excellent in shape transferability.

  Furthermore, the curable composition in this invention is excellent in sclerosis | hardenability, and can harden | cure rapidly by performing light irradiation and / or heat processing, and can form hardened | cured material.

  When a curable composition containing a photocationic polymerization initiator is used as the cationic polymerization initiator (C), it can be cured by light irradiation. Any of infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays, and the like can be used as light (active energy rays) used for the light irradiation. In the present invention, among these, ultraviolet rays are preferable in terms of excellent handleability. For UV irradiation, for example, a UV-LED (wavelength: 350 to 450 nm), a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, a laser, or the like can be used. Since the curable composition in this invention has the outstanding sclerosis | hardenability, hardening reaction can be advanced rapidly also by the light irradiation by UV-LED.

Irradiation conditions of light, when irradiated with ultraviolet rays, it is preferable to adjust the accumulated light quantity, for example, in 5000 mJ / cm ² or less (e.g. 2500~5000mJ / cm ^2).

  After light irradiation, a post-bake treatment (for example, heating at 80 to 180 ° C. for 5 to 30 minutes) may be performed as necessary.

  When a curable composition containing a thermal cationic polymerization initiator is used as the cationic polymerization initiator (C), heat treatment (for example, heating at a temperature of 100 to 200 ° C. for about 0.5 to 2 hours) is performed. It can be cured.

  The cured product has excellent heat resistance, and the thermal decomposition temperature is, for example, 200 ° C. or higher (eg, 200 to 500 ° C.), preferably 260 ° C. or higher, particularly preferably 330 ° C. or higher, and most preferably 350 ° C. or higher. In addition, the thermal decomposition temperature is calculated | required by the method as described in an Example. Therefore, the shape can be maintained even when subjected to a substrate mounting process in which soldering (particularly lead-free soldering) is performed using a reflow furnace.

[Optical parts]
The optical component of the present invention is an optical component made of a cured product of the curable composition, and has at least one coating layer having a thickness of 0.1 mm or less on a part of the surface of the optical component.

  The thickness of the coating layer (the thickness of one layer) is 0.1 mm or less (for example, 0.005 to 0.1 mm), preferably 0.09 mm or less (for example, 0.01 to 0.09 mm), particularly preferably. It is 0.08 mm or less (for example, 0.01 to 0.08 mm).

  The number of coating layers is not particularly limited and can be appropriately adjusted as necessary, for example, about 1 to 5 layers. When two or more coating layers are provided, each layer may be the same or different.

  The total thickness of the coating layer is, for example, 10 to 500 μm, preferably 15 to 300 μm, particularly preferably 15 to 100 μm, and most preferably 15 to 50 μm.

  The place where the coating layer is formed in the optical component can be adjusted as appropriate according to the application. For example, the optical component is a lens, and the coating layer is formed for the purpose of imparting reflectivity or light shielding to the lens. Is preferably provided with a coating layer on the outer edge of the lens.

  For example, when the optical component of the present invention has a white coating layer, the optical component can be provided with reflectivity, and when the optical component of the present invention has a black coating layer, the optical component has light shielding properties. Can be granted.

  For example, when the optical component of the present invention is a flash lens, the flash lens is used together with the imaging camera, and light leakage from the flash lens may adversely affect the imaging camera. Therefore, the flash lens preferably has a high light shielding property, and it is preferable to provide a coating layer having a transmittance of, for example, 5% or less (particularly 1% or less). Further, it is preferable that the flash lens has high reflectivity in terms of improving light extraction efficiency, and it is preferable to provide a coating layer having a reflectivity of, for example, 60% or more (particularly 70% or more). .

  The coating material that forms the coating layer contains, for example, a resin, a colorant (pigment), a solvent, and an additive (for example, a flame retardant, a lubricant, an antibacterial agent, an antistatic agent, and the like).

  Examples of the resin include polyolefin resin, polystyrene resin, vinyl chloride resin, fluorine resin, acrylic resin, unsaturated polyester resin, epoxy resin, polyurethane resin, phenol resin, and the like. These can be used alone or in combination of two or more.

  Examples of the colorant include inorganic pigments [titanium oxide, zinc oxide, chromium oxide, iron oxide, carbon black, ultramarine, titanium black, acetylene black, lamp black, bone black, graphite, iron black, and copper chromium black. , Copper iron manganese black, cobalt iron chromium black, ruthenium oxide, graphite, metal fine particles (such as aluminum), metal oxide fine particles, composite oxide fine particles, metal sulfide fine particles, metal nitride fine particles, etc.], organic Pigments [perylene black, cyanine black, aniline black, azo pigment, anthraquinone pigment, isoindolinone pigment, indanthrene pigment, indigo pigment, quinacridone pigment, dioxazine pigment, tetraazaporphyrin pigment, tria Reel methane pigment It can be mentioned phthalocyanine pigments, perylene pigments, benzimidazolone pigments, rhodamine-based pigments, etc.] or the like. These can be used alone or in combination of two or more.

  Examples of the solvent include aromatic solvents such as toluene and xylene, ester solvents such as ethyl acetate, and the like. These can be used alone or in combination of two or more.

  The content of each component contained in the coating material is not particularly limited and can be appropriately adjusted as necessary.

  The maximum thickness of the optical component (including the coating layer) is 2 mm or less (for example, 0.1 to 2 mm), preferably 1.8 mm or less (for example, 0.1 to 1.8 mm), particularly preferably 1. It is 6 mm or less (for example, 0.1 to 1.6 mm).

  The maximum width of the optical component in plan view (maximum width in a plan view viewed from directly above) is 10 mm or less (for example, 1 to 10 mm), preferably 8 mm or less (for example, 1 to 8 mm), and particularly preferably 7 mm. Or less (for example, 1 to 7 mm), particularly preferably 5 mm or less (for example, 1 to 5 mm).

  The optical component of the present invention includes a lens [for example, a Fresnel lens, particularly preferably a flash Fresnel lens for a camera (for example, an imaging camera used in a portable electronic device such as a smartphone), an infrared sensor Fresnel lens], etc. Is included.

  The Fresnel lens is a lens having a light diffusing or condensing effect, having two or more angle-shaped prisms having a reflecting surface (a surface that changes the traveling direction of light) and a refracting surface (a surface that transmits light) on the surface. The two or more mountain-shaped prisms continuously become smaller (or larger) toward the center (for example, FIG. 1).

[Manufacturing method of optical components]
The optical component of the present invention is manufactured by casting, more specifically, through the following steps.
Step 1: Filling a mold having two or more optical component mold recesses with a curable composition containing an epoxy compound (A), and then performing light irradiation and / or heat treatment to produce two or more optical components. A cured product having a shape is obtained. Step 2: A cured product is separated into pieces to obtain a separated product. Step 3: A coating layer is formed on the separated product.

  The mold has two or more desired optical component-type concave portions [that is, concave portions having an inverted shape of an optical component (for example, a Fresnel lens)). The two or more optical component mold recesses may be arranged at random or may be arranged at equal intervals, but in particular, a mold having two or more optical component mold recesses arranged at equal intervals is used. It is preferable in terms of excellent workability such as singulation.

  Examples of the method for filling the mold with the curable composition in Step 1 include a method using a dispenser, a screen printing method, a curtain coating method, and a spray method. Since the curable composition in the present invention is excellent in fluidity, it is possible to produce a Fresnel lens having high filling property and excellent mold shape transferability (= excellent reproducibility of mold concave shape). . The mold may be composed of a plurality of parts such as a bottom and a lid. The mold may be subjected to a mold release process (for example, application of a mold release agent) in advance.

  Examples of the material of the mold include metal, glass, plastic, and silicone. Especially, since it has transparency, it can be used for molding of a curable composition that is cured by light irradiation, and a silicone mold (for example, polydimethylsiloxane is used as a raw material in terms of excellent shape transferability and releasability. Silicone mold) is preferred.

  In addition, the “light irradiation and / or heat treatment” in step 1 is carried out with light irradiation when a curable composition containing a photocationic polymerization initiator is used as the cationic polymerization initiator (C) to initiate cationic polymerization. When a curable composition containing a thermal cationic polymerization initiator is used as the agent (C), a heat treatment is performed.

  Any of infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays, and the like can be used as light (active energy rays) used for the light irradiation. In the present invention, among these, ultraviolet rays are preferable in terms of excellent handleability. For UV irradiation, for example, a UV-LED (wavelength: 350 to 450 nm), a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, a laser, or the like can be used. Since the curable composition in this invention has the outstanding sclerosis | hardenability, hardening reaction can be advanced rapidly also by the light irradiation by UV-LED. Moreover, when making it harden | cure by light irradiation, it is preferable to use a transparent mold as a mold.

Irradiation conditions of light, when irradiated with ultraviolet rays, it is preferable to adjust the accumulated light quantity, for example, in 5000 mJ / cm ² or less (e.g. 2500~5000mJ / cm ^2).

  After the light irradiation, the Fresnel lens array is obtained by releasing the mold. Moreover, you may perform a post-baking process (for example, heating for 5 to 30 minutes at 80-180 degreeC) as needed before mold release or after mold release.

  The heating temperature in the heat treatment is, for example, about 100 to 200 ° C., and the heating time is, for example, about 0.5 to 2 hours.

  Step 2 is a cured product obtained through Step 1 [more specifically, a cured product having a shape of two or more optical components (preferably having a shape of two or more optical components at equal intervals). And a cured product having a configuration in which two or more optical components are joined via a connecting portion] (preferably, cutting at the connecting portion) to separate the optical components into pieces, that is, a dicing step. . The cutting is performed using a cutting means such as a dicing blade.

  In the method for producing an optical component of the present invention, a curable composition containing an epoxy compound (A) is used, and the curable composition has a small shrinkage rate or expansion rate upon curing, and thus has excellent transferability. It is possible to manufacture a product, and it is possible to accurately manufacture a cured product having the shape of two or more optical components at regular intervals. The deviation of the interval between two adjacent optical components on the cured product is, for example, 15 μm or less, preferably 10 μm or less, and particularly preferably 8 μm or less. Therefore, in the dicing process, it can be separated into pieces with high accuracy using a cutting means such as a dicing blade, and high-precision optical components can be mass-produced efficiently.

  Step 3 is a step of forming a coating layer on the singulated cured product (that is, the singulated product) obtained through Steps 1 and 2. Only one coating layer may be formed, or two or more coating layers may be formed. That is, the coating layer may have a single layer structure or a multilayer structure.

  In step 3, before the coating layer is formed, the cured product may be subjected to a surface treatment in order to improve the adhesion between the cured product and the coating layer. Examples of the surface treatment include undercoating, corona treatment, plasma treatment, ozone treatment, and excimer treatment. These can be performed singly or in combination of two or more.

  The coating layer can be formed by applying a coating material on the surface of an individualized product (or a surface-treated individualized product). As the coating material, one or two of the above-mentioned coating materials can be used. More than seeds can be used.

  Examples of the method for applying the coating material include a method using a dispenser, a screen printing method, a curtain coating method, and a spray method. After the coating material is applied, the coating material can be formed by solidifying or curing the coating material by drying and heating treatment and / or light irradiation as necessary. By repeating the above operation, a coating layer having a multilayer structure of two or more layers can be formed.

  Further, before applying the coating material, it is preferable to perform masking by sticking an adhesive tape or the like to a portion where the coating layer is not formed, and the adhesive tape used for the masking is removed after applying the coating material. It is preferable.

  Furthermore, in step 2, the singulation process is performed in a state where the cured product obtained through step 1 is fixed to a support (for example, attached to an adhesive tape such as a dicing tape), thereby causing a positional shift or the like. The coating layer can be formed in a lump by subjecting the individualized product fixed to the support to the subsequent step 3 and coating finely individualized products efficiently. It is preferable at the point which can form a layer. When the interval between the individualized products is narrow after completion of the individualization processing, it is preferable to widen the interval by expanding the adhesive tape or the like. This is because the coating layer can be formed also on the cut surface (side surface of the optical component) by applying the coating material in a state where the interval between the separated pieces is moderately spaced.

Accordingly, the steps 2 and 3 of the present invention are preferably as follows.
Step 2: The cured product is singulated in a state of being fixed to the support to obtain a singulated product fixed to the support. Step 3: A coating layer is formed on the singulated product fixed to the support.

  And after forming a coating layer in the state which fixed the singulated material with the adhesive tape, it picks up from an adhesive tape and attaches | subjects to board | substrate mounting etc.

An example of the manufacturing method of the optical component of the present invention is shown in FIG. Each step in FIG. 2 will be described below.
[1] A mask (2) is attached to a cured product (1) having a shape of two or more optical components (= masking).
[2] Dicing the cured product (1) along the cutting line (3) to obtain an individualized product (4) having a mask (2) [3] Applying a coating material to form a coating layer (5) [4] The mask (2) is removed to obtain the optical component (6, 7) (= single product having a coating layer).

  According to the method for producing an optical component of the present invention, even a fine optical component (for example, a Fresnel lens, particularly a Fresnel lens for a flash of a camera) can be easily and efficiently produced by casting. Further, by changing the coating material, it is possible to easily make optical components having a wide variety of coating layers. Furthermore, it is easy to form a coating layer having a multilayer structure. Therefore, the method for manufacturing an optical component of the present invention is suitable as a method for manufacturing an optical component having a coating layer (for example, a flash lens used in a portable electronic device such as a smartphone). Optical components can be provided at low cost.

[Optical device]
The optical device of the present invention mounts the optical component. The optical device of the present invention includes, for example, portable electronic devices such as mobile phones, smartphones, tablet PCs, infrared sensors, near infrared sensors, millimeter wave radars, LED spot illumination devices, near infrared LED illumination devices, In-vehicle electronic devices such as a mirror monitor, a meter panel, a head-mounted display (projection type) combiner, and a head-up display combiner are included.

  The optical component has sufficient heat resistance to be mounted on a substrate by high-temperature heat treatment (for example, high-temperature treatment at 260 ° C. or higher such as reflow soldering). Therefore, the optical device of the present invention does not require the optical component to be mounted in a separate process, and can be optically mounted on the substrate by high-temperature heat treatment (for example, reflow soldering). And it can manufacture at low cost. In addition, since the optical component is excellent in heat resistance, it can be used for in-vehicle electronic devices.

  Therefore, as a method for manufacturing the optical device of the present invention, a method of obtaining an optical component by the above-described optical component manufacturing method and mounting the obtained optical component on a substrate by reflow soldering is preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

[Preparation Example 1: Synthesis of (3,4,3 ′, 4′-diepoxy) bicyclohexyl (a-1)]
A dehydration catalyst was prepared by stirring and mixing 70 g (0.68 mol) of 95 wt% sulfuric acid and 55 g (0.36 mol) of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU).
Into a 3 L flask equipped with a stirrer, a thermometer, and a distillation pipe filled with a dehydrating agent and kept warm, 1000 g (5.05 mol) of hydrogenated biphenol (4,4′-dihydroxybicyclohexyl), 125 g of the prepared dehydration catalyst (0.68 mol as sulfuric acid) and 1500 g of pseudocumene were added, and the flask was heated. The generation of water was confirmed when the internal temperature exceeded 115 ° C. The temperature was further raised to raise the temperature to the boiling point of pseudocumene (internal temperature 162 to 170 ° C.), and dehydration reaction was carried out at normal pressure. By-product water was distilled off and discharged out of the system through a dehydration tube. The dehydration catalyst was liquid under the reaction conditions and was finely dispersed in the reaction solution. After about 3 hours, almost theoretical amount of water (180 g) was distilled, and the reaction was terminated.
Pseudocumene was distilled off using a 10-stage Oldershaw type distillation column, and the reaction-terminated liquid was distilled at an internal pressure of 10 Torr (1.33 kPa) and an internal temperature of 137 to 140 ° C. to obtain 731 g of bicyclohexyl-3. , 3′-diene was obtained.

The obtained bicyclohexyl-3,3′-diene (243 g) and ethyl acetate (730 g) were charged into a reactor, and nitrogen was blown into the gas phase portion, and the temperature in the reaction system was controlled to 37.5 ° C. Then, 274 g of 30 wt% peracetic acid in ethyl acetate (water content: 0.41 wt%) was added dropwise over about 3 hours.
After completion of the dropwise addition, the reaction was terminated by aging at 40 ° C. for 1 hour. Further, the crude liquid at the end of the reaction was washed with water at 30 ° C., and the low boiling point compound was removed at 70 ° C./20 mmHg to obtain 270 g of a reaction product. The oxirane oxygen concentration of the reaction product was 15.0% by weight.
In ¹ H-NMR measurement, a peak derived from an internal double bond near δ4.5 to 5 ppm disappeared, and a proton peak derived from an epoxy group was confirmed near δ3.1 ppm. The product was confirmed to be (3,4,3 ′, 4′-diepoxy) bicyclohexyl.

[Preparation Example 2: Synthesis of bis (3,4-epoxycyclohexylmethyl) ether (a-2)]
To a 5 L reactor, 499 g (12.48 mol) of sodium hydroxide (granular) and 727 mL of toluene were added, and after purging with nitrogen, a solution of 484 mL of toluene in 420 g (3.74 mol) of tetrahydrobenzyl alcohol was added. For 1.5 hours. Next, 419 g (2.20 mol) of methanesulfonic acid tetrahydrobenzyl was added, and the mixture was aged for 3 hours under reflux, and then cooled to room temperature. The reaction was stopped by adding 1248 g of water, followed by liquid separation.
After concentration of the separated organic layer, distillation under reduced pressure was performed to obtain ditetrahydrobenzyl ether as a colorless transparent liquid (yield: 85%). The ¹ H-NMR spectrum of the obtained ditetrahydrobenzyl ether was measured.
¹ H-NMR (CDCl ₃ ): δ 1.23-1.33 (m, 2H), 1.68-1.94 (m, 6H), 2.02-2.15 (m, 6H), 3.26-3.34 (m, 4H), 5.63-7.70 (m, 4H)

  200 g (0.97 mol) of the obtained ditetrahydrobenzyl ether, 0.39 g of 20% SP-D (acetic acid solution) and 669 mL of ethyl acetate were added to the reactor, and the temperature was raised to 40 ° C. Next, 608 g of 29.1% peracetic acid was added dropwise over 5 hours and aged for 3 hours. Thereafter, the organic layer was washed three times with an aqueous alkaline solution and twice with ion-exchanged water, and then distilled under reduced pressure to obtain bis (3,4-epoxycyclohexylmethyl) ether as a colorless transparent liquid (yield) : 77%).

Synthesis Examples 1 to 3
Each component was mixed according to the prescription (unit: parts by weight) shown in Table 1 below to obtain a curable composition. The viscosity of the curable composition obtained in Synthesis Example 1 is 120 mPa · s, the viscosity of the curable composition obtained in Synthesis Example 2 is 145 mPa · s, and the viscosity of the curable composition obtained in Synthesis Example 3 is It was 583 mPa · s. The viscosity was measured using a rheometer (trade name “PHYSICA UDS200”, manufactured by Anton Paar) under the conditions of a temperature of 25 ° C. and a shear rate of 20 (1 / s).

  The obtained curable composition was poured into a silicone mold (bottom), and a spacer was sandwiched so that the thickness became 1.0 mm. The mold is closed with a silicone mold (lid), and UV-LED (365 nm, manufactured by OMRON Corporation) is irradiated (100 mW × 30 seconds) to cure the curable composition, so that a total of 36 rectangular parallelepiped shapes Cured material having a combined shape in which concave portions (3.6 mm × 3.6 mm × 0.8 mm) of the above are arranged with a pitch width of 4.1 mm (6 vertical × 6 horizontal) via the connecting portion (see FIG. 3). Got.

[Evaluation of transfer accuracy]
The distance (pitch) between the center points of two adjacent recesses in the obtained cured product was measured using a CNC image measurement system (trade name “NEXIVE VMZ-3020”, manufactured by Nikon Corporation), The deviation from the design value (ideal grid point) was measured to evaluate the transfer accuracy.

Example 1 [cured product having a coating layer]
A masking tape of 3.6 mm × 3.6 mm was attached to the surface of the cured product obtained in Synthesis Example 1 on the side opposite to the surface having the recesses with a pitch width of 4.1 mm in accordance with the recesses. Thereafter, the dicing tape is applied to the back side of the cured product (the surface opposite to the surface on which the masking tape is applied), and then a dicing saw (trade name “DFD6361”, manufactured by DISCO Corporation, dicing blade thickness 0. 1 mm), cut the connecting portion to separate the cured product, and separate 36 pieces of the cured product (single product) (4.0 mm × 4.0 mm × 1.0 mm) on the dicing tape. Obtained in a fixed state.

  Thereafter, the surface of the singulated material was subjected to corona treatment to obtain a surface-treated singulated material (hereinafter, sometimes referred to as “single product before coating”).

The trade name “6080” (manufactured by Labsphere) was used as the white coating material.
The above-mentioned coating material was sprayed on the obtained surface-treated singulated material using a spray gun so as to have a uniform film thickness. Then, the coating material was solidified by drying at 120 ° C. for 2 hours to obtain an individualized product having a coating layer (one layer) (see FIG. 4).

For the individualized product having the obtained coating layer, the wall thickness was measured using a micrometer (manufactured by Mitutoyo Corporation), the wall thickness of the individualized product before coating was also measured, and the following formula The film thickness of the coating layer was calculated.
(Thickness of coating layer) = (Thickness of wall of individualized product having coating layer) − (Thickness of wall of individualized product before coating)

[Appearance evaluation]
The appearance of the individualized product having the obtained coating layer was visually observed, and the appearance was evaluated according to the following criteria.
○: Abnormality of foaming, dirt, cracks, molding failure, dripping, and coating failure was not observed. ×: Selected from foaming, dirt, cracking, molding failure, dripping, and coating failure. One or more abnormalities were observed

[Optical characteristics evaluation]
The LED light source (the distance between the individualized product and the light source is 1.0 mm) immediately after the individualized product having the obtained coating layer (the central illuminance of the following projection plate is about 100 lux without the individualized product being disposed) Was used to irradiate light. Illuminance at the center of the projection plate (1.2 m × 0.92 m) placed in front of the individualized object (1.2 m × 0.92 m) and the peripheral part (at a radius of 0.77 m from the center) The average illuminance at four locations was measured using an illuminometer (trade name “CL-200A”, manufactured by Konica Minolta, Inc.).

[Light shielding evaluation]
The obtained singulated material having a coating layer is placed on an LED light source placed on a ceramic substrate, placed in the opening of the light shielding film, and inside the light shielding film when the LED light source is turned on. The presence or absence of light leakage was visually confirmed, and the light shielding property was evaluated according to the following criteria (see FIG. 5).
○: No light leakage was observed ×: Light leakage was observed

[Heat resistance evaluation]
A part of the singulated material having the obtained coating layer was cut out, and using a thermal analyzer (trade name “TG-DTA6300”, manufactured by Seiko Denshi Kogyo Co., Ltd.) under a nitrogen atmosphere, the heating rate was 10 ° C. / The thermal decomposition temperature (T) was measured by thermogravimetric analysis under the conditions of minutes. As shown in FIG. 6, the thermal decomposition temperature (T) is a tangential line where there is no initial weight decrease or is gradually decreasing (range indicated by A in the figure), and a sudden weight decrease. It is the temperature at which the tangent of the inflection point where it is occurring (range indicated by B in the figure) intersects.

Examples 3 to 5 (Example 4 is a reference example)
The coating material and the coating layer thickness were changed as shown in the table, and with the change of the coating material, the same procedure was performed as in Example 1 except that the coating layer forming method was changed as follows. The appearance, optical properties, light shielding properties, and heat resistance were evaluated. In Examples 3 and 5, an individualized product having a coating layer (two layers) was obtained.

Example 2
The cured product obtained in Synthesis Example 2 was used in place of the cured product obtained in Synthesis Example 1, and the coating material and coating layer thickness were changed as described in the table. Except having changed the formation method of a layer as follows, it carried out similarly to Example 1 and obtained the singulated material which has a coating layer, and evaluated the external appearance, the optical characteristic, light-shielding property, and heat resistance.

Comparative Example 2
The cured product obtained in Synthesis Example 3 was used in place of the cured product obtained in Synthesis Example 1, and the coating material and coating layer thickness were changed as described in the table. Except having changed the formation method of a layer as follows, it carried out similarly to Example 1 and obtained the singulated material which has a coating layer, and evaluated the external appearance, the optical characteristic, light-shielding property, and heat resistance.

As the silver coating material, the product name “Hiurex P UNP79” (2 liquid type) is used by mixing 2 liquids, dried at 80 ° C. for 10 minutes, and further heated at 100 ° C. for 1 hour. Was cured.
As the black coating material, the trade name “GT-7II” (manufactured by Canon Kasei Co., Ltd.) was used, dried at 80 ° C. for 2 hours, and further heated at 120 ° C. for 1 hour to cure the coating material. .
As a transparent coating material, the product name “Z-700K-2” (manufactured by Aika Industry Co., Ltd.) is used, dried at 80 ° C. for 5 minutes, and further irradiated with 50 mW / cm ² of light for 30 seconds. The material was cured.

Comparative Example 1
About the hardened | cured material (surface-processed individualized material) before providing the coating layer obtained in Example 1, the external appearance, the optical characteristic, light-shielding property, and heat resistance were evaluated similarly.

Abbreviations in Table 1 are as follows.
<Curable compound>
CELLOXIDE 2021P: 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, molecular weight 252, trade name “Celoxide 2021P”, manufactured by Daicel Corporation (a-1): the compound obtained in Preparation Example 1, (3,4,3 ′, 4′-diepoxy) bicyclohexyl, molecular weight 194
(A-2): Compound obtained in Preparation Example 2, bis (3,4-epoxycyclohexylmethyl) ether, molecular weight 238
OXT101: 3-ethyl-3-hydroxymethyloxetane, molecular weight 116, trade name “Aron oxetane OXT-101”, manufactured by Toagosei Co., Ltd. YX8000: hydrogenated bisphenol A type epoxy compound, molecular weight 353, trade name “YX8000”, <Surface modifier> manufactured by Mitsubishi Chemical Corporation
BYK-333: Polyether-modified polydimethylsiloxane, trade name “BYK-333”, manufactured by Big Chemie Japan Co., Ltd. <cationic polymerization initiator>
CPI-101A: Diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate, trade name “CPI-101A”, manufactured by San Apro Co., Ltd.

DESCRIPTION OF SYMBOLS 1 Hardened | cured material which has a shape which two or more optical components couple | bonded through the connection part 2 Mask 3 Cutting line 4 Individualized product 5 Cured material 5 Coating layer 6 Individualized product (optical component) which has a coating layer (plan view) )
7 Individualized product (optical component) having a coating layer (perspective view)
8 Cured product 9 obtained in Example 9 Recess 10 Light shielding curtain 11 LED light 12 Coating layer 13 in singulated product 13 Layer 14 made of cured product of curable composition in singulated product LED device 15 Ceramic substrate 16 Observation viewpoint

Claims (6)

A flash lens comprising a cured product of a curable composition containing an epoxy compound (A) , the coating having a thickness of 0.1 mm or less and a reflectance of 60% or more on the outer edge and side surface of the flash lens A flash lens having at least one layer and having a maximum thickness of 2 mm or less and a maximum width of 10 mm or less in plan view. The flash lens according to claim 1, wherein the coating layer having a reflectance of 60% or more is a white or silver coating layer. The flash lens according to claim 1 or 2 , wherein the epoxy compound (A) contains a compound represented by the following formula (a).

[Wherein, R ^{1 to} R ¹⁸ are the same or different and each represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group that may contain a halogen atom, or an alkoxy group that may have a substituent. . X represents a single bond or a linking group] The flash lens according to any one of claims 1 to 3, wherein the curable composition contains an epoxy compound (A), an oxetane compound (B), and a cationic polymerization initiator (C). The flash lens according to any one of claims 1 to 4 , wherein a thermal decomposition temperature is 200 ° C or higher. The manufacturing method of the flash lens which manufactures the flash lens of any one of Claims 1-5 through the following process.
Step 1: A mold is filled with a curable composition containing an epoxy compound (A), and then light irradiation and / or heat treatment is performed, so that two or more flash lenses are bonded via a connecting portion. Obtaining a lens array Step 2: Divide the lens array to obtain a flash lens Step 3: Form a coating layer on the outer edge and side of the flash lens

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