JP6503026B2 - Optical part and optical apparatus provided with the same - Google Patents

Description

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

  In a camera mounted on a portable electronic device such as a smartphone, a flash lens is installed immediately in front of the light source in order to diffuse light from the light source. And as the said flash lens, the Fresnel lens which can respond to thickness reduction and size reduction is mainly used.

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

  Here, as a manufacturing method of a lens, the method of injection-molding using thermoplastic resins, such as a polycarbonate, a polymethyl methacrylate, a cycloolefin polymer, for example is known (patent documents 1-2). However, in injection molding, it has been difficult to manufacture a fine lens used for a camera mounted on a portable electronic device such as a smartphone. Furthermore, it is very difficult to coat the fine lenses obtained by injection molding one by one. In addition, the method of forming a lens by two-color molding is expensive in equipment, and it has been difficult to inexpensively produce a large amount of lenses. Furthermore, the lens obtained by using a thermoplastic resin is inferior in heat resistance, and can not be mounted on a substrate by reflow soldering (especially lead-free soldering) together with other parts. .

JP, 2013-212593, A JP, 2013-224349, A

Therefore, an object of the present invention is to provide an optical component which is fine and excellent in heat resistance, and which has a coating layer on a part thereof.
Another object of the present invention is to provide a method for easily and efficiently producing the optical component.
Another object of the present invention is to provide an optical device provided with the optical component.

  As a result of intensive studies to solve the above problems, the inventors of the present invention 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, The curable composition is subjected to casting molding using a mold having a plurality of optical part-type recesses to form a cured product having the shape of two or more optical parts, and then obtained by cutting. It has been found that by applying a coating to the surface of the cured product, it is possible to easily and efficiently manufacture a fine optical component having a coating layer. 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), wherein at least one coating layer having a thickness of 0.1 mm or less is formed on part of the surface of the optical component. Provided is an optical component having a maximum thickness of 2 mm or less and a maximum width of 10 mm or less in plan view.

［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 represent a hydrogen atom, a halogen atom, a hydrocarbon group which may contain an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent] . X represents a single bond or a linking group]

  The present invention also provides the optical component as described above, 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 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 a method of producing an optical component which obtains the above optical component through the following steps.
Step 1: The curable composition containing the epoxy compound (A) is filled in a mold having two or more optical component-type recesses, and then light irradiation and / or heat treatment is performed to obtain two or more optical components. Step 2: Obtain a cured product having a shape Step 2: singulate the cured product to obtain an individualized product Step 3: form a coating layer on the individualized component

  The present invention also provides a method of producing the above-mentioned optical component, which performs light irradiation using a UV-LED (wavelength: 350 to 450 nm).

  The present invention also provides an optical device mounted with the above optical component.

  The present invention also provides a method for producing an optical device, wherein an optical component is obtained by the method for producing an optical component, 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 an epoxy compound (A). Therefore, it is excellent in heat resistance, and can be mounted on a substrate by reflow soldering (especially lead-free soldering) together with other parts, and an optical device mounted with the above-mentioned optical component 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.
Further, according to the manufacturing method of the present invention, the above-mentioned optical component can be manufactured simply and efficiently. And in the manufacturing method of the present invention, since the curable composition containing the epoxy compound (A) and having excellent transferability is used, an optical component having a fine structure (for example, a portable lens such as a Fresnel lens, especially a smartphone) Even if it is a flash Fresnel lens of a camera mounted on a device, it 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 individualization of the hardened | cured material obtained by the Example, FIG. (4-1) is a top view of individualization, (4-2) is a perspective view of individualization. It is a schematic diagram which shows the apparatus produced in order to evaluate the light-shielding property of the individualization of the hardened | cured material obtained by the Example, The figure (5-1) is a perspective view of an apparatus, (5-2) is an apparatus. FIG. It is explanatory drawing (a 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 cationically curable compound).

  As an epoxy compound, for example, aromatic glycidyl ether type epoxy compounds (for example, bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, etc.); alicyclic glycidyl ether type epoxy compounds (for example, hydrogenated bisphenol A type di) Glycidyl ether, hydrogenated bisphenol F type diglycidyl ether, etc.); aliphatic glycidyl ether epoxy compound; glycidyl ester epoxy compound; glycidyl amine epoxy compound; alicyclic epoxy compound; epoxy-modified siloxane compound etc. . The epoxy compounds can be used singly or in combination of two or more.

  In the present invention, among these, containing an alicyclic epoxy compound is preferable in that a cured product having excellent mechanical strength can be obtained. In the present invention, the alicyclic epoxy compound is a compound having an alicyclic epoxy group (for example, a cyclohexene oxide group etc.) composed of two adjacent carbon atoms constituting an alicyclic ring and an oxygen atom. .

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

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

As the halogen atom in R ¹ to R ^18, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

As the hydrocarbon group for R ¹ to R ^18, preferably a hydrocarbon group having 1 to 20 carbon atoms. 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.

The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having a carbon number of 1 to 20, and examples thereof include C _1- , such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, isooctyl, decyl and dodecyl groups. 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 _-C2-20 alkenyl group (preferably _C2-10 alkenyl group, particularly preferably _C2-4 alkenyl group) such as pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 5-hexenyl group; ethynyl, Mention may be made of a C _2-20 alkynyl group such as propynyl group (preferably a C _2-10 alkynyl group, particularly preferably a C _2-4 alkynyl group) and the like.

The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having a carbon number of 3 to 15, and examples thereof include C _3-12 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and _cyclododecyl groups; Examples thereof include C _3-12 cycloalkenyl groups such as hexenyl group; and C _4-15 bridged cyclic hydrocarbon groups such as bicycloheptanyl and bicycloheptenyl group.

As said aromatic hydrocarbon group, a C6-C14 aromatic hydrocarbon group is preferable, For example, _C6-14 aryl groups (preferably _C6-10 aryl group), such as a phenyl group and a naphthyl group, etc. are mentioned. be able to.

In addition, an aliphatic hydrocarbon group and an alicyclic hydrocarbon group in a group in which two or more groups selected from the above-mentioned aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group are bonded are Examples of the bonded group include a C _3-12 cycloalkyl substituted C _1-20 alkyl group such as a cyclohexyl methyl group; a C _1-20 alkyl substituted C _3-12 cycloalkyl group such as a methylcyclohexyl group and the like. Can. Examples of the group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include C _7-18 aralkyl groups such as benzyl group and phenethyl group (in particular, C _7-10 aralkyl group); C such as cinnamyl 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 a hydrocarbon group which may contain an oxygen atom or a halogen atom for R ^{1 to} R ^18, at least one hydrogen atom in the above-mentioned hydrocarbon group is substituted with a group having an oxygen atom or a group having a halogen atom And the like. The group having an oxygen atom is, for example, a hydroxyl group; a hydroperoxy group; a C _1-10 alkoxy group such as methoxy, ethoxy, propoxy, isopropyloxy, butoxy and isobutyloxy group; a C _2-10 such as an allyloxy group An alkenyloxy group; a C _6-14 aryloxy group which may have 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, , tolyloxy, naphthyloxy group, etc.); benzyloxy, C _7-18 aralkyloxy groups such as phenethyloxy; acetyloxy, propionyloxy, (meth) acryloyloxy, C _1-10 acyloxy group such as benzoyloxy group; 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 containing such as ethyl oxetanyloxy group Group; C _1-10 acyl group such as acetyl, propionyl, benzoyl group; isocyanate group; sulfo group; carbamoyl group; oxo group; and two or more of these are bonded through a single bond or a C _1-10 alkylene group etc. And the like. As a group which has the said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. can be mentioned, for example.

The alkoxy group in R ¹ to R ^18, examples thereof include methoxy, ethoxy, propoxy, isopropyloxy, butoxy, C _1-10 alkoxy group such as isobutyl group.

Examples of the substituent which the alkoxy group may have include a halogen atom, a hydroxyl group, a C _1-10 alkoxy group, a C _2-10 alkenyloxy group, a C _6-14 aryloxy group, and 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 Examples thereof include an acyl group, an oxo group, and a group in which two or more of these are bonded via a single bond or a C _1-10 alkylene group.

Among them, a hydrogen atom is preferable as R ^{1 to} R ¹⁸ .

  X in the said Formula (a) shows a single bond or a coupling group (bivalent group which has one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which a part or all of carbon-carbon double bonds are 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, methyl methylene, dimethyl methylene, ethylene, propylene and trimethylene groups (preferably linear or branched C ₁ -C ₃ alkylene groups of ₁ ), 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, Mention may be made of C _3-12 cycloalkylene groups such as a cyclohexylidene group, and C _3-12 cycloalkylidene groups (preferably C _3-6 cycloalkylene groups and C _3-6 cycloalkylidene groups).

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

  Representative examples of the compounds represented by the above formula (a) include 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate, (3,4,3 ′, 4′-diepoxy) bi Cyclohexyl, bis (3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexan-1-yl) ethane, 2,2-bis (3,4-epoxy) Examples include cyclohexane-1-yl) propane, 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane and the like. These can be used singly or in combination of two or more. These are preferable in that they have small shrinkage or expansion during curing.

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

  The content (total amount of the epoxy compound (A) in the case of containing two or more) in the total amount (100% by weight) of the curable compound contained in the curable composition is, for example, 30 to 90% by weight, preferably 50 to 90 % By weight, particularly preferably 60 to 85% by weight. When the content of the component (A) falls below the above range, the strength of the cured product tends to decrease. On the other hand, when the content of the component (A) exceeds the above range, the curability of the cured product tends to decrease.

  The content (total amount of two or more types) of the alicyclic epoxy compound in the total amount (100% by weight) of the curable compound contained in the curable composition is, for example, 30 to 80% by weight, preferably 30 To 70% by weight, particularly preferably 40 to 60% by weight. When the content of the alicyclic epoxy compound is below the above range, the curability tends to be lowered. 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 (in particular, cationically curable compounds) in addition to the above-mentioned epoxy compound (A), and containing an oxetane compound is a cured product. It is preferable at the point which can improve 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).

(Wherein, 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 for R ^a is, for example, ^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 group, N-arylcarbamoyl group etc.), acyl groups (aliphatic acyl groups such as acetyl group; aromatic acyl groups such as benzoyl group), and two or more of them are It includes monovalent groups bonded through a single bond or a linking group.

As said monovalent hydrocarbon group, the example similar to R < ¹ > -R < ¹⁸ > in said Formula (a) can be mentioned.

  The monovalent hydrocarbon group may have various substituents [eg, a halogen atom, an oxo group, a hydroxyl group, a substituted oxy group (eg, an alkoxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, etc.), a 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. May be included. The hydroxyl group or carboxyl group may be protected by a conventional protecting group in the field of organic synthesis.

The heterocyclic ring constituting the heterocyclic group is a 3- to 10-membered ring (preferably having a carbon atom and at least one hetero atom (for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.) at the atoms constituting the ring Are 4- to 6-membered rings) and fused rings thereof. Specifically, a heterocyclic ring containing an oxygen atom as a hetero atom (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 ring such as oxo-4H-pyran ring, tetrahydropyran ring and morpholine ring; benzofuran ring, isobenzofuran ring, 4-oxo-4H-chromene ring, chroman ring, fused ring such as isochroman ring and the like; [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), hetero atom And a 5-membered ring such as thiophene ring, thiazole ring, isothiazole ring, thiadiazole ring and the like; a 6-membered ring such as 4-oxo-4H-thiopyran ring; A fused ring such as a thiophene ring, etc.), a heterocyclic ring containing a nitrogen atom as a hetero atom (eg, a 5-membered ring such as a pyrrole ring, a pyrrolidine ring, a pyrazole ring, a pyrazole ring, an imidazole ring, or a triazole ring; a pyridine ring, a pyridazine ring, a pyrimidine ring, And 6-membered rings such as pyrazine ring, piperidine ring and piperazine ring; indole ring, indoline ring, quinoline ring, acridine ring, naphthyridine ring, fused ring such as quinazoline ring, purine ring and the like) and the like. As a monovalent | monohydric heterocyclic group, the group which remove | eliminated 1 hydrogen atom from Structural formula of the said heterocyclic ring can be mentioned.

The heterocyclic group may have a substituent, and as the substituent, in addition to the substituent which the hydrocarbon group may have, an alkyl group (for example, C 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 and naphthyl group) and the like can be mentioned.

  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-), silyl bond (-Si-), and a group in which a plurality of these are linked can be mentioned.

  Examples of the compound represented by the above formula (b) include 3-methoxyoxetane, 3-ethoxyoxetane, 3-propoxyoxetane, 3-isopropoxyoxetane, 3- (n-butoxy) oxetane, 3-isobutoxyoxetane 3- (s-butoxy) oxetane, 3- (t-butoxy) oxetane, 3-pentyloxy oxetane, 3-hexyloxy oxetane, 3-heptyloxy oxetane, 3-octyloxy oxetane, 3- (1-propenyloxy 3) Oxetane, 3-Cyclohexyloxyoxetane, 3- (4-Methylcyclohexyloxy) oxetane, 3-[(2-Perfluorobutyl) ethoxy] oxetane, 3-Phenoxyoxetane, 3- (4-Methylphenoxy) oxetane, 3 -(3-chloro-1-pro X) Oxetane, 3- (3-bromo-1-propoxy) oxetane, 3- (4-fluorophenoxy) oxetane, compounds represented by the following formulas (b-1) to (b-15), etc. Can.

  As an oxetane compound, for example, "Aron oxetane OXT-101", "Aron oxetane OXT-121", "Aron oxetane OXT-212", "Aron oxetane OXT-211", "Aron oxetane OXT-213", "Aron oxetane" Commercially available products such as OXT-221 "and" Aron oxetane OXT-610 "(all manufactured by Toagosei Co., Ltd.) can be used.

  The content of the oxetane compound (the total amount of two or more types thereof) in the total amount (100% by weight) of the curable compound contained in the curable composition is, for example, 5 to 40% by weight, preferably 5 to 30% by weight Particularly preferred is 10 to 30% by weight. It is preferable to contain the oxetane compound in the above-mentioned range in that the effect of improving the curability can be obtained while securing 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) If it is contained, the total amount) is, for example, 30% by weight or less, preferably 20% by weight or less, particularly preferably 10% by weight or less, most preferably the total amount (100% by weight) of the curable compound contained in the curable composition. It is 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 be obtained.

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

  The cationic photopolymerization initiator is a compound that generates an acid upon irradiation with light to initiate a curing reaction of the cationically curable compound contained in the curable composition, and is a cationic part that absorbs light and a source of the acid. Of the anion moiety The cationic photopolymerization initiators can be used alone or in combination of two or more.

  Examples of the cationic photopolymerization 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 There can be mentioned, for example, based compounds.

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

As an anion part of a 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, Represents 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: alkyl group in which at least 80% of the hydrogen atoms are substituted with fluorine atoms, t: 1 to 5 ^{_{integer), AsF 6 -, SbF 6}} -, SbF 5 OH - or the like Can be mentioned. In the present invention, among others the anion portion is SbF ₆ ^- that it can be a cationic photopolymerization initiator which is found more active as initiator, having a high curability, obtain a cured product excellent in heat resistance Preferred.

  Examples of the cationic photopolymerization 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) Trifluorophosphate, diphenyl [4- (phenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, 4- (4-biphenylylthio) phenyl-4-bipheny Lylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide phenyltris (pentafluorophenyl) borate, [4- (2-thioxanthonylthio) phenyl] phenyl-2 -Thioxanthonyl sulfonium Phenyl tris (pentafluorophenyl) borate, trade name "Cyracure UVI-6970", "Cyracure UVI 6974", "Cyra Sure UVI-6990 "," Cyracure UVI-950 "(above, made by Union Carbide Corporation," Irgacure 250 "," Irgacure 261 "," Irgacure 264 "," CG-24-61 "(above, made by BASF Corporation), "CG-24-61" (manufactured by Ciba Geigy), "Optomer SP-150", "Optomer SP-151", "Optomer SP-170", "Optomer SP-171" (all manufactured by ADEKA), "DAICAT II" (made by Daicel Co., Ltd.), "UVAC 1590", "UVAC 1591" (above, Daicel Cytech Co., Ltd. made), "CI-2064", "CI-2639", "CI-2624", " CI-2481 "," CI-2734 "," CI-2855 "," CI-2823 ", CI-2758 "," CIT-1682 "(above, Nippon Soda Co., Ltd. product)," PI-2074 "(made by Rhodia, tetrakis (pentafluorophenyl) borate toluylcumyliodonium salt)," FFC 509 "(3 M Company), "BBI-102", "BBI-101", "BBI-103", "MPI-103", "TPS-103", "MDS-103", "DTS-103", "NAT-103" “NDS-103” (above, Midori Chemical Co., Ltd. product), “CD-1010”, “CD-1011”, “CD-1012” (above, US product made by Sartomer), “CPI-100P” Commercial products, such as "CPI-101A" (above, San-Apro Co., Ltd. product) can be used.

  The thermal cationic polymerization initiator is a compound that generates an acid by heat treatment to initiate a curing reaction of the cationic curable compound contained in the curable composition, and generates a cationic part that absorbs heat and an acid. It consists of the anion part which becomes a source. The thermal cationic polymerization initiators can be used alone or in combination of two or more.

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

  As a cation part of the thermal cationic polymerization initiator, for example, 4-hydroxyphenyl-methyl-benzylsulfonium, 4-hydroxyphenyl-methyl- (2-methylbenzyl) sulfonium, 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium And p-methoxycarbonyloxyphenyl-benzyl-methylsulfonium (in particular, monoarylsulfonium ion) and the like.

  As an anion part of a thermal cationic polymerization initiator, the example similar to the anion part of the said photocationic polymerization initiator can be mentioned.

  As a thermal cationic polymerization initiator, for example, 4-hydroxyphenyl-methyl-benzylsulfonium phenyltris (pentafluorophenyl) borate, 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.

  The content of the cationic polymerization initiator is, for example, 0.1 to 10 parts by weight with respect to 100 parts by weight of the curable compound (in particular, the cationic curable compound, in the case of containing two or more kinds thereof) contained in the curable composition. The amount is 0.5 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 the content of the cationic polymerization initiator is below the above range, the curability tends to be reduced. 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 above epoxy compound (A), oxetane compound (B) and polymerization initiator (C) as long as the effects of the present invention are not impaired. Good. As another component, an antioxidant, a photosensitizer, an antifoamer, a surface modifier, a coupling agent, surfactant, a flame retardant, an ultraviolet absorber etc. can be mentioned, for example. These can be used singly or in combination of two or more.

  As said surface modifier, surfactant of a silicone type, an acryl type, or a fluorine type can be mentioned, for example. By adding a surface modifier to the curable composition, the wettability to the mold can be improved, and the effect of reducing foaminess when filling the curable composition into the mold can be obtained. In the present invention, in particular, silicone surfactants are preferable in that they are particularly excellent in the effect of reducing the tendency of bubbles.

  Examples of silicone surfactants include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane having an acryl group, polyester-modified polydimethylsiloxane having an acryl group, and the like. In the present invention, for example, trade names “BYK-333”, “BYK-345”, “BYK-UV 3510”, “BYK-UV 3500”, “BYK-UV 3530”, “BYK-UV 3570” (all, Big Chemie Japan, Inc.) Commercially available products such as Co., Ltd.) can be suitably used.

  The content of the surface modifier (the total amount of two or more, if any) is, for example, 0.01 to 3 parts by weight with respect to the total amount (100 parts by weight) of the curable compound 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 phenol-based antioxidants, phosphorus-based antioxidants, thioester-based antioxidants, amine-based antioxidants and the like. In the present invention, it is preferable to use a phenolic antioxidant and / or a phosphorus antioxidant because the heat resistance of the resulting cured product can be further improved.

  As a phenolic antioxidant, for example, 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'-hexamethylene bis [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 biphenyl [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 1425WL” Commercially available products such as BASF Corporation) can be used.

  As a phosphorus antioxidant, for example, 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 can be mentioned. In the present invention, for example, trade names “PEP-8”, “PEP-8W”, “PEP-36 / 36A”, “HP-10”, “2112”, “2112 RG”, “1178” Commercial products, such as (made by ADEKA), can be used.

  The content of the antioxidant (in the case of containing two or more, the total amount thereof) is 100 parts by weight of the curable compound (in particular, the cationic curable compound, in the case of containing two or more, the total amount) contained in the curable composition For example, it is 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 degassing under vacuum if 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 possible to manufacture a high-precision optical component which is excellent in the filling property to the mold, can reduce the bubbles, and is excellent in the shape transferability.

  Furthermore, the curable composition in the present invention is excellent in curability and can be rapidly cured to form a cured product by light irradiation and / or heat treatment.

  When a curable composition containing a photocationic polymerization initiator is used as the cationic polymerization initiator (C), the composition can be cured by light irradiation. As light (active energy ray) used for the light irradiation, any of infrared ray, visible light, ultraviolet ray, X ray, electron beam, α ray, β ray, γ ray and the like can be used. In the present invention, among these, ultraviolet light is 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 ultra high 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 hardenability, even if it is light irradiation by UV-LED, hardening reaction can be advanced rapidly.

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

  When using a curable composition containing a thermal cationic polymerization initiator 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 is excellent in heat resistance, and the thermal decomposition temperature is, for example, 200 ° C. or more (eg, 200 to 500 ° C.), preferably 260 ° C. or more, particularly preferably 330 ° C. or more, most preferably 350 ° C. or more. The thermal decomposition temperature can be determined by the method described in the examples. Therefore, the shape can be maintained even when it is subjected to a substrate mounting process in which soldering (in particular, lead-free soldering) is performed using a reflow furnace.

[Optical parts]
The optical component of the present invention is an optical component comprising a cured product of the above-mentioned 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), and particularly preferably It is 0.08 mm or less (for example, 0.01-0.08 mm).

  The number of laminated layers of the coating layer is not particularly limited, and can be appropriately adjusted as needed. For example, it is 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 appropriately adjusted according to the application. For example, when the optical component is a lens and the coating layer is formed for the purpose of providing the lens with reflectivity or light shielding property Preferably, a coating layer is provided 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 a light shielding property. It can be granted.

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

  The coating material which forms a coating layer contains resin, a coloring agent (pigment), a solvent, and an additive (for example, a flame retardant, a lubricating material, an antimicrobial agent, an antistatic agent etc.), for example.

  Examples of the resin include polyolefin resins, polystyrene resins, vinyl chloride resins, fluorine resins, acrylic resins, unsaturated polyester resins, epoxy resins, polyurethane resins, and phenol resins. These can be used singly 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, copper-chromium black] Copper-iron-manganese black, cobalt-iron-chromium black, ruthenium oxide, graphite, metal particles (eg, aluminum etc.), metal oxide particles, complex oxide particles, metal sulfide particles, metal nitride particles etc.], organic Pigment [perylene black, cyanine black, aniline black, azo pigment, anthraquinone pigment, isoindolinone pigment, indanthrene pigment, indigo pigment, quinacridone pigment, dioxazine pigment, tetraazaporphyrin pigment, Reel methane pigment It can be mentioned phthalocyanine pigments, perylene pigments, benzimidazolone pigments, rhodamine-based pigments, etc.] or the like. These can be used singly or in combination of two or more.

  Examples of the solvent include aromatic solvents such as toluene and xylene, and ester solvents such as ethyl acetate. These can be used singly 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 (eg, 0.1 to 2 mm), preferably 1.8 mm or less (eg, 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 (the maximum width in a plan view as viewed from directly above) is 10 mm or less (eg, 1 to 10 mm), preferably 8 mm or less (eg, 1 to 8 mm), 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 Fresnel lens for flash of a camera (for example, a camera (for example, an imaging camera used for a portable electronic device such as a smartphone), Is included.

  The Fresnel lens is a lens having a light diffusing or condensing effect, having two or more mountain-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 chevron shaped prisms are continuously smaller (or larger) as they move toward the center (for example, FIG. 1).

[Method of manufacturing optical parts]
The optical component of the present invention is characterized by being manufactured by casting, more specifically, through the following steps.
Step 1: The curable composition containing the epoxy compound (A) is filled in a mold having two or more optical component-type recesses, and then light irradiation and / or heat treatment is performed to obtain two or more optical components. Step 2: Obtain a cured product having a shape Step 2: singulate the cured product to obtain an individualized product Step 3: form a coating layer on the individualized component

  The mold has two or more desired optical component type recesses [that is, recesses having an inverted shape of an optical component (for example, a Fresnel lens or the like)]. The two or more optical component mold recesses may be arranged randomly or at equal intervals, but in particular, a mold in which two or more optical component mold recesses are arranged at equal intervals is used It is preferable from the viewpoint of excellent workability such as singulation.

  Examples of the method for filling the mold with the curable composition in the step 1 include a method using a dispenser, a screen printing method, a curtain coating method, a spray method and the like. 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 recess shape). . The mold may be composed of a plurality of parts, such as a bottom and a lid. Further, the mold may be subjected to release treatment (for example, application of a release agent) in advance.

  As a material of a mold, metal, glass, plastic, silicone etc. can be mentioned, for example. Among them, since it has transparency, it can be used for molding of a curable composition that is cured by light irradiation, and it is a silicone mold (for example, polydimethylsiloxane as a raw material) in terms of excellent shape transferability and releasability. Silicone molds) are preferred.

  In addition, in the case of using a curable composition containing a photocationic polymerization initiator as the cationic polymerization initiator (C), the “light irradiation and / or heat treatment” in step 1 performs light irradiation to start cationic polymerization. When a curable composition containing a thermal cationic polymerization initiator is used as the agent (C), heat treatment is performed.

  As light (active energy ray) used for the light irradiation, any of infrared ray, visible light, ultraviolet ray, X ray, electron beam, α ray, β ray, γ ray and the like can be used. In the present invention, among these, ultraviolet light is 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 ultra high 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 hardenability, even if it is light irradiation by UV-LED, hardening reaction can be advanced rapidly. In the case of curing by light irradiation, it is preferable to use a transparent mold as the 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 light irradiation, the Fresnel lens array is obtained by releasing the mold. Further, before or after the mold release, a post bake treatment (for example, heating at 80 to 180 ° C. for 5 to 30 minutes) may be performed as necessary.

  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 the shapes of two or more optical components (preferably having the shapes of two or more optical components at equal intervals)] A step of cutting (preferably, cutting at the connection portion) the separated optical component, ie, a dicing step, of a cured product having a configuration in which two or more optical components are connected via the connection portion . The cutting is performed using cutting means such as a dicing blade.

  A curable composition containing an epoxy compound (A) is used in the method of producing an optical component of the present invention, and the curable composition has a small shrinkage or expansion during curing, so that curing having excellent transferability is achieved. A product can be manufactured, and a cured product having the shapes of two or more optical components at equal intervals can be manufactured with high accuracy. The gap between two adjacent optical components on the cured product is, for example, 15 μm or less, preferably 10 μm or less, particularly preferably 8 μm or less. Therefore, in the dicing step, the pieces can be separated with high accuracy using cutting means such as a dicing blade, and high-precision optical components can be efficiently mass-produced.

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

  In the step 3, before forming the coating layer, the cured product may be subjected to surface treatment 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 carried out singly or in combination of two or more.

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

  As a coating method of a coating material, the method of using a dispenser, the screen-printing method, the curtain coat method, the spray method etc. can be mentioned, for example. After the coating material is applied, it may be dried if necessary, and heat treatment and / or light irradiation may be performed to solidify or cure the coating material to form a coating layer. And the coating layer which has a multilayer structure of two or more layers can be formed by repeating the said operation.

  Moreover, before applying a coating material, it is preferable to mask by sticking an adhesive tape etc. to the part which does not form a coating layer, and the adhesive tape etc. used for the said masking are removed after applying a coating material Is preferred.

  Furthermore, in the step 2, performing the singulation treatment in a state where the cured product obtained through the step 1 is fixed to a support (for example, adhered to an adhesive tape such as dicing tape) causes positional deviation and the like. By applying the individualized products fixed to the support to the subsequent step 3, the coating layer can be formed at one time, and the fine individualized products can be efficiently coated. It is preferable at the point which can form a layer. After completion of the singulation treatment, when the spacing between the individual pieces is narrow, it is preferable to widen the spacing by expanding the adhesive tape or the like. It is because it becomes possible to form a coating layer also on a cut surface (the side of an optical component) by applying a coating material in the state where the interval of individualization has opened appropriately.

Therefore, as steps 2 and 3 of the present invention, it is preferable to be as follows.
Step 2: Separating the cured product in a fixed state to a support to obtain a fixed piece fixed to the support Step 3: Forming a coating layer on the fixed pieces fixed to the support

  Then, after the coating layer is formed in a state where the individual pieces are fixed by the adhesive tape, the adhesive layer is picked up from the adhesive tape and attached to a substrate mounting or the like.

An example of the manufacturing method of the optical component of this invention is shown in FIG. Each process in FIG. 2 will be described below.
[1] Attach a mask (2) to a cured product (1) having the shape of two or more optical components (= masking)
[2] The cured product (1) is diced along a cutting line (3) to obtain a discrete (4) having a mask (2). [3] a coating material is applied to form a coating layer (5) [4] removing the mask (2) to obtain an optical component (6, 7) (= individualized product having a coating layer)

  According to the method of manufacturing an optical component of the present invention, even a fine optical component (for example, a Fresnel lens, in particular, a flash lens for a camera flash) can be simply and efficiently manufactured by casting. In addition, by changing the coating material, optical components having various coating layers can be easily produced. Furthermore, the formation of a coating layer having a multilayer structure is also easy. Therefore, the method for producing an optical component according to the present invention is suitable as a method for producing an optical component having a coating layer (for example, a flash lens used in portable electronic devices such as smartphones). Optical components can be provided at low cost.

[Optical device]
The optical device of the present invention mounts the above-mentioned optical component. The optical device according to the present invention includes, for example, portable electronic devices such as mobile phones, smartphones and tablet PCs, infrared sensors, near infrared sensors, millimeter wave radars, LED spot illumination devices, near infrared LED illumination devices, These include car-mounted electronic devices such as mirror monitors, meter panels, combiners for head-mounted displays (projection type), and combiners for head-up displays.

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

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

  EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited by these examples.

Preparation Example 1: Synthesis of (3,4,3 ′, 4′-diepoxy) bicyclohexyl (a-1)
70 g (0.68 mol) of 95% by weight sulfuric acid and 55 g (0.36 mol) of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) were stirred and mixed to prepare a dehydration catalyst.
1000 g (5.05 moles) of hydrogenated biphenol (4,4'-dihydroxybicyclohexyl) in a 3 L flask equipped with a stirrer, a thermometer, and a distillation piping filled with a dehydrating agent and kept warm The prepared dehydration catalyst 125 g (0.68 mol as sulfuric acid) and 1500 g of pseudocumene were charged, and the flask was heated. The formation of water was confirmed when the internal temperature exceeded 115 ° C. The temperature was further raised to raise the boiling point of pseudocumene (internal temperature: 162 to 170 ° C.), and the dehydration reaction was performed at normal pressure. The by-produced water was distilled off and discharged out of the system through a dehydration pipe. The dehydration catalyst was liquid under the reaction conditions and was finely dispersed in the reaction solution. After 3 hours, almost theoretical amount of water (180 g) was distilled off.
After distilling off the pseudocumene using a 10-stage aldershaw-type distillation column, the reaction solution is 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 reactor was charged with 243 g of the obtained bicyclohexyl-3,3'-diene and 730 g of ethyl acetate, and the temperature in the reaction system was controlled to 37.5 ° C. while nitrogen was blown into the gas phase. While dropping, 274 g of a 30% by weight solution of peracetic acid in ethyl acetate (water content: 0.41% by weight) was dropped over about 3 hours.
After completion of the dropwise addition, the reaction was terminated by aging at 40 ° C. for 1 hour. Furthermore, the crude solution at the end of the reaction at 30 ° C. was washed with water, and the low boiling point compounds were 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.
Moreover, in the measurement of ¹ H-NMR, the peak derived from the internal double bond around δ 4.5 to 5 ppm disappears, and the generation of the peak of the proton derived from the epoxy group is confirmed around δ 3.1 ppm, so reaction generation The product was confirmed to be (3,4,3 ′, 4′-diepoxy) bicyclohexyl.

Preparation Example 2: Synthesis of bis (3,4-epoxycyclohexylmethyl) ether (a-2)
In a 5 L reactor, 499 g (12.48 moles) of sodium hydroxide (in the form of granules) and 727 mL of toluene were added, and after nitrogen substitution, a solution of 484 mL of toluene of 420 g (3.74 moles) of tetrahydrobenzyl alcohol was added. Aged for 1.5 hours. Next, 419 g (2.20 moles) of tetrahydrobenzyl methanesulfonate was added, and the mixture was aged under reflux for 3 hours, cooled to room temperature, and quenched by adding 1248 g of water to separate the layers.
The separated organic layer was concentrated and distilled under reduced pressure to obtain ditetrahydrobenzyl ether as a colorless and 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 dropped over 5 hours, and aging was performed 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: weight part) shown in following Table 1, and the curable composition was obtained. 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 conditions of a temperature of 25 ° C. and a shear rate of 20 (1 / s).

  The resulting curable composition was poured into a silicone mold (bottom), and the spacer was sandwiched so as to have a thickness of 1.0 mm. The mold is closed with a silicone mold (lid) and irradiated (100 mW × 30 seconds) with a UV-LED (365 nm, Omron Co., Ltd.) to cure the curable composition to form 36 rectangular parallelepipeds A cured product having a combined shape in which concave portions (3.6 mm × 3.6 mm × 0.8 mm) are arranged at a pitch width of 4.1 mm (6 longitudinal × 6 lateral) via the connection portion (see FIG. 3) I got

[Transfer accuracy evaluation]
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), Deviation from the design value (ideal grid point) was measured to evaluate transfer accuracy.

Example 1 (As a reference example) [Cured product having a coating layer]
On the surface of the cured product obtained in Synthesis Example 1 on the opposite side of the surface having the concave portion, a 3.6 mm × 3.6 mm masking tape was attached at a pitch width of 4.1 mm in accordance with the concave portion. Thereafter, a dicing tape is attached to the back side of the cured product (the side opposite to the side to which the masking tape is attached), and then a dicing saw (trade name “DFD6361” manufactured by Disco Corporation, dicing blade thickness 0. Using 1 mm), cut the connection part to separate the cured product, and separate the separated cured product (separate product) (4.0 mm x 4.0 mm x 1.0 mm) onto the dicing tape It was obtained in the state fixed to.

  Thereafter, the surface of the individualized product was subjected to a corona treatment to obtain a surface-treated individualized product (hereinafter sometimes referred to as "the individualized product before coating").

A trade name "6080" (manufactured by Labsphere Co., Ltd.) was used as a white coating material.
The above-mentioned coating material was sprayed onto the obtained surface-treated particles with a spray gun so as to give a uniform film thickness. Thereafter, 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).

The thickness of the wall of the individualized product having the coating layer obtained was measured using a micrometer (manufactured by Mitutoyo Co., Ltd.), and the thickness of the wall of the individualized product before coating was also measured similarly. The film thickness of the coating layer was calculated.
(Film thickness of coating layer) = (thickness of wall of individualized product having coating layer)-(thickness of wall of individualized wall 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.
○: no bubbles, dirt, cracks, molding defects, dripping, and coating defects were observed. ×: foam, dirt, cracks, and molding defects, dripping, and coating defects were selected. One or more anomalies were seen

[Optical characterization]
The central illumination of the following projection plate is about 100 lux with the LED light source (separately placed) placed immediately after (the distance between the individualized and the light source is 1.0 mm) the singulated with the obtained coating layer The light was emitted using The illuminance of the central part of the projection plate (1.2 m × 0.92 m) located directly in front of the individualized product 1.0 m (a position directly opposite the individualized product) and the peripheral area (a radius of 0.77 m from the central area) The average illuminance of certain four places was measured using a luminometer (trade name “CL-200A, manufactured by Konica Minolta Co., Ltd.).

[Shading evaluation]
An individualized product having the obtained coating layer disposed on the ceramic substrate so as to cover the LED light source is disposed at the opening of the light shielding film, and the inside of 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 based on the following criteria (see FIG. 5).
○: no light leakage was observed ×: light leakage was observed

[Heat resistance evaluation]
Using a thermal analyzer (trade name "TG-DTA6300", manufactured by Seiko Instruments Inc.), a part of the individualized product having the obtained coating layer is cut away under a nitrogen atmosphere at a temperature rising rate of 10 ° C / The thermal decomposition temperature (T) was measured by thermogravimetric analysis under conditions of minutes. In addition, with thermal decomposition temperature (T), as shown in FIG. 6, there is no initial weight loss or there is a gradual decrease in weight (a range shown by A in the figure), and a rapid weight loss. It is the temperature where the tangent of the inflection point where it is happening (the range indicated by B in the figure) intersects.

Examples 3 to 5 (Examples 4 and 5 are reference examples)
The same procedure as in Example 1 was carried out except that the coating material and the thickness of the coating layer were changed as described in the table, and the method of forming the coating layer was changed as follows along with the change of the coating material. And the appearance, optical characteristics, light shielding ability, and heat resistance were evaluated. In Examples 3 and 5, individual pieces having a coating layer (two layers) were obtained.

Example 2
Instead of the cured product obtained in Synthesis Example 1, the cured product obtained in Synthesis Example 2 is used, the coating material and the thickness of the coating layer are changed as described in the table, and the coating material is changed. An individual piece having a coating layer was obtained in the same manner as in Example 1 except that the formation method of the layer was changed as follows, to obtain an appearance, an optical property, a light shielding property, and a heat resistance.

Comparative example 2
Instead of the cured product obtained in Synthesis Example 1, the cured product obtained in Synthesis Example 3 is used, the coating material and the thickness of the coating layer are changed as described in the table, and the coating material is changed. An individual piece having a coating layer was obtained in the same manner as in Example 1 except that the formation method of the layer was changed as follows, to obtain an appearance, an optical property, a light shielding property, and a heat resistance.

As a silver-colored coating material, the coating material is used by mixing and using two brand names of “Hyurex P UNP 79” (two-component type), drying at 80 ° C. for 10 minutes and further heating at 100 ° C. for 1 hour Cured.
As a black-colored coating material, using a brand name "GT-7II" (made by Canon Chemical Co., Ltd.), it dried at 80 degreeC for 2 hours, and hardened the coating material by heating at 120 degreeC further for 1 hour. .
As a transparent coating material, using a trade name “Z-700K-2” (manufactured by Aika Kogyo Co., Ltd.), it is dried at 80 ° C. for 5 minutes and further irradiated with a light of 50 mW / cm ² for 30 seconds. The material was allowed to cure.

Comparative Example 1
The appearance, the optical properties, the light shielding property, and the heat resistance were similarly evaluated for the cured product (surface-treated individualized product) before the coating layer obtained in Example 1 was provided.

The abbreviations in Table 1 above are as follows.
<Curable compound>
CELLOXIDE 2021 P: 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane carboxylate, molecular weight 252, trade name “Ceroxide 2021 P”, manufactured by Daicel Corporation (a-1): 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-hydroxymethyl oxetane, molecular weight 116, trade name "Aron oxetane OXT-101", Toagosei Co., Ltd. YX 8000: hydrogenated bisphenol A type epoxy compound, molecular weight 353, trade name "YX 8000", Mitsubishi Chemical Corporation <surface modifier>
BYK-333: Polyether modified polydimethylsiloxane, trade name "BYK-333", manufactured by Big Chemie Japan KK <cationic polymerization initiator>
CPI-101A: diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate, trade name "CPI-101A", manufactured by San-Apro Co., Ltd.

1 A cured product 2 having a shape in which two or more optical components are bonded via a connecting part 2 mask 3 cutting line 4 individualized product of cured product 5 coating layer 6 discrete product (optical component) having a coating layer (plan view )
7 Individualized product with coating layer (optical component) (perspective view)
8 Cured product 9 obtained in Example 9 Recess 10 Shading curtain 11 LED light 12 Coating layer in individual pieces 13 Layer made of cured product of curable composition in individual pieces 14 LED device 15 Ceramic substrate 16 Observation viewpoint

Claims (4)

A flash lens made of a cured product of a curable composition containing the epoxy compound (A), the outer edge portion of the flash lens, at least one color selected from white Iro及 beauty silver, the total thickness of 20 to 100 [mu] m, A flash lens having a maximum thickness of 2 mm or less and a maximum width of 10 mm or less in plan view, having a coating layer having a reflectance of 60% or more. The flash lens according to claim 1, 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 represent a hydrogen atom, a halogen atom, a hydrocarbon group which may contain an oxygen atom or a halogen atom, or an alkoxy group which may have a substituent] . X represents a single bond or a linking group]   The flash lens according to claim 1 or 2, 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 3, which has a thermal decomposition temperature of 200 ° C or higher.

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