WO2017073268A1 - 重合体及びそれを含む樹脂組成物 - Google Patents
重合体及びそれを含む樹脂組成物 Download PDFInfo
- Publication number
- WO2017073268A1 WO2017073268A1 PCT/JP2016/079507 JP2016079507W WO2017073268A1 WO 2017073268 A1 WO2017073268 A1 WO 2017073268A1 JP 2016079507 W JP2016079507 W JP 2016079507W WO 2017073268 A1 WO2017073268 A1 WO 2017073268A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- formula
- resin composition
- polymer
- meth
- Prior art date
Links
- 0 CC(Cc(cc12)ccc1C1=CC[C@@](C=CCC(C)(C)C)C=C1C2(c1ccccc1)C1=CCCC=C1)*(C)C Chemical compound CC(Cc(cc12)ccc1C1=CC[C@@](C=CCC(C)(C)C)C=C1C2(c1ccccc1)C1=CCCC=C1)*(C)C 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N C1CCCCC1 Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SOIRJRVZKAJNRG-UHFFFAOYSA-N CC1CC#CCC1 Chemical compound CC1CC#CCC1 SOIRJRVZKAJNRG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/12—Polythioether-ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
- C09D181/02—Polythioethers; Polythioether-ethers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B3/00—Simple or compound lenses
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/02—Polythioethers; Polythioether-ethers
Definitions
- the present invention relates to a polymer having a specific structural unit and a resin composition containing the polymer, and more particularly to a resin composition capable of forming a cured film having high transparency and a high refractive index.
- optical electronic materials such as anti-reflection coating agents for liquid crystal displays, transparent coating agents for solar cells, light emitting diodes, light receiving parts of CCD image sensors and CMOS image sensors.
- optical electronic materials not only transparency but also a high refractive index is often required for improving light extraction efficiency and light collection.
- introduction of an aromatic ring introduction of a halogen atom other than fluorine, introduction of a sulfur atom, introduction of a metal atom, introduction of a hydrogen bond, or the like is used as a technique for increasing the refractive index of a plastic material.
- resins widely used for plastic materials include those obtained by radical polymerization of diethylene glycol bis (allyl carbonate).
- the composition described in Patent Document 1 containing the resin as an essential component is excellent in storage stability, can be used as it is by a conventional plastic casting method, and is difficult to cause mold damage during curing.
- Plastic lenses obtained by curing an object have various characteristics such as less dyeing unevenness than conventional products. However, since the plastic lens obtained by curing this resin composition has a low refractive index of around 1.50, the center thickness or edge (edge) thickness of the lens becomes thick, and the lens has a higher refractive index. A resin was desired.
- Patent Document 2 and Patent Document 3 are compounds containing sulfur atoms for optical resins, sulfur atoms increase the refractive index because of their high polarizability, stability, and ease of introduction into polymers. Often used.
- an etch back method is known as one of manufacturing methods of a micro lens for a CCD / CMOS image sensor (Patent Documents 5 and 6). That is, a resist pattern is formed on the microlens resin layer formed on the color filter layer, and this resist pattern is reflowed by heat treatment to form a lens pattern. Using the lens pattern formed by reflowing the resist pattern as an etching mask, the lower microlens resin layer is etched back, and the lens pattern shape is transferred to the microlens resin layer to produce a microlens.
- An object of the present invention is to provide a cured film having a high refractive index, excellent transparency and heat resistance, and a dry etching rate equivalent to that of a resist, which solves the above-mentioned problems of the prior art and satisfies the performance required for a resin for microlenses. It is providing the resin composition which can be formed, and the polymer used for the said resin composition. Another object of the present invention is to provide a microlens having a high refractive index, excellent transparency and heat resistance.
- this invention is a polymer which has a structural unit represented by following formula (1).
- a 1 and A 2 each independently represent an —O— group or a —C ( ⁇ O) O— group
- X represents a divalent organic group having at least one aromatic ring or heterocyclic ring;
- the rings may be bonded via a single bond, bonded via a hetero atom, or may form a condensed ring.
- Y represents a divalent organic group having at least one aromatic ring or condensed ring.
- This invention is also the resin composition containing the said polymer, a crosslinking agent, and a solvent.
- the resin composition of the present invention is, for example, a microlens resin composition.
- the present invention is also a method for forming a cured film by applying the resin composition onto a substrate and then baking the resin composition using a heating unit.
- the resin composition of the present invention can form a cured film having a high refractive index, high transparency and high heat resistance, and a dry etching rate equivalent to that of a resist. Therefore, the resin composition of the present invention can provide a microlens having a high refractive index, excellent transparency and heat resistance.
- the present invention is a polymer having the structural unit represented by the formula (1) and a resin composition containing the polymer, a crosslinking agent and a solvent, and is heated at 230 ° C. or higher after film formation.
- the refractive index of the obtained cured film is preferably 1.68 or more, more preferably 1.70 or more.
- the transmittance of the cured film at a wavelength of 400 nm is 90% or more.
- the solid content obtained by removing the solvent from the resin composition of the present invention is usually 0.01% by mass to 70% by mass.
- the monomer forming the polymer of the present invention that is, the raw material monomer of the polymer is a dimercapto compound represented by the following formula (2) and a diglycidyl compound represented by the following formula (3).
- a 1 , A 2 , X and Y have the same definitions as in formula (1)).
- Examples of the divalent organic group represented by X include groups represented by the following formulas (a) to (e). (Wherein R 0 represents a methyl group, m represents an integer of 0 to 2, R 1 and R 2 each independently represents a single bond or a methylene group, and Z represents a single bond or a —S— group) , R 3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a branched structure, an aryl group, an alkenyl group having 2 or 3 carbon atoms, or an alkynyl group having 2 or 3 carbon atoms.
- R 4 represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkenyl group having 2 or 3 carbon atoms, or an alkynyl group having 2 or 3 carbon atoms, which may have a branched structure.
- Examples of the divalent organic group represented by Y include groups represented by the following formula (f) and formula (g).
- dimercapto compound represented by the formula (2) examples include 1,4-benzenedithiol, 1,3-benzenedithiol, 4,5-bis (mercaptomethyl) -o-xylene, bismuthiol, 6-anilino- 1,3,5-triazine-2,4-dithiol, 6- (diallylamino) -1,3,5-triazine-2,4-dithiol, 4,4'-biphenyldithiol, 1,5-dimercaptonaphthalene 4,4'-thiobisbenzenethiol, and 2,7-dimercaptothianthrene.
- Examples of the diglycidyl compound represented by the formula (3) include bisglycidyl terephthalate, resorcinol diglycidyl ether, 2,2-bis (4-glycidyloxyphenyl) propane, bisphenol fluorenediglycidyl ether, bisnaphthol fluorenedin Examples include glycidyl ether, monoallyl diglycidyl isocyanurate, and bis [4- (2,3-epoxypropylthio) phenyl] sulfide.
- the weight average molecular weight of the polymer is usually 1,000 to 300,000, preferably 3,000 to 150,000.
- the weight average molecular weight is a value obtained by using gel as a standard sample by gel permeation chromatography (GPC).
- the content of the polymer contained in the resin composition of the present invention is usually 1% by mass to 99% by mass, preferably 5% by mass based on the content in the solid content of the resin composition. To 95% by mass.
- the method for obtaining the polymer is not particularly limited, but generally, the compound represented by the formula (2) and the compound (monomer) represented by the formula (3) may be added as necessary. It can be obtained by a polymerization reaction in a solvent in the presence of a catalyst, usually at a temperature of 23 to 200 ° C.
- the compound represented by the formula (2) and the compound represented by the formula (3) are used in a molar ratio of 1: 9 to 9: 1, preferably 3: 5 to 5: 3.
- the polymer thus obtained is usually in a solution state dissolved in a solvent, and can be used in the resin composition of the present invention without isolation in this state.
- the copolymer solution obtained as described above is poured into a stirred poor solvent such as hexane, diethyl ether, methanol, water and the like to reprecipitate the copolymer, and the generated precipitate is obtained.
- the copolymer can be made into powder by drying at normal temperature or under reduced pressure at room temperature or heating. By such an operation, a polymerization initiator and an unreacted compound that coexist with the copolymer can be removed.
- the powder of the copolymer may be used as it is, or the powder may be redissolved, for example, in a solvent described later and used as a solution.
- the preparation method of the resin composition of this invention is not specifically limited, For example, the method which melt
- the solvent is not particularly limited as long as it dissolves the polymer having the structural unit represented by the formula (1).
- examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate.
- propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, Cyclopentanone, cyclohexanone, ethyl lactate, dimethylacetamide, N-methyl-2-pyrrolidone and ⁇ -butyrolactone are preferred.
- the resin composition of this invention can also contain surfactant for the purpose of improving applicability
- the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene Polyoxyethylene alkyl aryl ethers such as ethylene nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan Sorbitan fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as rubitan monopalmitate, polyoxyethylene
- content in the resin composition of this invention is 3 mass% or less based on content in the solid content of the said resin composition, Preferably it is 1 mass%. Or less, more preferably 0.5% by mass or less.
- the resin composition of the present invention has a crosslinking agent, a catalyst for accelerating the crosslinking reaction, an ultraviolet absorber, a sensitizer, a plasticizer, and an antioxidant as long as the effects of the present invention are not impaired.
- An additive such as an agent and an adhesion aid can be included.
- crosslinking agent added to the resin composition of the present invention examples include a polyfunctional (meth) acrylate compound, a hydroxymethyl group-substituted phenol compound, a compound having an alkoxyalkylated amino group, and a polyfunctional block isocyanate compound. Can be mentioned. These crosslinking agents can be used alone or in combination of two or more. The content of the crosslinking agent varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but is 0.001 based on the total solid content of the resin composition of the present invention.
- the mass is from 80% by mass to 80% by mass, preferably from 0.01% by mass to 50% by mass, and more preferably from 0.05% by mass to 40% by mass.
- These crosslinking agents may cause a crosslinking reaction by self-condensation, but when a crosslinking substituent is present in the above-described polymer compound of the present invention, it can cause a crosslinking reaction with those crosslinking substituents.
- (meth) acrylate means methacrylate and acrylate.
- polyfunctional (meth) acrylate compound examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, dicyclo Tantanyl di (meth) acrylate, bisphenol A di (meth) acrylate, ethoxylated bisphenol A di (meth)
- polyfunctional (meth) acrylate compound examples include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta.
- polyfunctional (meth) acrylate compound examples include (meth) acrylate monomers having an epoxy group such as glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate.
- a polyfunctional epoxy (meth) acrylate synthesized by reacting (meth) acrylic acid with a homopolymer or copolymer obtained by radical polymerization of can also be mentioned.
- the copolymer means a polymer obtained by polymerizing two or more monomers.
- the copolymer may be a copolymer obtained by polymerizing two or more kinds of (meth) acrylates having an epoxy group, or may be obtained by polymerizing (meth) acrylates having an epoxy group and other (meth) acrylates. It may be a copolymer.
- the following product can be mentioned, for example.
- Aronix [registered trademark] M-208, M-210, M-211B, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M-303, M-305, M-306, M-309, M-310, M-313, M-315, M-321, M-321 M-350, M-360, M-400, M-402, M-403, M-404, M-405, M-406, M-408, M-450, M-450 M-452, M-460, M-510, M-520, M-1100, M-1200, M-1210, M-1310, M-1600, M-1960, M-1960 M-6100, M-6200, M-6250, M-6500, M-7100, M 7300K, the M-8030, the M-8060, the M-8100, the M-8530, the M-8560, the M-9050 (registered trademark] M-208, M-210, M-211
- KAYARAD registered trademark
- NPGDA PEG400DA
- FM-400 R-167, HX-220, HX-620, R-526, R-551, R-712, R-604, R-684, GPO-303, TMPTA, HDDA, TPGDA, KS-HDDA, KS-TPGDA, MANDA, THE-330, TPA-320, TPA-330, PET- 30, T-1420, T-1420 (T), RP-1040, DPHA, DPEA-12, D-310, D-310, D-330, DPCA-20, DPCA-30, DPCA -60, DPCA-120, FM-700, DN-0075, DN-2475, TC-120S, R-115, R-130, R-38 EAM-2160, CCR-1291H, CCR-1235, ZAR-1035, ZAR-2000, ZFR-1401H, ZFA-1491H, ZCR-1569H, ZCR-1601H, ZCR-1797H ZCR-1798
- Purple light (registered trademark) UV-1400B, UV-1700B, UV-2000B, UV-2010B, UV-2750B, UV-3000B, UV-3200B, UV-3210EA, UV-3210EA, UV-3300B UV-3310B, UV-3500BA, UV-3520TL, UV-3610D80, UV-3630D80, UV-3640PE80, UV-3700B, UV-6100B, UV-6300B, UV-6640B, UV-6640B UV-7000, UV-7000B, UV-7461TE, UV-7510B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7630B, UV-7640B, UV-7650B, UV-N 001, the same UV-NS034, the UV-NS054, the UV-NS063, the UV-NS077 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
- Beamset [registered trademark] 243NS, 255, 261, 271, 502H, 504H, 505A-6, 550B, 575, 577, 700, 710, 730, 750, 750 AQ-17, EM-90, EM-92, 371, 381 (above Arakawa Chemical Industries, Ltd.).
- FANCLIL registered trademark
- polyfunctional (meth) acrylate compounds may be used alone or in combination of two or more.
- hydroxymethyl group-substituted phenol compound examples include 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene, and 3,5-dihydroxymethyl-4-methoxytoluene [2, 6-bis (hydroxymethyl) -p-cresol].
- Examples of the compound having an alkoxyalkylated amino group include (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea, And a nitrogen-containing compound having a plurality of active methylol groups, wherein at least one hydrogen atom of the hydroxy group in the methylol group is substituted with an alkyl group such as a methyl group or a butyl group.
- the alkoxyalkylated amino group-containing compound may be a mixture in which a plurality of substituted compounds are mixed, and there is a mixture containing an oligomer component that is partially self-condensed, and such a mixture is also used. be able to.
- hexamethoxymethylmelamine CYTEC, CYMEL (registered trademark) 303, 303LF
- CYTEC, CYMEL (registered trademark) 1170 tetrabutoxymethylglycoluril
- CYTEC, CYMEL (registered trademark) 1170 tetramethoxymethylbenzoguanamine CYMEL series products
- CYTEC, CYMEL (registered trademark) 1123 POWDERLINK series products such as tetramethoxymethyl glycoluril
- methylated melamine resin ( Mika Chemical Co., Ltd., Nicarak [registered trademark] MW-30HM, MW-390, MW-100LM, MX-750LM), methylated urea resin (manufactured by Sanwa Chemical Co., Ltd., Nicarac [registered trademark]) MX 270, the MX-280, Nika rack series of products
- the polyfunctional blocked isocyanate compound has two or more isocyanate groups in which one or more isocyanate groups are blocked by an appropriate protecting group.
- the protecting group block portion
- the resulting isocyanate group causes a crosslinking reaction with the resin.
- Such a polyfunctional blocked isocyanate compound can be obtained, for example, by reacting an appropriate blocking agent with a polyfunctional isocyanate compound having two or more isocyanate groups in one molecule.
- polyfunctional isocyanate compound examples include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,3,6-hexamethylene triisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-cyclohexyl diisocyanate, 2,6 -Bis (isocyanatomethyl) tetrahydrodicyclopentadiene, bis (isocyanatemethyl) dicyclopentadiene, bis (isocyanatemethyl) adamantane, 2,5-diisocyanatomethyl Borene, norbornane diisocyanate, dicycloheptane triisocyanate
- the blocking agent examples include methanol, ethanol, isopropanol, n-butanol, heptanol, hexanol, 2-ethoxyhexanol, cyclohexanol, octanol, isononyl alcohol, stearyl alcohol, benzyl alcohol, 2-ethoxyethanol, methyl lactate, Ethyl lactate, amyl lactate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether), tri Ethylene glycol monoethyl ether, N, -Alcohols such as dimethylaminoethanol, N, N-diethylaminoethanol, N, N-dibuty
- the following product can be mentioned, for example. Takenate (registered trademark) B-815N, B-830, B-842N, B-84N, B-870, B-870N, B-874, B-874N, B-882, B-882N, B-5010, B-7005, B-7030, B-7075 (Mitsui Chemicals, Inc.).
- Duranate (registered trademark) ME20-B80S, MF-B60B, MF-B60X, MF-B90B, MF-K60B, MF-K60X, SBN-70D, 17B-60P, 17B-60PX, TPA-B80E, TPA-B80X, E402-B80B, E402-B80T, K6000 (above, manufactured by Asahi Kasei Chemicals Corporation), Coronate (registered trademark) 2503, 2507, 2512, 2513, 2515, 2520, 2520, 2554, BI-301, AP-M, Millionate MS-50 (above, manufactured by Tosoh Corporation).
- Vernock [registered trademark] D-500, D-550, DB-980K (above, manufactured by DIC Corporation).
- Sumidur (registered trademark) BL-3175, BL-4165, BL-4265, BL-1100, BL-1265, Death module (registered trademark) TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, BL-3475, Desmotherm (registered trademark) 2170, 2265 (manufactured by Sumika Bayer Urethane Co., Ltd.).
- VESTANAT (registered trademark) B1358A, B1358 / 100, B1370, VESTAGON (registered trademark) B1065, B1400, B1530, BF1320, BF1540 (above, manufactured by Evonik Industries).
- the polyfunctional blocked isocyanate compound examples include a homopolymer or a copolymer obtained by radical polymerization of a (meth) acrylate having a blocked isocyanate group.
- the copolymer means a polymer obtained by polymerizing two or more monomers.
- the copolymer may be a copolymer obtained by polymerizing two or more kinds of (meth) acrylates having a blocked isocyanate group, or may be obtained by polymerizing (meth) acrylates having a blocked isocyanate group and other (meth) acrylates. The resulting copolymer may be used.
- Examples of such commercially available (meth) acrylates having a blocked isocyanate group include Karenz [registered trademark] MOI-BM, AOI-BM, MOI-BP, AOI-BP, manufactured by Showa Denko KK MOI-DEM, MOI-CP, MOI-MP, MOI-OEt, MOI-OBu, MOI-OiPr.
- These polyfunctional blocked isocyanate compounds may be used alone or in combination of two or more.
- a catalyst for promoting the crosslinking reaction p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid And / or a thermal acid generator such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters.
- the blending amount is 0.0001% by mass to 20% by mass, preferably 0.0005% by mass to 10% by mass, based on the total solid content of the resin composition of the present invention.
- Substrate for example, a semiconductor substrate such as silicon covered with a silicon oxide film, a semiconductor substrate such as silicon covered with a silicon nitride film or a silicon oxynitride film, a silicon nitride substrate, a quartz substrate, a glass substrate (non-alkali glass, low (Including alkali glass and crystallized glass), a glass substrate on which an ITO film is formed ⁇ , the resin composition of the present invention is applied by an appropriate application method such as a spinner or a coater, and then a heating means such as a hot plate The cured film is formed by baking using
- Baking conditions are appropriately selected from baking temperatures of 80 ° C. to 270 ° C. and baking times of 0.3 minutes to 60 minutes, preferably at baking temperatures of 100 ° C. to 250 ° C. and baking times of 0.5 minutes to 5 minutes. is there.
- the thickness of the cured film formed from the resin composition of the present invention is 0.005 ⁇ m to 4.0 ⁇ m, preferably 0.01 ⁇ m to 3.0 ⁇ m, more preferably 0.1 ⁇ m to 3.0 ⁇ m. is there.
- a resist solution is applied onto the cured film formed from the resin composition of the present invention, exposed through a predetermined mask, and post-exposure heating (PEB) is performed as necessary, followed by alkali development, rinsing, and drying.
- PEB post-exposure heating
- alkali development, rinsing, and drying Thus, a predetermined resist pattern is formed.
- g-line, i-line, KrF excimer laser, ArF excimer laser can be used for the exposure.
- the resist pattern is reflowed by heat treatment to form a lens pattern.
- this lens pattern as an etching mask, the underlying cured film is etched back, and the lens pattern shape is transferred to the cured film to produce a microlens.
- Example 2 15.0 g of the solution containing the copolymer obtained in Synthesis Example 2; 0.00473 g of DFX-18 (manufactured by Neos) as a surfactant; and the homopolymer obtained in Synthesis Example 13 as a crosslinking agent.
- 0.923 g of the solution was dissolved in 30.9 g of cyclohexanone to obtain a solution. Thereafter, the obtained solution was filtered using a polyethylene microfilter having a pore diameter of 0.45 ⁇ m to prepare a resin composition.
- Example 3 15.0 g of the copolymer obtained in Synthesis Example 3, 0.00180 g of DFX-18 (manufactured by Neos) as a surfactant, CYMEL (registered trademark) 303LF (manufactured by CYTEC) as a cross-linking agent 300 g and 0.0150 g of p-toluenesulfonic acid monohydrate as an acid catalyst were dissolved in 16.0 g of cyclohexanone to obtain a solution. Thereafter, the obtained solution was filtered using a polyethylene microfilter having a pore diameter of 0.45 ⁇ m to prepare a resin composition.
- DFX-18 manufactured by Neos
- CYMEL registered trademark
- 303LF manufactured by CYTEC
- Example 4 15.0 g of the solution containing the copolymer obtained in Synthesis Example 4, 0.0050 g of DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant, 0.750 g of CYMEL 303LF (manufactured by CYTEC Co., Ltd.) as a cross-linking agent
- 0.0375 g of p-toluenesulfonic acid monohydrate as an acid catalyst was dissolved in 28.8 g of cyclohexanone to obtain a solution. Thereafter, the obtained solution was filtered using a polyethylene microfilter having a pore diameter of 0.45 ⁇ m to prepare a resin composition.
- Example 5 25.0 g of the solution containing the copolymer obtained in Synthesis Example 5, 0.020 g of DFX-18 (manufactured by Neos) as a surfactant, 1.00 g of CYMEL 303LF (manufactured by CYTEC) as a crosslinking agent, As an acid catalyst, 0.100 g of p-toluenesulfonic acid monohydrate was dissolved in 36.0 g of cyclohexanone and 14.1 g of propylene glycol monomethyl ether to prepare a solution. Thereafter, the obtained solution was filtered using a polyethylene microfilter having a pore diameter of 0.45 ⁇ m to prepare a resin composition.
- Example 6 15.0 g of the copolymer obtained in Synthesis Example 6, 0.0180 g of DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant, 3.00 g of CYMEL 303LF (manufactured by CYTEC Co., Ltd.) as a crosslinking agent, and an acid catalyst
- a solution 0.0150 g of p-toluenesulfonic acid monohydrate was dissolved in 16.0 g of cyclohexanone. Thereafter, the obtained solution was filtered using a polyethylene microfilter having a pore diameter of 0.45 ⁇ m to prepare a resin composition.
- Example 7 15.0 g of the solution containing the copolymer obtained in Synthesis Example 7, 0.00450 g of DFX-18 (manufactured by Neos) as a surfactant, 0.750 g of CYMEL 303LF (manufactured by CYTEC) as a crosslinking agent, As an acid catalyst, 0.0375 g of p-toluenesulfonic acid monohydrate was dissolved in 28.8 g of cyclohexanone to prepare a solution. Thereafter, the obtained solution was filtered using a polyethylene microfilter having a pore diameter of 0.45 ⁇ m to prepare a resin composition.
- Example 8 15.0 g of the copolymer obtained in Synthesis Example 8, 0.0180 g of DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant, 3.00 g of CYMEL 303LF (manufactured by CYTEC Co., Ltd.) as a crosslinking agent, and an acid catalyst
- a solution 0.150 g of p-toluenesulfonic acid monohydrate was dissolved in 16.0 g of cyclohexanone. Thereafter, the obtained solution was filtered using a polyethylene microfilter having a pore diameter of 0.45 ⁇ m to prepare a resin composition.
- Example 9 15.0 g of the copolymer obtained in Synthesis Example 9, 0.0180 g of DFX-18 (manufactured by Neos Co., Ltd.) as a surfactant, 3.00 g of CYMEL 303LF (manufactured by CYTEC Co., Ltd.) as a crosslinking agent, and an acid catalyst
- a solution 0.150 g of p-toluenesulfonic acid monohydrate was dissolved in 16.0 g of cyclohexanone. Thereafter, the obtained solution was filtered using a polyethylene microfilter having a pore diameter of 0.45 ⁇ m to prepare a resin composition.
- Example 10 25.0 g of the solution containing the copolymer obtained in Synthesis Example 10, 0.0200 g of DFX-18 (manufactured by Neos) as a surfactant, 1.0 g of CYMEL 303LF (manufactured by CYTEC) as a crosslinking agent, As an acid catalyst, 0.100 g of p-toluenesulfonic acid monohydrate was dissolved in 36.0 g of cyclohexanone and 14.1 g of propylene glycol monomethyl ether to prepare a solution. Thereafter, the obtained solution was filtered using a polyethylene microfilter having a pore diameter of 0.45 ⁇ m to prepare a resin composition.
- ⁇ Comparative example 2 11.0 g of the solution containing the copolymer obtained in Synthesis Example 12, 0.00396 g of DFX-18 (manufactured by Neos) as a surfactant, 0.660 g of CYMEL 303LF (manufactured by CYTEC) as a crosslinking agent, Then, 0.0330 g of p-toluenesulfonic acid monohydrate as an acid catalyst was dissolved in 27.6 g of cyclohexanone to prepare a solution. Then, it filtered using the polyethylene micro filter with the hole diameter of 0.45 micrometer, and prepared the resin composition.
- the resin compositions prepared in Examples 1 to 10 and Comparative Examples 1 and 2 were applied on a silicon wafer using a spin coater, respectively, on a hot plate at 100 ° C. for 1 minute, and further at 230 ° C. Baking was performed for 5 minutes to form a cured film having a thickness of 0.5 ⁇ m. Using the etcher and the etching gas, the dry etching rate of these cured films was measured. Similarly, a resist solution (THMR-iP1800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.)) was applied on a silicon wafer using a spin coater, and baked on a hot plate at 90 ° C.
- THMR-iP1800 manufactured by Tokyo Ohka Kogyo Co., Ltd.
- the cured film formed from the resin composition of the present invention has a refractive index of 1.68 or more, and in particular, the resin compositions prepared in Example 2 and Examples 6 to 10.
- a cured film formed from a material has a high refractive index of 1.70 or higher, and is highly transparent and has a high heat resistance showing a transmittance of 90% or higher even after heating at 260 ° C. there were.
- the cured film obtained from the resin composition containing the polymer of the present invention can satisfy high refractive index, high transparency, and high heat resistance, and can be suitably used as a microlens for a solid-state imaging device. .
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Epoxy Resins (AREA)
Abstract
Description
しかしながら、この樹脂組成物を硬化して得られるプラスチックレンズは、屈折率が1.50前後と低いため、レンズの中心厚又はコバ(縁)厚が厚くなってしまい、より屈折率の高いレンズ用樹脂が望まれていた。
(式中、A1及びA2はそれぞれ独立に-O-基又は-C(=O)O-基を表し、Xは少なくとも1つの芳香環又は複素環を有する二価の有機基を表し、該Xが2つ以上の芳香環又は複素環を有する場合、環同士が単結合を介して結合していても、ヘテロ原子を介して結合していても、縮合環を形成していてもよく、Yは少なくとも1つの芳香環又は縮合環を有する二価の有機基を表す。)
(式中、A1、A2、X及びYは前記式(1)における定義と同義である。)
(式中、R0はメチル基を表し、mは0乃至2の整数を表し、R1及びR2はそれぞれ独立に単結合又はメチレン基を表し、Zは単結合又は-S-基を表し、R3は水素原子、分岐構造を有していてもよい炭素原子数1乃至10のアルキル基、アリール基、炭素原子数2もしくは3のアルケニル基又は炭素原子数2もしくは3のアルキニル基を表し、R4は分岐構造を有していてもよい炭素原子数1乃至10のアルキル基、アリール基、炭素原子数2もしくは3のアルケニル基又は炭素原子数2もしくは3のアルキニル基を表す。)
前記式(2)で表されるジメルカプト化合物としては、例えば、1,4-ベンゼンジチオール、1,3-ベンゼンジチオール、4,5-ビス(メルカプトメチル)-o-キシレン、ビスムチオール、6-アニリノ-1,3,5-トリアジン-2,4-ジチオール、6-(ジアリルアミノ)-1,3,5-トリアジン-2,4-ジチオール、4,4’-ビフェニルジチオール、1,5-ジメルカプトナフタレン、4,4’-チオビスベンゼンチオール、及び2,7-ジメルカプトチアントレンが挙げられる。
前記式(3)で表されるジグリシジル化合物としては、例えば、テレフタル酸ビスグリシジル、レゾルシノールジグリシジルエーテル、2,2-ビス(4-グリシジルオキシフェニル)プロパン、ビスフェノールフルオレンジグリシジルエーテル、ビスナフトールフルオレンジグリシジルエーテル、モノアリルジグリシジルイソシアヌレート、及びビス[4-(2,3-エポキシプロピルチオ)フェニル]スルフィドが挙げられる。
そのような溶剤としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノブチルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、2-ヒドロキシプロピオン酸エチル、2-ヒドロキシ-2-メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、2-ヒドロキシ-3-メチルブタン酸メチル、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸エチル、3-エトキシプロピオン酸メチル、ピルビン酸メチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、ジメチルアセトアミド、2-ヘプタノン、N-メチル-2-ピロリドン、及びγ-ブチロラクトンを挙げることができる。これらの溶剤は、単独で使用しても、2種以上を組み合わせて使用してもよい。
当該界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー類、ソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタントリステアレート等のソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリオレエート、ポリオキシエチレンソルビタントリステアレート等のポリオキシエチレンソルビタン脂肪酸エステル類等のノニオン系界面活性剤、エフトップ〔登録商標〕EF301、同EF303、同EF352(以上、三菱マテリアル電子化成(株)製)、メガファック〔登録商標〕F171、同F173、同R-30、同R-40、同R-40-LM(以上、DIC(株)製)、フロラードFC430、同FC431(以上、住友スリーエム(株)製)、アサヒガード〔登録商標〕AG710、サーフロン〔登録商標〕S-382、同SC101、同SC102、同SC103、同SC104、同SC105、同SC106(旭硝子(株)製)、DFX-18、FTX-206D、FTX-212D、FTX-218、FTX-220D、FTX-230D、FTX-240D、FTX-212P、FTX-220P、FTX-228P、FTX-240G等フタージェントシリーズ((株)ネオス製)等のフッ素系界面活性剤、オルガノシロキサンポリマーKP341(信越化学工業(株)製)を挙げることができる。これらの界面活性剤は、単独で又は2種以上を組み合わせて使用することができる。
アロニックス〔登録商標〕M-208、同M-210、同M-211B、同M-215、同M-220、同M-225、同M-233、同M-240、同M-245、同M-260、同M-270、同M-303、同M-305、同M-306、同M-309、同M-310、同M-313、同M-315、同M-321、同M-350、同M-360、同M-400、同M-402、同M-403、同M-404、同M-405、同M-406、同M-408、同M-450、同M-452、同M-460、同M-510、同M-520、同M-1100、同M-1200、同M-1210、同M-1310、同M-1600、同M-1960、同M-6100、同M-6200、同M-6250、同M-6500、同M-7100、同M-7300K、同M-8030、同M-8060、同M-8100、同M-8530、同M-8560、同M-9050(以上、東亜合成(株)製)。
NKエコノマーA-PG5009E、同A-PG5027E、同A-PG5054E、
NKオリゴU-2PPA、同U-6LPA、同U-10HA、同U-10PA、同UA-1100H、同U-4H、同U-6H、同U-4HA、同U-6HA、同U-15HA、同UA-32P、同UA-33H、同UA-53H、同U-200PA、同U-324A、同UA-160TM、同UA-290TM、同UA-4200、同UA-4400、同UA-122P、同UA-7100、同UA-W2A(以上、新中村化学工業(株)製)。
タケネート〔登録商標〕B-815N、同B-830、同B-842N、同B-846N、同B-870、同B-870N、同B-874、同B-874N、同B-882、同B-882N、同B-5010、同B-7005、同B-7030、同B-7075(以上、三井化学(株)製)。
コロネート〔登録商標〕2503、同2507、同2512、同2513、同2515、同2520、同2554、同BI-301、同AP-M、ミリオネート MS-50(以上、東ソー(株)製)。
〔下記合成例で得られた共重合体の重量平均分子量の測定〕
装置:日本分光(株)製GPCシステム
カラム:Shodex〔登録商標〕KF-804L及び803L
カラムオーブン:40℃
流量:1mL/分
溶離液:テトラヒドロフラン
<合成例1>
1,4-ベンゼンジチオール4.15g、ビスフェノールフルオレンジグリシジルエーテル15.0g、及びエチルトリフェニルホスホニウムブロミド0.649gをシクロヘキサノン59.4gに溶解させた後、室温で18時間反応させることにより、下記式(4)で表される構造単位を有する共重合体を含む溶液(固形分濃度25質量%)を得た。得られた共重合体の重量平均分子量Mwは14,800(ポリスチレン換算)であった。
4,4’-チオビスベンゼンチオール3.89g、ビスフェノールフルオレンジグリシジルエーテル8.00g、及びエチルトリフェニルホスホニウムブロミド0.346gをシクロヘキサノン28.6gに溶解させた後、室温で18時間反応させることにより、下記式(5)で表される構造単位を有する共重合体を含む溶液(固形分濃度30質量%)を得た。得られた共重合体の重量平均分子量Mwは6,800(ポリスチレン換算)であった。
6-アニリノ-1,3,5-トリアジン-2,4-ジチオール5.24g、ビスフェノールフルオレンジグリシジルエーテル10.0g、及びエチルトリフェニルホスホニウムブロミド0.247gをシクロヘキサノン61.9gに溶解させた後、室温で18時間反応させ、メタノールを用いて再沈殿させることにより、下記式(6)で表される構造単位を有する共重合体を得た。得られた共重合体の重量平均分子量Mwは14,100(ポリスチレン換算)であった。
ビスムチオール4.38g、ビスフェノールフルオレンジグリシジルエーテル15.0g、及びエチルトリフェニルホスホニウムブロミド0.649gをシクロヘキサノン60.1gに溶解させた後、室温で18時間反応させることにより、下記式(7)で表される構造単位を有する共重合体を含む溶液(固形分濃度25質量%)を得た。得られた共重合体の重量平均分子量Mwは24,200(ポリスチレン換算)であった。
6-(ジアリルアミノ)-1,3,5-トリアジン-2,4-ジチオール4.7g、ビスフェノールフルオレンジグリシジルエーテル10.0g、及びエチルトリフェニルホスホニウムブロミド0.400gをシクロヘキサノン60.5gに溶解させた後、室温で18時間反応させることにより、下記式(8)で表される構造単位を有する共重合体を含む溶液(固形分濃度20質量%)を得た。得られた共重合体の重量平均分子量Mwは68,000(ポリスチレン換算)であった。
1,4-ベンゼンジチオール3.60g、ビスナフトールフルオレンジグリシジルエーテル15.0g、及びエチルトリフェニルホスホニウムブロミド0.564gをシクロヘキサノン57.5gに溶解させた後、室温で18時間反応させ、メタノールを用いて再沈殿させることにより、下記式(9)で表される構造単位を有する共重合体を得た。得られた共重合体の重量平均分子量Mwは26,600(ポリスチレン換算)であった。
4,4’-チオビスベンゼンチオール1.69g、ビスナフトールフルオレンジグリシジルエーテル4.00g、及びエチルトリフェニルホスホニウムブロミド0.150gをシクロヘキサノン17.5gに溶解させた後、室温で18時間反応させることにより、下記式(10)で表される構造単位を有する共重合体を含む溶液(固形分濃度25質量%)を得た。得られた共重合体の重量平均分子量Mwは12,600(ポリスチレン換算)であった。
6-アニリノ-1,3,5-トリアジン-2,4-ジチオール2.79g、ビスナフトールフルオレンジグリシジルエーテル7.00g、及びエチルトリフェニルホスホニウムブロミド0.263gをシクロヘキサノン23.5gに溶解させた後、室温で18時間反応させ、メタノールを用いて再沈殿させることにより、下記式(11)で表される構造単位を有する共重合体を得た。得られた共重合体の重量平均分子量Mwは3,800(ポリスチレン換算)であった。
ビスムチオール3.80g、ビスナフトールフルオレンジグリシジルエーテル15.0g、及びエチルトリフェニルホスホニウムブロミド0.564gをシクロヘキサノン58.1gに溶解させた後、室温で18時間反応させ、メタノールを用いて再沈殿させることにより、下記式(12)で表される構造単位を有する共重合体を得た。得られた共重合体の重量平均分子量Mwは22,900(ポリスチレン換算)であった。
6-(ジアリルアミノ)-1,3,5-トリアジン-2,4-ジチオール3.8g、ビスナフトールフルオレンジグリシジルエーテル10.0g、及びエチルトリフェニルホスホニウムブロミド0.300gをシクロヘキサノン57.0gに溶解させた後、室温で18時間反応させることにより、下記式(13)で表される構造単位を有する共重合体を含む溶液(固形分濃度20質量%)を得た。得られた共重合体の重量平均分子量Mwは99,000(ポリスチレン換算)であった。
2,3-ジヒドロキシブタン二酸4.38g、ビスフェノールフルオレンジグリシジルエーテル15.0g、及びエチルトリフェニルホスホニウムブロミド1.30gをシクロヘキサノン48.2gに溶解させた後、還流下で18時間反応させることにより、下記式(14)で表される構造単位を有する共重合体を含む溶液(固形分濃度30質量%)を得た。得られた共重合体の重量平均分子量Mwは3,700(ポリスチレン換算)であった。
2,3-ジヒドロキシブタン二酸3.80g、ビスナフトールフルオレンジグリシジルエーテル15.0g、及びエチルトリフェニルホスホニウムブロミド1.13gをシクロヘキサノン49.5gに溶解させた後、還流下で18時間反応させることにより、下記式(15)で表される構造単位を有する共重合体を含む溶液(固形分濃度30質量%)を得た。得られた共重合体の重量平均分子量Mwは5,800(ポリスチレン換算)であった。
<合成例13>
2-[(3,5-ジメチルピラゾリル)カルボニルアミノ]エチルメタクリレート40.0g及び2,2’-アゾビスイソブチロニトリル2.61gをプロピレングリコールモノメチルエーテル79.1gに溶解させた後、この溶液を、プロピレングリコールモノメチルエーテル48.7gを80℃に保持したフラスコ中に3時間かけて滴下した。滴下終了後、18時間反応させることにより、下記式(16)で表される構造単位を有する単独重合体を含む溶液(固形分濃度24.3質量%)を得た。得られた単独重合体の重量平均分子量Mwは14,500(ポリスチレン換算)であった。
<実施例1>
合成例1で得られた共重合体を含む溶液15.0g、界面活性剤としてDFX-18(ネオス(株)製)0.00413g、架橋剤として合成例13で得られた単独重合体を含む溶液0.154gを、シクロヘキサノン24.3gに溶解させて溶液とした。その後、得られた溶液を孔径0.45μmのポリエチレン製ミクロフィルターを用いてろ過して樹脂組成物を調製した。
合成例2で得られた共重合体を含む溶液15.0g、界面活性剤としてDFX-18(ネオス(株)製)0.00473g、架橋剤として合成例13で得られた単独重合体を含む溶液0.923gを、シクロヘキサノン30.9gに溶解させて溶液とした。その後、得られた溶液を孔径0.45μmのポリエチレン製ミクロフィルターを用いてろ過して樹脂組成物を調製した。
合成例3で得られた共重合体15.0g、界面活性剤としてDFX-18(ネオス(株)製)0.00180g、架橋剤としてCYMEL〔登録商標〕303LF(CYTEC(株)製)0.300g、及び酸触媒としてp-トルエンスルホン酸一水和物0.0150gを、シクロヘキサノン16.0gに溶解させて溶液とした。その後、得られた溶液を孔径0.45μmのポリエチレン製ミクロフィルターを用いてろ過して樹脂組成物を調製した。
合成例4で得られた共重合体を含む溶液15.0g、界面活性剤としてDFX-18(ネオス(株)製)0.00450g、架橋剤としてCYMEL 303LF(CYTEC(株)製)0.750g、及び酸触媒としてp-トルエンスルホン酸一水和物0.0375gを、シクロヘキサノン28.8gに溶解させて溶液とした。その後、得られた溶液を孔径0.45μmのポリエチレン製ミクロフィルターを用いてろ過して樹脂組成物を調製した。
合成例5で得られた共重合体を含む溶液25.0g、界面活性剤としてDFX-18(ネオス(株)製)0.020g、架橋剤としてCYMEL303LF(CYTEC(株)製)1.00g、及び酸触媒としてp-トルエンスルホン酸一水和物0.100gを、シクロヘキサノン36.0g及びプロピレングリコールモノメチルエーテル14.1gに溶解させて溶液とした。その後、得られた溶液を孔径0.45μmのポリエチレン製ミクロフィルターを用いてろ過して樹脂組成物を調製した。
合成例6で得られた共重合体15.0g、界面活性剤としてDFX-18(ネオス(株)製)0.0180g、架橋剤としてCYMEL303LF(CYTEC(株)製)3.00g、及び酸触媒としてp-トルエンスルホン酸一水和物0.0150gを、シクロヘキサノン16.0gに溶解させて溶液とした。その後、得られた溶液を孔径0.45μmのポリエチレン製ミクロフィルターを用いてろ過して樹脂組成物を調製した。
合成例7で得られた共重合体を含む溶液15.0g、界面活性剤としてDFX-18(ネオス(株)製)0.00450g、架橋剤としてCYMEL303LF(CYTEC(株)製)0.750g、及び酸触媒としてp-トルエンスルホン酸一水和物0.0375gを、シクロヘキサノン28.8gに溶解させて溶液とした。その後、得られた溶液を孔径0.45μmのポリエチレン製ミクロフィルターを用いてろ過して樹脂組成物を調製した。
合成例8で得られた共重合体15.0g、界面活性剤としてDFX-18(ネオス(株)製)0.0180g、架橋剤としてCYMEL303LF(CYTEC(株)製)3.00g、及び酸触媒としてp-トルエンスルホン酸一水和物0.150gを、シクロヘキサノン16.0gに溶解させて溶液とした。その後、得られた溶液を孔径0.45μmのポリエチレン製ミクロフィルターを用いてろ過して樹脂組成物を調製した。
合成例9で得られた共重合体15.0g、界面活性剤としてDFX-18(ネオス(株)製)0.0180g、架橋剤としてCYMEL303LF(CYTEC(株)製)3.00g、及び酸触媒としてp-トルエンスルホン酸一水和物0.150gを、シクロヘキサノン16.0gに溶解させて溶液とした。その後、得られた溶液を孔径0.45μmのポリエチレン製ミクロフィルターを用いてろ過して樹脂組成物を調製した。
合成例10で得られた共重合体を含む溶液25.0g、界面活性剤としてDFX-18(ネオス(株)製)0.0200g、架橋剤としてCYMEL303LF(CYTEC(株)製)1.0g、及び酸触媒としてp-トルエンスルホン酸一水和物0.100gを、シクロヘキサノン36.0g及びプロピレングリコールモノメチルエーテル14.1gに溶解させて溶液とした。その後、得られた溶液を孔径0.45μmのポリエチレン製ミクロフィルターを用いてろ過して樹脂組成物を調製した。
合成例11で得られた共重合体を含む溶液11.0g、界面活性剤としてDFX-18(ネオス(株)製)0.00396g、架橋剤としてCYMEL303LF(CYTEC(株)製)0.660g、及び酸触媒としてp-トルエンスルホン酸一水和物0.0330gを、シクロヘキサノン27.6gに溶解させて溶液とした。その後、得られた溶液を孔径0.45μmのポリエチレン製ミクロフィルターを用いてろ過して樹脂組成物を調製した。
合成例12で得られた共重合体を含む溶液11.0g、界面活性剤としてDFX-18(ネオス(株)製)0.00396g、架橋剤としてCYMEL303LF(CYTEC(株)製)0.660g、及び酸触媒としてp-トルエンスルホン酸一水和物0.0330gを、シクロヘキサノン27.6gに溶解させて溶液とした。その後、孔径0.45μmのポリエチレン製ミクロフィルターを用いてろ過して樹脂組成物を調製した。
実施例1乃至実施例10並びに比較例1及び比較例2で調製した樹脂組成物をそれぞれ、シリコンウエハー上にスピンコーターを用いて塗布し、ホットプレート上において100℃で1分間、さらに230℃で5分間ベークを行い、膜厚0.5μmの硬化膜を形成した。これらの硬化膜に対して、高速分光エリプソメーターM-2000((株)ジェー・エー・ウーラム・ジャパン)を用いて波長550nmの屈折率を測定した。評価結果を表1に示す。
実施例1乃至実施例10並びに比較例1及び比較例2で調製した樹脂組成物をそれぞれ、石英基板上にスピンコーターを用いて塗布し、ホットプレート上において100℃で1分間、さらに230℃で5分間ベークを行い、膜厚0.5μmの硬化膜を形成した。これらの硬化膜に対して、紫外線可視分光光度計UV-2550((株)島津製作所製)を用いて波長400nmの透過率を測定した。さらにこれらの硬化膜を260℃で5分間加熱した後、波長400nmの透過率を測定した。評価結果を表1に示す。
実施例1乃至実施例10並びに比較例1及び比較例2で調製した樹脂組成物をそれぞれ、シリコンウエハー上にスピンコーターを用いて塗布し、ホットプレート上において100℃で1分間、さらに230℃で5分間ベークを行い、膜厚0.5μmの硬化膜を形成した。これらの硬化膜に対して、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、乳酸エチル、シクロヘキサノンに、それぞれ23℃の温度条件下、5分間浸漬する試験を行った。浸漬前後において膜厚変化を測定した結果、上記全ての溶剤について膜厚増減が5%未満であった。
ドライエッチングレートの測定に用いたエッチャー及びエッチングガスは、以下の通りである。
エッチャー:RIE-10NR(サムコ(株)製)
エッチングガス:CF4
Claims (9)
- 前記Xで表される二価の有機基は下記式(a)、式(b)、式(c)、式(d)又は式(e)で表される、請求項1又は請求項2に記載の重合体。
(式中、R0はメチル基を表し、mは0乃至2の整数を表し、R1及びR2はそれぞれ独立に単結合又はメチレン基を表し、Zは単結合又は-S-基を表し、R3は水素原子、分岐構造を有していてもよい炭素原子数1乃至10のアルキル基、アリール基、炭素原子数2もしくは3のアルケニル基又は炭素原子数2もしくは3のアルキニル基を表し、R4は分岐構造を有していてもよい炭素原子数1乃至10のアルキル基、アリール基、炭素原子数2もしくは3のアルケニル基又は炭素原子数2もしくは3のアルキニル基を表す。) - [規則91に基づく訂正 17.10.2016]
前記重合体の重量平均分子量は1,000乃至150,000である、請求項1乃至請求項4のいずれか一項に記載の重合体。 - 前記式(2)で表される化合物及び式(3)で表される化合物を3:5乃至5:3のモル比で使用し、23℃乃至200℃の温度下で重合反応させる、請求項1乃至請求項5のいずれか一項に記載の重合体の合成方法。
- 請求項1乃至請求項6のいずれか一項に記載の重合体、架橋剤及び溶剤を含有する樹脂組成物。
- マイクロレンズ用組成物である請求項7に記載の樹脂組成物。
- 請求項7に記載の樹脂組成物を基板上に塗布した後、加熱手段を用いて前記樹脂組成物をベークすることによる、硬化膜の形成方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020187011131A KR102649126B1 (ko) | 2015-10-27 | 2016-10-04 | 중합체 및 이것을 포함하는 수지 조성물 |
CN201680057605.1A CN108137808B (zh) | 2015-10-27 | 2016-10-04 | 聚合物和含有该聚合物的树脂组合物 |
JP2017547696A JP6944128B2 (ja) | 2015-10-27 | 2016-10-04 | 重合体及びそれを含む樹脂組成物 |
US15/771,280 US10793677B2 (en) | 2015-10-27 | 2016-10-04 | Polymer and resin composition containing the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015211168 | 2015-10-27 | ||
JP2015-211168 | 2015-10-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017073268A1 true WO2017073268A1 (ja) | 2017-05-04 |
Family
ID=58630355
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/079507 WO2017073268A1 (ja) | 2015-10-27 | 2016-10-04 | 重合体及びそれを含む樹脂組成物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10793677B2 (ja) |
JP (1) | JP6944128B2 (ja) |
KR (1) | KR102649126B1 (ja) |
CN (1) | CN108137808B (ja) |
TW (1) | TWI764873B (ja) |
WO (1) | WO2017073268A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20190085430A (ko) * | 2018-01-10 | 2019-07-18 | 동우 화인켐 주식회사 | 바인더 수지, 착색 감광성 수지 조성물, 이를 포함하는 디스플레이 격벽 구조물 및 이를 포함하는 표시장치 |
JP7418244B2 (ja) | 2020-02-28 | 2024-01-19 | 三星電子株式会社 | トリアジン環含有ポリマーならびにこれを含む熱可塑性成形品、射出成形品および光学部品 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7269716B2 (ja) * | 2018-11-22 | 2023-05-09 | 東京応化工業株式会社 | 硬化性組成物、硬化物、マイクロレンズ、及び光学素子 |
JP2020132749A (ja) * | 2019-02-19 | 2020-08-31 | メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングMerck Patent GmbH | ポリマー、ポリマーを含んでなる半導体組成物、および半導体組成物を用いた膜の製造方法 |
CN112625217B (zh) * | 2020-12-23 | 2022-07-12 | 江南大学 | 一种含硫含芴结构高折射率光学树脂的制备方法 |
Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06340730A (ja) * | 1993-04-05 | 1994-12-13 | Takeda Chem Ind Ltd | 共重合体及びその製造法 |
JPH09110983A (ja) * | 1995-05-12 | 1997-04-28 | Mitsui Toatsu Chem Inc | ポリスルフィド系樹脂組成物、該樹脂及びその樹脂よりなる光学材料 |
JP2000351846A (ja) * | 1998-09-08 | 2000-12-19 | Mitsui Chemicals Inc | 含硫(チオ)エーテル(共)重合体およびその用途 |
JP2003086353A (ja) * | 2001-09-11 | 2003-03-20 | Nissan Chem Ind Ltd | 有機el素子用透明性基板および有機el素子 |
JP2005003991A (ja) * | 2003-06-12 | 2005-01-06 | Seiko Epson Corp | プラスチックレンズの被膜除去方法及びプラスチックレンズの製造方法 |
JP2009062459A (ja) * | 2007-09-06 | 2009-03-26 | Nippon Shokubai Co Ltd | 有機無機複合樹脂組成物及び該有機無機複合樹脂組成物を硬化させてなる硬化物 |
US20090093570A1 (en) * | 2007-10-09 | 2009-04-09 | Industrial Technology Research Institute | Encapsulant composition for a light-emitting diode |
JP2009084310A (ja) * | 2007-09-27 | 2009-04-23 | Nippon Shokubai Co Ltd | 熱・光硬化性樹脂組成物、光学材料及び光学部材 |
JP2009227936A (ja) * | 2008-03-25 | 2009-10-08 | Nippon Shokubai Co Ltd | 硬化性樹脂組成物、その硬化物、光学部材及び光学ユニット |
JP2011016887A (ja) * | 2009-07-08 | 2011-01-27 | Yasuhara Chemical Co Ltd | 脂環式ジエポキシ化合物、脂環式ジエポキシ化合物の製造方法、エポキシ樹脂組成物および硬化物 |
JP2011162765A (ja) * | 2010-01-14 | 2011-08-25 | Canon Inc | 有機・無機複合材料及びその製造方法、並びに光学部材 |
JP2011184331A (ja) * | 2010-03-05 | 2011-09-22 | Yasuhara Chemical Co Ltd | 脂環式エポキシ化合物、脂環式エポキシ化合物の製造方法、エポキシ樹脂組成物および硬化物 |
JP2011190413A (ja) * | 2010-03-16 | 2011-09-29 | Kumamoto Univ | シロキサンポリマー架橋硬化物 |
WO2012032868A1 (ja) * | 2010-09-09 | 2012-03-15 | Hoya株式会社 | 表面修飾チタニア粒子の製造方法、チタニア粒子分散液およびチタニア粒子分散樹脂 |
JP5716878B1 (ja) * | 2013-10-15 | 2015-05-13 | 三菱瓦斯化学株式会社 | 光学材料用組成物及びそれを用いた光学材料 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2776810B2 (ja) | 1987-07-03 | 1998-07-16 | ソニー株式会社 | 固体撮像装置の製造方法 |
JP3254759B2 (ja) | 1992-09-25 | 2002-02-12 | ソニー株式会社 | 光学素子およびオンチップレンズの製造方法 |
JP4617331B2 (ja) | 1996-05-29 | 2011-01-26 | 三井化学株式会社 | チオール化合物、含硫o−(メタ)アクリレート化合物およびその用途 |
US6320020B1 (en) * | 1998-09-08 | 2001-11-20 | Mitsui Chemicals, Inc. | Sulfur-containing (thio)ether (co)polymer and a use thereof |
JP2001091702A (ja) | 1999-07-22 | 2001-04-06 | Showa Denko Kk | プラスチックレンズ用組成物、視力矯正用プラスチックレンズ及び該プラスチックレンズの製造方法 |
US7371804B2 (en) * | 2004-09-07 | 2008-05-13 | Ophthonix, Inc. | Monomers and polymers for optical elements |
JP4749201B2 (ja) | 2006-03-31 | 2011-08-17 | 三井化学株式会社 | 半導体発光素子封止用組成物 |
JP2012188379A (ja) | 2011-03-10 | 2012-10-04 | Asahi Kasei Corp | チイラン化合物及びその硬化物 |
US9994685B2 (en) * | 2011-07-07 | 2018-06-12 | Nissan Chemical Industries, Ltd. | Resin composition |
-
2016
- 2016-10-04 CN CN201680057605.1A patent/CN108137808B/zh active Active
- 2016-10-04 US US15/771,280 patent/US10793677B2/en active Active
- 2016-10-04 KR KR1020187011131A patent/KR102649126B1/ko active IP Right Grant
- 2016-10-04 JP JP2017547696A patent/JP6944128B2/ja active Active
- 2016-10-04 WO PCT/JP2016/079507 patent/WO2017073268A1/ja active Application Filing
- 2016-10-19 TW TW105133724A patent/TWI764873B/zh active
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06340730A (ja) * | 1993-04-05 | 1994-12-13 | Takeda Chem Ind Ltd | 共重合体及びその製造法 |
JPH09110983A (ja) * | 1995-05-12 | 1997-04-28 | Mitsui Toatsu Chem Inc | ポリスルフィド系樹脂組成物、該樹脂及びその樹脂よりなる光学材料 |
JP2000351846A (ja) * | 1998-09-08 | 2000-12-19 | Mitsui Chemicals Inc | 含硫(チオ)エーテル(共)重合体およびその用途 |
JP2003086353A (ja) * | 2001-09-11 | 2003-03-20 | Nissan Chem Ind Ltd | 有機el素子用透明性基板および有機el素子 |
JP2005003991A (ja) * | 2003-06-12 | 2005-01-06 | Seiko Epson Corp | プラスチックレンズの被膜除去方法及びプラスチックレンズの製造方法 |
JP2009062459A (ja) * | 2007-09-06 | 2009-03-26 | Nippon Shokubai Co Ltd | 有機無機複合樹脂組成物及び該有機無機複合樹脂組成物を硬化させてなる硬化物 |
JP2009084310A (ja) * | 2007-09-27 | 2009-04-23 | Nippon Shokubai Co Ltd | 熱・光硬化性樹脂組成物、光学材料及び光学部材 |
US20090093570A1 (en) * | 2007-10-09 | 2009-04-09 | Industrial Technology Research Institute | Encapsulant composition for a light-emitting diode |
JP2009227936A (ja) * | 2008-03-25 | 2009-10-08 | Nippon Shokubai Co Ltd | 硬化性樹脂組成物、その硬化物、光学部材及び光学ユニット |
JP2011016887A (ja) * | 2009-07-08 | 2011-01-27 | Yasuhara Chemical Co Ltd | 脂環式ジエポキシ化合物、脂環式ジエポキシ化合物の製造方法、エポキシ樹脂組成物および硬化物 |
JP2011162765A (ja) * | 2010-01-14 | 2011-08-25 | Canon Inc | 有機・無機複合材料及びその製造方法、並びに光学部材 |
JP2011184331A (ja) * | 2010-03-05 | 2011-09-22 | Yasuhara Chemical Co Ltd | 脂環式エポキシ化合物、脂環式エポキシ化合物の製造方法、エポキシ樹脂組成物および硬化物 |
JP2011190413A (ja) * | 2010-03-16 | 2011-09-29 | Kumamoto Univ | シロキサンポリマー架橋硬化物 |
WO2012032868A1 (ja) * | 2010-09-09 | 2012-03-15 | Hoya株式会社 | 表面修飾チタニア粒子の製造方法、チタニア粒子分散液およびチタニア粒子分散樹脂 |
JP5716878B1 (ja) * | 2013-10-15 | 2015-05-13 | 三菱瓦斯化学株式会社 | 光学材料用組成物及びそれを用いた光学材料 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20190085430A (ko) * | 2018-01-10 | 2019-07-18 | 동우 화인켐 주식회사 | 바인더 수지, 착색 감광성 수지 조성물, 이를 포함하는 디스플레이 격벽 구조물 및 이를 포함하는 표시장치 |
KR102377269B1 (ko) | 2018-01-10 | 2022-03-22 | 동우 화인켐 주식회사 | 바인더 수지, 착색 감광성 수지 조성물, 이를 포함하는 디스플레이 격벽 구조물 및 이를 포함하는 표시장치 |
JP7418244B2 (ja) | 2020-02-28 | 2024-01-19 | 三星電子株式会社 | トリアジン環含有ポリマーならびにこれを含む熱可塑性成形品、射出成形品および光学部品 |
Also Published As
Publication number | Publication date |
---|---|
US20190055359A1 (en) | 2019-02-21 |
US10793677B2 (en) | 2020-10-06 |
JPWO2017073268A1 (ja) | 2018-09-13 |
KR102649126B1 (ko) | 2024-03-20 |
TW201731900A (zh) | 2017-09-16 |
KR20180072697A (ko) | 2018-06-29 |
JP6944128B2 (ja) | 2021-10-06 |
CN108137808B (zh) | 2020-12-25 |
CN108137808A (zh) | 2018-06-08 |
TWI764873B (zh) | 2022-05-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6944128B2 (ja) | 重合体及びそれを含む樹脂組成物 | |
JP7073845B2 (ja) | 重合体及びそれを含む樹脂組成物 | |
JP6421964B2 (ja) | 熱硬化性樹脂組成物 | |
JP7464911B2 (ja) | ネガ型感光性樹脂組成物 | |
TWI608021B (zh) | Resin composition for forming a cured film | |
CN110573963A (zh) | 感光性树脂组合物 | |
TWI765854B (zh) | 無溶劑型光硬化性接著劑用組成物 | |
KR101411294B1 (ko) | 고평탄화막 형성용 수지 조성물 | |
KR20150052080A (ko) | 경화막 형성 조성물 | |
JP5585796B2 (ja) | 末端に不飽和基を有する化合物を含有するポジ型感光性樹脂組成物 | |
CN110537146A (zh) | 感光性树脂组合物 | |
JPWO2017077932A1 (ja) | マイクロレンズ用光硬化性樹脂組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16859505 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017547696 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20187011131 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 16859505 Country of ref document: EP Kind code of ref document: A1 |