WO2015108167A1 - Method for producing cyclobutane tetracarboxylic acid derivative - Google Patents
Method for producing cyclobutane tetracarboxylic acid derivative Download PDFInfo
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- WO2015108167A1 WO2015108167A1 PCT/JP2015/051146 JP2015051146W WO2015108167A1 WO 2015108167 A1 WO2015108167 A1 WO 2015108167A1 JP 2015051146 W JP2015051146 W JP 2015051146W WO 2015108167 A1 WO2015108167 A1 WO 2015108167A1
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- 0 *C(C(O1)=O)=CC1=O Chemical compound *C(C(O1)=O)=CC1=O 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
Definitions
- the present invention relates to a method for producing an alicyclic tetracarboxylic dianhydride that can be a raw material monomer such as polyimide for optical materials.
- a polyimide resin is widely used as an electronic material such as a protective material or an insulating material in a liquid crystal display element or a semiconductor because of its high mechanical strength, heat resistance, insulation, solvent resistance, and the like.
- an optical communication material such as an optical waveguide material is also expected.
- the development of this field has been remarkable, and correspondingly, higher and higher properties are required for the materials used. That is, it is expected not only to be excellent in heat resistance and solvent resistance, but also to have a large number of performances depending on the application.
- Patent Document 3 shows the following scheme.
- 1,3-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid-1,2: 3,4-dianhydride is obtained by photodimerization reaction of citraconic anhydride (abbreviated as MMA).
- MMA citraconic anhydride
- Product (1,3-DMCBDA) and 1,2-dimethylcyclobutane-1,2,3,4-tetracarboxylic acid-1,2: 3,4-dianhydride (1,2-DMCBDA) Is disclosed.
- 1,3-DMCBDA when 1,3-DMCBDA is compared with 1,2-DMCBDA, the former 1,3-DMCBDA, which is an isomer having a highly symmetric structure, has a molecular weight higher than that of the latter 1,2-DMCBDA. It is known that a high polyimide can be produced and is more useful.
- Patent Document 3 describes that a mixture of 1,3-DMCBDA and 1,2-DMCBDA can be obtained, the former is a highly useful isomer having a highly symmetric structure. There is no description on the selective and high yield production of 1,3-DMCBDA.
- Japanese Patent Publication No. 2-24294 Japanese Unexamined Patent Publication No. 58-208322 Japanese Unexamined Patent Publication No. 4-106127
- the object of the present invention is to use 1,2-dialkylcyclobutane-1,2,3,4-tetracarboxylic acid-1,2 by a photodimerization reaction using a specific maleic anhydride compound as a raw material, as compared with the conventional method.
- 1,3-dialkylcyclobutane-1,2, which is a highly useful isomer having a highly symmetric structure than 3,4-dianhydride hereinafter also referred to as 1,2-DACBDA
- Novel production capable of improving the selectivity of 3,4-tetracarboxylic acid-1,2 3,4-dianhydride (hereinafter also referred to as 1,3-DACBDA) and producing it in high yield It is to provide a method.
- the present invention has the following gist.
- the maleic anhydride compound represented by the following formula (1) is photodimerized in a reaction solvent 100 mass times or more with respect to the maleic anhydride compound. , 2,3,4-cyclobutanetetracarboxylic acid-1,2: 3,4-dianhydride (1,3-DACBDA) derivative.
- R represents an alkyl group having 1 to 20 carbon atoms.
- 2. The production method according to 1 above, wherein R is a methyl group. 3. 3.
- a sensitizer consisting of benzophenone, acetophenone, benzaldehyde, benzophenone substituted with an electron withdrawing group, acetophenone substituted with an electron withdrawing group, benzaldehyde substituted with an electron withdrawing group, or anthraquinone
- 7. The production method according to any one of 1 to 6. 8).
- the electron withdrawing group is at least one selected from the group consisting of a fluoro group, a chloro group, a bromo group, an iodo group, a nitro group, a cyano group, and a trifluoromethyl group. . 9.
- the present invention is a mixture of 1,3-DACBDA and 1,2-DACBDA by photodimerization reaction of a specific maleic anhydride compound, but it has a highly symmetrical structure as compared with the conventional method.
- 1,3-DACBDA which is a useful isomer
- the increase in the conversion rate of the photodimerization reaction of maleic anhydride compound a production method capable of obtaining 1,3, -DACBDA in high yield is provided.
- 1,2,3,4-cyclobutanetetracarboxylic acid-1,2 3,4-dianhydride represented by formula (2) by photodimerization reaction of maleic anhydride compound represented by formula (1)
- the production method of (1,3-DACBDA) is represented by the following reaction scheme.
- R represents an alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
- the alkyl group having 1 to 20 carbon atoms may be either a linear or branched saturated alkyl group or a linear or branched unsaturated alkyl group. Specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl- n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n- Saturated alkyl groups such as butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, n-heptyl, n-octyl, n-nonyl, n-decyl
- maleic anhydride compound represented by the formula (1) examples include citraconic anhydride, 2-ethyl maleic anhydride, 2-isopropyl maleic anhydride, 2-n-butyl maleic anhydride, 2-t-butyl anhydride.
- citraconic anhydride 2-ethylmaleic anhydride, 2-isopropylmaleic anhydride, 2-n-butylmaleic anhydride, 2-t-butylmaleic anhydride, 2 -N-pentylmaleic anhydride, 2-n-hexylmaleic anhydride, 2-n-heptylmaleic anhydride, 2-n-octylmaleic anhydride, 2-n-nonylmaleic anhydride, 2 -N-decylmaleic anhydride, 2-n-dodecylmaleic anhydride and the like are preferable, citraconic anhydride, 2-ethylmaleic anhydride, 2-isopropylmaleic anhydride, 2-n-butylmaleic anhydride, 2-t-butylmaleic anhydride, 2-n-pentylmaleic anhydride, or 2-n-hexylmaleic anhydride is more preferred.
- the reaction solvent an organic solvent generally used in a photochemical reaction is used.
- a solvent that can be employed industrially (1) a carbonyl compound having a high photosensitizing effect, (2) the raw material maleic anhydride compound has high solubility, and the decomposition reaction of the produced CBDA derivative compound is carried out.
- Low solubility of CBDA derivative compound to suppress (3) High solubility of by-product, CBDA derivative compound can be purified only by washing with the same solvent, (4) Not low boiling point that has danger of flammability
- the CBDA derivative compound is a compound having a boiling point of about 50 to 150 ° C. so that it does not remain, (5) safe for the environment, (6) stable during the photoreaction, and (7) inexpensive.
- reaction solvent an organic carboxylic acid ester or anhydride, or a carbonic acid ester is preferred.
- the ester of the organic carboxylic acid is represented by the formula: R 1 COOR 2 (where R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and R 2 has a carbon number. 1 to 4 and more preferably 1 to 3 alkyl groups).
- esters of organic carboxylic acids include methyl formate, ethyl formate, n-propyl formate, i-propyl formate, n-butyl formate, i-butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, i-acetate -Propyl, n-butyl acetate, i-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, i-propyl propionate, n-butyl propionate, i-butyl propionate.
- ethylene glycol diformate ethylene glycol diacetate, ethylene glycol dipropionate and the like can be used.
- anhydride of an organic carboxylic acid the formula: (R 1 CO) 2 O (.
- R 1 is a preferred embodiment be included as defined above) are preferably those represented by.
- Preferred examples thereof are propionic anhydride, butyric anhydride, trifluoroacetic anhydride, or acetic anhydride. Of these, acetic anhydride is preferred because 1,3-DACBDA can be obtained at a higher recovery rate.
- carbonic acid ester a carbonic acid dialkyl ester having 1 to 3 carbon atoms, more preferably 1 or 2, is preferable.
- Preferred examples include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, or a mixture thereof.
- reaction solvents are ethyl formate, methyl acetate, ethyl acetate, i-propyl acetate, i-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, i-propyl propionate, ethylene glycol di- Formate, ethylene glycol diacetate, dimethyl carbonate, or diethyl carbonate, and the most preferred solvent is ethyl acetate or dimethyl carbonate.
- Each of the above solvents may be used alone or in combination of two or more. However, when used alone, there is an advantage that the treatment after the reaction is easy.
- the reaction solvent contains ethyl acetate, dimethyl carbonate, diethyl carbonate, or ethylene glycol diacetate
- the solubility of the raw material maleic anhydride compound is high
- the produced 1,3-DACBDA Since the target compound is precipitated as a crystal during the reaction due to low solubility, side reactions such as reverse reaction from DACBDA to maleic anhydride compound and oligomer formation can be suppressed.
- the amount of the reaction solvent used is important, and by using a very large amount of such a reaction solvent, 1,3-DACBDA in the mixture of 1,3-DACBDA and 1,2-DACBDA to be produced is used. It has been found that the selectivity of increases. That is, the reaction solvent is present in an amount of 100 mass times or more, preferably 100 to 300 mass times, more preferably 150 to 250 mass times with respect to the raw material maleic anhydride compound. The selectivity of 3-DACBDA is increased, and a product having a high content of 1,3-DACBDA can be obtained.
- the wavelength of light is 200 to 400 nm, more preferably 250 to 350 nm, and particularly preferably 280 to 330 nm.
- a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, an electrodeless lamp, a light-emitting diode and the like are preferably used because they give a CBDA derivative compound in a particularly high yield.
- the light source cooling tube from quartz glass to Pyrex (registered trademark) glass as a photochemical reaction device, coloring polymer adhesion to the light source cooling tube and impurities are reduced, and the yield of the CBDA derivative compound is improved.
- the reaction temperature is preferably from ⁇ 20 to 80 ° C., more preferably, since a polymer is by-produced when the temperature is high, and the solubility of the maleic anhydride compound decreases and the production efficiency decreases when the temperature is low. -10 to 50 ° C. In particular, at 0 to 20 ° C., the production of by-products is greatly suppressed, and 1,3-DACBDA can be obtained with high selectivity and yield.
- the reaction time varies depending on the amount of maleic anhydride compound, the type of light source, and the amount of irradiation, but it is carried out until the unreacted maleic anhydride compound reaches 0 to 40%, preferably 0 to 10%. it can. Specifically, the reaction time is usually 1 to 200 hours, preferably 1 to 100 hours, and more preferably 1 to 60 hours. The conversion rate can be easily obtained by analyzing the reaction solution by gas chromatography or the like.
- reaction time becomes longer, the conversion rate of the maleic anhydride compound increases, and the amount of CBDA derivative compound deposited increases, the produced CBDA derivative compound begins to adhere to the outer wall (reaction liquid side) of the light source cooling tube, and the decomposition reaction The coloration of crystals due to the simultaneous use of light and a decrease in light efficiency (yield per unit of power x time) are observed. Therefore, in order to increase the conversion rate of the maleic anhydride compound, it is not preferable to spend a long time in one batch with a decrease in production efficiency in practice.
- reaction can be performed by a batch type or a distribution type, a batch type is used preferably.
- the pressure during the reaction may be normal pressure or increased pressure, preferably normal pressure.
- the production method of the present invention can also be performed by adding a sensitizer.
- the sensitizer include benzophenone, acetophenone, benzaldehyde, anthraquinone, benzophenone substituted with an electron withdrawing group, acetophenone substituted with an electron withdrawing group, and benzaldehyde substituted with an electron withdrawing group.
- Examples of the electron withdrawing group include at least one selected from the group consisting of a fluoro group, a chloro group, a bromo group, an iodo group, a nitro group, a cyano group, and a trifluoromethyl group, such as a fluoro group, a chloro group, A bromo group, a cyano group, a trifluoromethyl group, and the like are preferable.
- Particularly preferred electron withdrawing groups are fluoro groups or chloro groups.
- the number of electron withdrawing groups is 1 to 10, preferably 1 to 5, and particularly preferably 1 to 3.
- substitution position of the electron withdrawing group examples include an ortho position, a meta position, and a para position with respect to the carbonyl group, and an ortho position or a para position is preferable.
- the electron withdrawing groups may be the same or different.
- anthraquinone in which a carbonyl group having an electron withdrawing effect is crosslinked at the ortho position may be used.
- benzophenone and benzophenone substituted with an electron withdrawing group include benzophenone, 2-fluorobenzophenone, 3-fluorobenzophenone, 4-fluorobenzophenone, 2-chlorobenzophenone, 3-chlorobenzophenone, 4-chlorobenzophenone, 2 -Cyanobenzophenone, 3-cyanobenzophenone, 4-cyanobenzophenone, 2-nitrobenzophenone, 3-nitrobenzophenone, 4-nitrobenzophenone, 2,4'-dichlorobenzophenone, 4,4'-difluorobenzophenone, 4,4'- Dichlorobenzophenone, 4,4′-dibromobenzophenone, 3,3′-bis (trifluoromethyl) benzophenone, 3,4′-dinitrobenzophenone, 3,3′-dinitrobenzophenone, , 4'-dinitrobenzophenone, 2-chloro-5-nitrobenzophenone, 1,3-bis (4-fluorobenzoyl)
- acetophenone and acetophenone substituted with an electron withdrawing group include acetophenone, 2′-fluoroacetophenone, 3′-fluoroacetophenone, 4′-fluoroacetophenone, 2′-chloroacetophenone, 3′-chloroacetophenone, 4 ′ '-Chloroacetophenone, 2'-cyanoacetophenone, 3'-cyanoacetophenone, 4'-cyanoacetophenone, 2'-nitroacetophenone, 3'-nitroacetophenone, 4'-nitroacetophenone, 2', 4'-difluoroacetophenone, 3 ′, 4′-difluoroacetophenone, 2 ′, 4′-dichloroacetophenone, 3 ′, 4′-dichloroacetophenone, 4′-chloro-3′-nitroacetophenone, 4′-bromo-3′-nitroacetophenone, 4 - fluor
- 4'-fluoroacetophenone, 4'-chloroacetophenone, 2 ', 4'-difluoroacetophenone, 3', 4'-difluoroacetophenone, 2 ', 4'-dichloroacetophenone, or 3', 4'-dichloro Acetophenone is preferred.
- benzaldehyde substituted with benzaldehyde and an electron withdrawing group examples include benzaldehyde, 2-fluorobenzaldehyde, 3-fluorobenzaldehyde, 4-fluorobenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2-cyanobenzaldehyde.
- 4-fluorobenzaldehyde, 4-chlorobenzaldehyde, 2,4-difluorobenzaldehyde, 3,4-difluorobenzaldehyde, 2,4-dichlorobenzaldehyde, or 3,4-dichlorobenzaldehyde is preferable.
- the amount of the sensitizer to be used is not particularly limited as long as the photoreaction rate is accelerated, but is preferably 0.1 to 20 mol%, more preferably 0.1 to 20 mol% based on the maleic anhydride compound. 5 mol%.
- the above-mentioned benzophenone derivative, acetophenone derivative, or benzaldehyde derivative may be used alone or in combination of one or more of these, but when used alone, Easy to process.
- the target compound can be obtained by photoreaction, filtering the precipitate in the reaction solution, washing the filtered product with an organic solvent, and drying under reduced pressure.
- the amount of the organic solvent used for washing the filtered material may be an amount that can transfer the precipitate remaining in the reaction tank to the filter, but when the amount of the organic solvent is large, the target compound is filtered. The recovery rate decreases.
- the amount of the organic solvent used for washing the filtered product is preferably 0.5 to 10 times by weight, more preferably 1 to 2 times by weight, based on the maleic anhydride compound used in the reaction.
- the organic solvent used for washing the filtered product is not particularly limited, but the use of a solvent having a high product solubility is not preferable because the target compound is transferred to the filtrate and the recovery rate is lowered. For this reason, as an organic solvent used for washing the filtered product, there are methyl formate, ethyl formate, n-propyl formate, i-propyl formate, n-butyl formate, and formic acid i, which are reaction solvents used for the photodimerization reaction.
- ⁇ 1 H NMR analysis conditions Apparatus: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (manufactured by Varian) 400 MHz, Solvent: DMSO-d6, internal standard substance: tetramethylsilane (TMS).
- FT-NMR Fourier transform type superconducting nuclear magnetic resonance apparatus
- Solvent DMSO-d6, internal standard substance: tetramethylsilane (TMS).
- TMS tetramethylsilane
- Melting point analysis conditions Equipment: DSC1 (Metler Toledo), Temperature: 35 ° C-5 ° C / min-400 ° C, Pan: Au (sealed).
- Example 1 Under a nitrogen atmosphere, in a 30 mL Pyrex glass test tube, 0.10 g (0.89 mmol) citraconic anhydride (CA) and 20 g (222 mmol, citraconic anhydride (CA) dimethyl carbonate 200 wt times) was added and dissolved by stirring with a magnetic stirrer. Thereafter, a 100 W high pressure mercury lamp was irradiated for 4 hours while stirring at 10-15 ° C. Thereafter, 2 g of the reaction solution in the reactor was collected, and the solvent was distilled off with an evaporator at 70-80 Torr.
- CA citraconic anhydride
- CA citraconic anhydride
- Examples 2 to 7 and Comparative Examples 1 to 5 A series of operations were carried out in the same manner as in Example 1 using the solvent shown in Table 1 below, whether or not 4,4′-dichlorobenzophenone (DClBP) was added, the amount of citraconic anhydride (CA) charged, and the amount of solvent. It carried out similarly. Further, the production ratio of 1,3-DM-CBDA and 1,2-DM-CBDA (1,3-DM-CBDA: 1,2-DM-CBDA) was calculated in the same manner as in Example 1. The following table shows the solvent, presence / absence of DCIBP addition, CA charge amount, solvent amount, and results.
- DClBP 4,4′-dichlorobenzophenone
- CA citraconic anhydride
- 1,3-DACBDA which is a cyclobutanetetracarboxylic acid derivative obtained in the present invention, is a compound useful as a raw material for polyamic acid, polyimide, and the like.
- the polyimide and the like are used as protective materials and insulating materials for liquid crystal display elements and semiconductors. It is widely used industrially as a resin composition used for electronic materials.
- the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2014-007185 filed on January 17, 2014 are incorporated herein as the disclosure of the specification of the present invention. Is.
Abstract
Description
近年、この分野の発展は目覚ましく、それに対応して、用いられる材料に対しても益々高度な特性が要求される様になっている。即ち、単に耐熱性、耐溶剤性に優れるだけでなく、用途に応じた性能を多数あわせもつことが期待されている。 In general, a polyimide resin is widely used as an electronic material such as a protective material or an insulating material in a liquid crystal display element or a semiconductor because of its high mechanical strength, heat resistance, insulation, solvent resistance, and the like. Recently, the use as an optical communication material such as an optical waveguide material is also expected.
In recent years, the development of this field has been remarkable, and correspondingly, higher and higher properties are required for the materials used. That is, it is expected not only to be excellent in heat resistance and solvent resistance, but also to have a large number of performances depending on the application.
しかし、特許文献3には、1,3-DMCBDAと1,2-DMCBDAとの混合物が得られることは記載されているが、対称性の高い構造を有する有用性の高い異性体である、前者の1,3-DMCBDAを選択的に、かつ高収率で製造することについての記載はない。
However, although Patent Document 3 describes that a mixture of 1,3-DMCBDA and 1,2-DMCBDA can be obtained, the former is a highly useful isomer having a highly symmetric structure. There is no description on the selective and high yield production of 1,3-DMCBDA.
本発明は、下記の要旨を有する。
1.下記式(1)で表される無水マレイン酸化合物を、無水マレイン酸化合物に対して100質量倍以上の反応溶媒中で光二量化反応させることを特徴とする、式(2)で表される1,2,3,4-シクロブタンテトラカルボン酸-1,2:3,4-二無水物(1,3-DACBDA)誘導体の製造方法。
2.Rがメチル基である、上記1に記載の製造方法。
3.無水マレイン酸化合物に対して100~300質量倍の反応溶媒中で光二量化反応させる、上記1又は2に記載の製造方法。
4.反応溶媒の使用量が、無水マレイン酸化合物に対して150~250質量倍の反応溶媒中で光二量化反応させる、上記1又は2に記載の製造方法。
5.反応溶媒が、有機カルボン酸のエステル若しくは無水物、又は炭酸エステルである、上記1~4のいずれかに記載の製造方法。
6.反応溶媒が、酢酸エチル又は炭酸ジメチルである、上記1~5のいずれかに記載の製造方法。
7.ベンゾフェノン、アセトフェノン、ベンズアルデヒド、電子求引性基が置換したベンゾフェノン、電子求引性基が置換したアセトフェノン、電子求引性基が置換したベンズアルデヒド、又はアントラキノンからなる増感剤の存在下に行う、上記1~6のいずれかに記載の製造方法。
8.前記電子求引性基が、フルオロ基、クロロ基、ブロモ基、ヨード基、ニトロ基、シアノ基、及びトリフルオロメチル基からなる群から選ばれる少なくとも1種である、上記7に記載の製造方法。
9.電子求引性基の数が1~5である、上記7又は8に記載の製造方法。
10.無水マレイン酸化合物に対し0.1~20モル%の増感剤を用いる、上記6~9のいずれかに記載の製造方法。
11.反応温度が0~20℃である、上記1~10のいずれかに記載の製造方法。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a novel production method for achieving the above object and completed the present invention.
The present invention has the following gist.
1. The maleic anhydride compound represented by the following formula (1) is photodimerized in a reaction solvent 100 mass times or more with respect to the maleic anhydride compound. , 2,3,4-cyclobutanetetracarboxylic acid-1,2: 3,4-dianhydride (1,3-DACBDA) derivative.
2. 2. The production method according to 1 above, wherein R is a methyl group.
3. 3. The production method according to 1 or 2 above, wherein the photodimerization reaction is performed in a reaction solvent 100 to 300 times by mass with respect to the maleic anhydride compound.
4). 3. The production method according to 1 or 2 above, wherein the reaction solvent is used in a photodimerization reaction in a reaction solvent of 150 to 250 times by mass with respect to the maleic anhydride compound.
5. 5. The production method according to any one of 1 to 4 above, wherein the reaction solvent is an ester or anhydride of an organic carboxylic acid or a carbonate ester.
6). 6. The production method according to any one of 1 to 5 above, wherein the reaction solvent is ethyl acetate or dimethyl carbonate.
7). In the presence of a sensitizer consisting of benzophenone, acetophenone, benzaldehyde, benzophenone substituted with an electron withdrawing group, acetophenone substituted with an electron withdrawing group, benzaldehyde substituted with an electron withdrawing group, or anthraquinone, 7. The production method according to any one of 1 to 6.
8). 8. The production method according to 7 above, wherein the electron withdrawing group is at least one selected from the group consisting of a fluoro group, a chloro group, a bromo group, an iodo group, a nitro group, a cyano group, and a trifluoromethyl group. .
9. 9. The production method according to 7 or 8 above, wherein the number of electron withdrawing groups is 1 to 5.
10. 10. The production method according to any one of 6 to 9 above, wherein 0.1 to 20 mol% of a sensitizer is used with respect to the maleic anhydride compound.
11. 11. The production method according to any one of 1 to 10 above, wherein the reaction temperature is 0 to 20 ° C.
その具体例としては、メチル、エチル、n-プロピル、i-プロピル、n-ブチル、i-ブチル、s-ブチル、t-ブチル、n-ペンチル、1-メチル-n-ブチル、2-メチル-n-ブチル、3-メチル-n-ブチル、1,1-ジメチル-n-プロピル、n-ヘキシル、1-メチル-n-ペンチル、2-メチル-n-ペンチル、1,1-ジメチル-n-ブチル、1-エチル-n-ブチル、1,1,2-トリメチル-n-プロピル、n-ヘプチル、n-オクチル、n-ノニル、n-デシル、n-ドデシル、n-エイコシルなどの飽和アルキル基、1-メチルビニル、2-アリル、1-エチルビニル、2-メチルアリル、2-ブテニル、2-メチル-2-ブテニル、3-メチル-2-ブテニル、3-メチル-3-ブテニル、2-ヘキセニル、4-メチル-3-ペンテニル、4-メチル-4-ペンテニル、2,3-ジメチル-2-ブテニル、1-エチル-2-ペンテニル、3-ドデセニル、プロパルギル、3-ブチニル、3-メチル-2-プロピニル、9-デシニル等の不飽和アルキル基が挙げられる。
なお、nはノルマルを、iはイソを、sはセカンダリーを、tはターシャリーを、それぞれ表す。 The alkyl group having 1 to 20 carbon atoms may be either a linear or branched saturated alkyl group or a linear or branched unsaturated alkyl group.
Specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl- n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n- Saturated alkyl groups such as butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-eicosyl 1-methylvinyl, 2-allyl, 1-ethylvinyl, 2-methylallyl, 2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 2-hexenyl, 4 Methyl-3-pentenyl, 4-methyl-4-pentenyl, 2,3-dimethyl-2-butenyl, 1-ethyl-2-pentenyl, 3-dodecenyl, propargyl, 3-butynyl, 3-methyl-2-propynyl, And unsaturated alkyl groups such as 9-decynyl.
Note that n represents normal, i represents iso, s represents secondary, and t represents tertiary.
有機カルボン酸のエステルの好ましい例としては、ギ酸メチル、ギ酸エチル、ギ酸n-プロピル、ギ酸i-プロピル、ギ酸n-ブチル、ギ酸i-ブチル、酢酸メチル、酢酸エチル、酢酸n-プロピル、酢酸i-プロピル、酢酸n-ブチル、酢酸i-ブチル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸n-プロピル、プロピオン酸i-プロピル、プロピオン酸n-ブチル、プロピオン酸i-ブチルが挙げられる。更に、エチレングリコールジホルメート、エチレングリコールジアセテート、エチレングリコールジプロピオネートなども使用できる。
また、有機カルボン酸の無水物としては、式:(R1CO)2O(但し、R1は、好ましい態様も含めて上記と同義である。)で表されるものが好ましい。その好ましい具体例は、無水プロピオン酸、酪酸無水物、無水トリフルオロ酢酸、又は無水酢酸である。なかでも、より高回収率で1,3-DACBDAが得られる点から無水酢酸が好ましい。 The ester of the organic carboxylic acid is represented by the formula: R 1 COOR 2 (where R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, and R 2 has a carbon number. 1 to 4 and more preferably 1 to 3 alkyl groups).
Preferred examples of esters of organic carboxylic acids include methyl formate, ethyl formate, n-propyl formate, i-propyl formate, n-butyl formate, i-butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, i-acetate -Propyl, n-butyl acetate, i-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, i-propyl propionate, n-butyl propionate, i-butyl propionate. Furthermore, ethylene glycol diformate, ethylene glycol diacetate, ethylene glycol dipropionate and the like can be used.
As the anhydride of an organic carboxylic acid, the formula: (R 1 CO) 2 O (. However, R 1 is a preferred embodiment be included as defined above) are preferably those represented by. Preferred examples thereof are propionic anhydride, butyric anhydride, trifluoroacetic anhydride, or acetic anhydride. Of these, acetic anhydride is preferred because 1,3-DACBDA can be obtained at a higher recovery rate.
上記溶媒は、それぞれの1種単独で、又は2種以上を併用してもよいが、単独で使用した場合は、反応後の処理のしやすい利点がある。
本発明において、反応溶媒が、酢酸エチル、炭酸ジメチル、炭酸ジエチル、又はエチレングリコールジアセテートを含有する場合、原料の無水マレイン酸化合物の溶解度が高いにも拘わらず、生成した1,3-DACBDAの溶解度が低く、目的化合物が結晶として反応中に析出するため、DACBDAからの無水マレイン酸化合物への逆反応やオリゴマー生成等の副反応を抑制することができる。 Among them, preferred reaction solvents are ethyl formate, methyl acetate, ethyl acetate, i-propyl acetate, i-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, i-propyl propionate, ethylene glycol di- Formate, ethylene glycol diacetate, dimethyl carbonate, or diethyl carbonate, and the most preferred solvent is ethyl acetate or dimethyl carbonate.
Each of the above solvents may be used alone or in combination of two or more. However, when used alone, there is an advantage that the treatment after the reaction is easy.
In the present invention, when the reaction solvent contains ethyl acetate, dimethyl carbonate, diethyl carbonate, or ethylene glycol diacetate, although the solubility of the raw material maleic anhydride compound is high, the produced 1,3-DACBDA Since the target compound is precipitated as a crystal during the reaction due to low solubility, side reactions such as reverse reaction from DACBDA to maleic anhydride compound and oligomer formation can be suppressed.
更に、光化学反応装置として、光源冷却管を石英ガラスからパイレックス(登録商標)ガラスに変えることにより、光源冷却管への着色ポリマー付着や不純物が減少し、CBDA誘導体化合物の収率改善が見られる。
反応温度は、高温になると重合物が副生し、又低温になると無水マレイン酸化合物の溶解度が低下し、生産効率が減少することから、-20~80℃で行うことが好ましく、更に好ましくは-10~50℃である。特に0~20℃では、副生物の生成が大幅に抑制され、高い選択率及び収率で1,3-DACBDAが得られる。 In the photoreaction of the present invention, the wavelength of light is 200 to 400 nm, more preferably 250 to 350 nm, and particularly preferably 280 to 330 nm. As the light source, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, an electrodeless lamp, a light-emitting diode and the like are preferably used because they give a CBDA derivative compound in a particularly high yield.
Further, by changing the light source cooling tube from quartz glass to Pyrex (registered trademark) glass as a photochemical reaction device, coloring polymer adhesion to the light source cooling tube and impurities are reduced, and the yield of the CBDA derivative compound is improved.
The reaction temperature is preferably from −20 to 80 ° C., more preferably, since a polymer is by-produced when the temperature is high, and the solubility of the maleic anhydride compound decreases and the production efficiency decreases when the temperature is low. -10 to 50 ° C. In particular, at 0 to 20 ° C., the production of by-products is greatly suppressed, and 1,3-DACBDA can be obtained with high selectivity and yield.
反応時間は、具体的には、通常、1~200時間、好ましくは1~100時間、さらに好ましくは、1~60時間である。
なお、転化率はガスクロマトグラフィーなどで反応液を分析することにより、容易に求めることができる。 The reaction time varies depending on the amount of maleic anhydride compound, the type of light source, and the amount of irradiation, but it is carried out until the unreacted maleic anhydride compound reaches 0 to 40%, preferably 0 to 10%. it can.
Specifically, the reaction time is usually 1 to 200 hours, preferably 1 to 100 hours, and more preferably 1 to 60 hours.
The conversion rate can be easily obtained by analyzing the reaction solution by gas chromatography or the like.
なお、反応は、バッチ式又は流通式で行うことができるが、バッチ式が好ましく用いられる。また、反応時の圧力は、常圧でも加圧でもよく、好ましくは、常圧である。 When the reaction time becomes longer, the conversion rate of the maleic anhydride compound increases, and the amount of CBDA derivative compound deposited increases, the produced CBDA derivative compound begins to adhere to the outer wall (reaction liquid side) of the light source cooling tube, and the decomposition reaction The coloration of crystals due to the simultaneous use of light and a decrease in light efficiency (yield per unit of power x time) are observed. Therefore, in order to increase the conversion rate of the maleic anhydride compound, it is not preferable to spend a long time in one batch with a decrease in production efficiency in practice.
In addition, although reaction can be performed by a batch type or a distribution type, a batch type is used preferably. Further, the pressure during the reaction may be normal pressure or increased pressure, preferably normal pressure.
電子求引性基の数としては、1~10個であるが、1~5個が好ましく、1~3個が特に好ましい。 Examples of the electron withdrawing group include at least one selected from the group consisting of a fluoro group, a chloro group, a bromo group, an iodo group, a nitro group, a cyano group, and a trifluoromethyl group, such as a fluoro group, a chloro group, A bromo group, a cyano group, a trifluoromethyl group, and the like are preferable. Particularly preferred electron withdrawing groups are fluoro groups or chloro groups.
The number of electron withdrawing groups is 1 to 10, preferably 1 to 5, and particularly preferably 1 to 3.
電子求引性基の数が2以上の場合は、電子求引性基は同一でも、それぞれ異なるものであってもよい。また、電子求引性の効果があるカルボニル基がオルト位で架橋するアントラキノンでもよい。 Examples of the substitution position of the electron withdrawing group include an ortho position, a meta position, and a para position with respect to the carbonyl group, and an ortho position or a para position is preferable.
When the number of electron withdrawing groups is 2 or more, the electron withdrawing groups may be the same or different. Further, anthraquinone in which a carbonyl group having an electron withdrawing effect is crosslinked at the ortho position may be used.
増感剤は、上記のベンゾフェノン誘導体、アセトフェノン誘導体、又はベンズアルデヒド誘導体をそれぞれ単独で、あるいは、これらの1種以上を共存させて使用してもよいが、単独で使用した場合には、反応後の処理のし易い。 The amount of the sensitizer to be used is not particularly limited as long as the photoreaction rate is accelerated, but is preferably 0.1 to 20 mol%, more preferably 0.1 to 20 mol% based on the maleic anhydride compound. 5 mol%.
As the sensitizer, the above-mentioned benzophenone derivative, acetophenone derivative, or benzaldehyde derivative may be used alone or in combination of one or more of these, but when used alone, Easy to process.
<GC分析条件>
装置 :GC-2010 Plus(SHIMADZU社製)、
カラム :DB-1(ジーエルサイエンス社製)直径0.25 mm×長さ30 m、膜厚0.25 um、
キャリアガス:He 、検出器:FID 、試料注入量:1 um 、注入口温度:160℃ 、検出器温度:220℃ 、カラム温度:70℃(20min)-40℃/min-220℃(15min) 、スプリット比:1:50 、内部標準物質:乳酸ブチル。
<1H NMR分析条件>
装置 :フーリエ変感型超伝導核磁気共鳴装置(FT-NMR)INOVA-400(Varian社製) 400 MHz、
溶媒:DMSO-d6 、内標準物質:テトラメチルシラン(TMS)。
<融点分析条件>
装置 :DSC1(メトラー・トレド社製)、
温度:35℃-5℃/min-400℃ 、パン:Au(密閉)。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The analytical methods used in the examples are as follows.
<GC analysis conditions>
Equipment: GC-2010 Plus (manufactured by SHIMADZU),
Column: DB-1 (manufactured by GL Sciences) Diameter 0.25 mm x length 30 m, film thickness 0.25 um,
Carrier gas: He, detector: FID, sample injection amount: 1 um, inlet temperature: 160 ° C, detector temperature: 220 ° C, column temperature: 70 ° C (20min)-40 ° C / min-220 ° C (15min) , Split ratio: 1:50, internal standard: butyl lactate.
<1 H NMR analysis conditions>
Apparatus: Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) INOVA-400 (manufactured by Varian) 400 MHz,
Solvent: DMSO-d6, internal standard substance: tetramethylsilane (TMS).
<Melting point analysis conditions>
Equipment: DSC1 (Metler Toledo),
Temperature: 35 ° C-5 ° C / min-400 ° C, Pan: Au (sealed).
1H NMR ( DMSO-d6, δ ppm ) ( 1,3-DM-CBDA ): 1.38 ( s, 6H ), 3.89 ( s, 2H ).
1H NMR ( DMSO-d6, δ ppm ) ( 1,2-DM-CBDA ): 1.37 ( s, 6H ), 3.72 ( s, 2H ).
mp. ( 1,3-DM-CBDA ):316-317℃ Example 1
1 H NMR (DMSO-d6, δ ppm) (1,3-DM-CBDA): 1.38 (s, 6H), 3.89 (s, 2H).
1 H NMR (DMSO-d6, δ ppm) (1,2-DM-CBDA): 1.37 (s, 6H), 3.72 (s, 2H).
mp. (1,3-DM-CBDA): 316-317 ° C
以下の表1に示す溶媒、4,4‘-ジクロロベンゾフェノン(DClBP)の添加の有無、シトラコン酸無水物(CA)の仕込量、及び溶媒量を使用して、一連の操作は実施例1と同様に実施した。また、実施例1と同様の方法で、1,3-DM-CBDAと1,2-DM-CBDAの生成比(1,3-DM-CBDA:1,2-DM-CBDA)を算出した。
溶媒、DClBP添加の有無、CA仕込量、溶媒量、及び結果を以下の表に示す。また、ここで得られた反応液の1,3-DM-CBDAと1,2-DM-CBDAの生成比を算出し、実施例1で得られた結果と併せて表に示す。なお、表1中、Neatは無溶媒で行ったことを表す。また、DClBPは、シトラコン酸無水物に対して0.1~10モル%を使用した。 Examples 2 to 7 and Comparative Examples 1 to 5
A series of operations were carried out in the same manner as in Example 1 using the solvent shown in Table 1 below, whether or not 4,4′-dichlorobenzophenone (DClBP) was added, the amount of citraconic anhydride (CA) charged, and the amount of solvent. It carried out similarly. Further, the production ratio of 1,3-DM-CBDA and 1,2-DM-CBDA (1,3-DM-CBDA: 1,2-DM-CBDA) was calculated in the same manner as in Example 1.
The following table shows the solvent, presence / absence of DCIBP addition, CA charge amount, solvent amount, and results. In addition, the production ratio of 1,3-DM-CBDA and 1,2-DM-CBDA in the reaction solution obtained here was calculated and shown in the table together with the results obtained in Example 1. In Table 1, “Neat” means that the reaction was performed without a solvent. Further, DCIBP was used in an amount of 0.1 to 10 mol% with respect to citraconic anhydride.
なお、2014年1月17日に出願された日本特許出願2014-007185号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 1,3-DACBDA, which is a cyclobutanetetracarboxylic acid derivative obtained in the present invention, is a compound useful as a raw material for polyamic acid, polyimide, and the like. The polyimide and the like are used as protective materials and insulating materials for liquid crystal display elements and semiconductors. It is widely used industrially as a resin composition used for electronic materials.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2014-007185 filed on January 17, 2014 are incorporated herein as the disclosure of the specification of the present invention. Is.
Claims (11)
- 下記式(1)で表される無水マレイン酸化合物を、無水マレイン酸化合物に対して100質量倍以上の反応溶媒中で光二量化反応させることを特徴とする、式(2)で表される1,2,3,4-シクロブタンテトラカルボン酸-1,2:3,4-二無水物誘導体の製造方法。
- Rがメチル基である、請求項1に記載の製造方法。 The production method according to claim 1, wherein R is a methyl group.
- 無水マレイン酸化合物に対して100~300質量倍の反応溶媒中で光二量化反応させる、請求項1又は2に記載の製造方法。 The production method according to claim 1 or 2, wherein the photodimerization reaction is carried out in a reaction solvent 100 to 300 times by mass with respect to the maleic anhydride compound.
- 反応溶媒の使用量が、無水マレイン酸化合物に対して150~250質量倍の反応溶媒中で光二量化反応させる、請求項1又は2に記載の製造方法。 The production method according to claim 1 or 2, wherein the reaction solvent is used in a photodimerization reaction in a reaction solvent of 150 to 250 times by mass with respect to the maleic anhydride compound.
- 反応溶媒が、有機カルボン酸のエステル若しくは無水物、又は炭酸エステルである、請求項1~4のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 4, wherein the reaction solvent is an ester or anhydride of an organic carboxylic acid or a carbonate ester.
- 反応溶媒が、酢酸エチル又は炭酸ジメチルである、請求項1~5のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 5, wherein the reaction solvent is ethyl acetate or dimethyl carbonate.
- ベンゾフェノン、アセトフェノン、ベンズアルデヒド、電子求引性基が置換したベンゾフェノン、電子求引性基が置換したアセトフェノン、電子求引性基が置換したベンズアルデヒド、又はアントラキノンからなる増感剤の存在下に行う、請求項1~6のいずれかに記載の製造方法。 In the presence of a sensitizer comprising benzophenone, acetophenone, benzaldehyde, benzophenone substituted with an electron withdrawing group, acetophenone substituted with an electron withdrawing group, benzaldehyde substituted with an electron withdrawing group, or anthraquinone Item 7. The production method according to any one of Items 1 to 6.
- 前記電子求引性基が、フルオロ基、クロロ基、ブロモ基、ヨード基、ニトロ基、シアノ基、及びトリフルオロメチル基からなる群から選ばれる少なくとも1種である、請求項7に記載の製造方法。 The production according to claim 7, wherein the electron withdrawing group is at least one selected from the group consisting of a fluoro group, a chloro group, a bromo group, an iodo group, a nitro group, a cyano group, and a trifluoromethyl group. Method.
- 電子求引性基の数が1~5である、請求項7又は8に記載の製造方法。 The production method according to claim 7 or 8, wherein the number of electron withdrawing groups is 1 to 5.
- 無水マレイン酸化合物に対し0.1~20モル%の増感剤を用いる、請求項7~9のいずれかに記載の製造方法。 The production method according to any one of claims 7 to 9, wherein a sensitizer is used in an amount of 0.1 to 20 mol% based on the maleic anhydride compound.
- 反応温度が0~20℃である、請求項1~10のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 10, wherein the reaction temperature is 0 to 20 ° C.
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KR20210134078A (en) * | 2014-01-17 | 2021-11-08 | 닛산 가가쿠 가부시키가이샤 | Method for producing cyclobutane tetracarboxylic acid derivative |
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JP2006328027A (en) * | 2005-05-30 | 2006-12-07 | Nof Corp | Method for producing cyclobutanetetracarboxylic acid dianhydrides |
JP2006347931A (en) * | 2005-06-15 | 2006-12-28 | Nissan Chem Ind Ltd | Dialkylcyclobutanoic acid dianhydride and method for producing the same |
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KR102653978B1 (en) | 2024-04-02 |
KR20210100756A (en) | 2021-08-17 |
JPWO2015108167A1 (en) | 2017-03-23 |
CN105916867A (en) | 2016-08-31 |
KR20160108335A (en) | 2016-09-19 |
TWI650304B (en) | 2019-02-11 |
TW201542498A (en) | 2015-11-16 |
JP6565686B2 (en) | 2019-08-28 |
CN110590798A (en) | 2019-12-20 |
KR20220063315A (en) | 2022-05-17 |
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