WO2024095928A1 - エポキシ化合物製品 - Google Patents

エポキシ化合物製品 Download PDF

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Publication number
WO2024095928A1
WO2024095928A1 PCT/JP2023/038956 JP2023038956W WO2024095928A1 WO 2024095928 A1 WO2024095928 A1 WO 2024095928A1 JP 2023038956 W JP2023038956 W JP 2023038956W WO 2024095928 A1 WO2024095928 A1 WO 2024095928A1
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Prior art keywords
compound represented
product
mass
epoxy
formula
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English (en)
French (fr)
Japanese (ja)
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真理子 岡
洋登 竹中
弘世 鈴木
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Daicel Corp
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Daicel Corp
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Priority to CN202380076792.8A priority Critical patent/CN120153006A/zh
Priority to JP2024554479A priority patent/JPWO2024095928A1/ja
Priority to EP23885684.3A priority patent/EP4613789A1/en
Priority to KR1020257017467A priority patent/KR20250100681A/ko
Publication of WO2024095928A1 publication Critical patent/WO2024095928A1/ja
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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
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/025—Polycondensates containing more than one epoxy group per molecule characterised by the purification methods used
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
    • C07D303/44—Esterified with oxirane-containing hydroxy compounds
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/223—Di-epoxy compounds together with monoepoxy compounds
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/226—Mixtures of di-epoxy compounds
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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

Definitions

  • alicyclic epoxy compounds with two or more epoxy groups are used as raw materials for sealing materials, coating agents, adhesives, inks, sealants, etc.
  • alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl (3',4'-epoxy) cyclohexane carboxylate and 3,4-epoxy-6-methyl-cyclohexylmethyl (3',4'-epoxy-6'-methyl) cyclohexane carboxylate (see Patent Documents 1 and 2).
  • the objective of this disclosure is therefore to provide an epoxy compound product that is resistant to cure shrinkage, is capable of forming a cured product that is excellent in heat resistance and transparency, and has a low viscosity.
  • the present disclosure relates to a compound represented by the following formula (1), the purity of which is 90% or more: Provided is an epoxy compound product in which the total content of a compound represented by the following formula (a), a compound represented by the following formula (b), a compound represented by the following formula (c), and a compound represented by the following formula (d) is 10 mass % or less.
  • the above epoxy compound product preferably has a Hazen color number of 105 or less.
  • the epoxy compound product may contain a total content of the compound represented by the following formula (a), the compound represented by the following formula (b), the compound represented by the following formula (c), and the compound represented by the following formula (d) of 0.1 mass% or more.
  • the present disclosure also provides a curable composition comprising the above-mentioned epoxy compound product and a curing agent and/or a curing catalyst.
  • the present disclosure also provides a curable composition comprising the above epoxy compound product and other epoxy compounds and/or oxetane compounds.
  • the curable composition is preferably an adhesive, a sealant, or a coating agent.
  • the present disclosure also provides a cured product of the above curable composition.
  • the present disclosure also relates to an optical member comprising the above-mentioned cured product.
  • the present disclosure also provides a method for producing the epoxy compound product, which produces the epoxy compound product through the following epoxidation step, the following low-boiling point removal step, and the following high-boiling point removal step.
  • Epoxidation step A step of reacting 6-methyl-3-cyclohexenylmethyl (6'-methyl-3'-cyclohexenyl) carboxylate with an organic peracid to obtain a reaction product.
  • Low-boiling point removal step A step of removing low-boiling points from the reaction product.
  • High-boiling point removal step A step of removing high-boiling points from the reaction product by thin-film evaporation.
  • the epoxy compound products disclosed herein are less susceptible to cure shrinkage, have excellent heat resistance and transparency, and have low viscosity.
  • the purity of the compound represented by formula (1) is preferably 91% or more, more preferably 94% or more, and even more preferably 96% or more, in that a cured product having a lower viscosity, excellent transparency, and particularly excellent heat resistance and transparency can be obtained.
  • the epoxy compound product contains a compound represented by the following formula (a), a compound represented by the following formula (b), a compound represented by the following formula (c), and a compound represented by the following formula (d) in a total content of 10 mass% or less, preferably 9 mass% or less, more preferably 6 mass% or less, and even more preferably 4 mass% or less, relative to the total amount (100 mass%) of the epoxy compound product.
  • the total content may be, for example, 0.1 mass% or more, 0.2 mass% or more, or 1 mass% or more.
  • the epoxy compound product has a lower viscosity, is excellent in transparency, and can give a cured product with particularly excellent heat resistance and transparency.
  • the content (total content) of impurities, particularly compounds having a molecular weight of 100 or less and compounds having a molecular weight of 290 or more (impurities including compounds represented by the above formulas (a) to (d)) is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 2% by mass or less, relative to the total amount (100% by mass) of the epoxy compound product.
  • the content may be 0.1% by mass or more.
  • the content of the compound represented by the formula (a) is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.
  • the content of the compound represented by the formula (a) may be 0.1% by mass or more.
  • the content of the compound represented by the formula (b) is preferably 1% by mass or less, more preferably 0.4% by mass or less, and even more preferably 0.2% by mass or less.
  • the content of the compound represented by the formula (b) may be 0.0001% by mass or more.
  • the content of the compound represented by the formula (c) is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.
  • the content of the compound represented by the formula (c) may be 0.1% by mass or more.
  • the content of the compound represented by the formula (d) is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.
  • the content of the compound represented by the formula (d) may be 0.1% by mass or more.
  • the purity of the compound represented by formula (1) in the epoxy compound product can be calculated as the ratio of the peak area by gel permeation chromatography (GPC). When the peak shoulders overlap, the peak area is divided by a perpendicular line to the baseline that passes through the valley of the peak.
  • the content ratios of the compound represented by the above formula (a), the compound represented by the above formula (b), the compound represented by the above formula (c), the compound represented by the above formula (d), the compound having a molecular weight of 100 or less, and the compound having a molecular weight of 290 or more can each be calculated as the peak area ratios by gas chromatography and mass spectrometry (GC-MS).
  • the Hazen color number (APHA) of the above epoxy compound product is preferably 105 or less, more preferably 103 or less, even more preferably 100 or less, even more preferably 50 or less, and particularly preferably 15 or less.
  • the viscosity of the epoxy compound product at 25°C is preferably 1300 mPa ⁇ s or less, more preferably 1200 mPa ⁇ s or less, even more preferably 1000 mPa ⁇ s or less, and particularly preferably 900 mPa ⁇ s or less.
  • the viscosity may be, for example, 50 mPa ⁇ s or more, 100 mPa ⁇ s or more, or 300 mPa ⁇ s or more.
  • the viscosity is measured using a digital viscometer (model number "DVU-E II type", manufactured by Tokimec Co., Ltd.) under the following conditions: rotor: standard 1°34' x R24, temperature: 25°C, rotation speed: 0.5 to 10 rpm.
  • Epoxidation step A step of obtaining a reaction product by reacting 6-methyl-3-cyclohexenylmethyl (6'-methyl-3'-cyclohexenyl) carboxylate with an organic peracid.
  • Low-boiling step A step of removing low-boiling components from the reaction product.
  • High-boiling step A step of removing high-boiling components from the reaction product by thin-film evaporation.
  • a step of washing the reaction product with water to remove the organic peracid used in the reaction and its decomposition products may be provided.
  • a step of subjecting crotonaldehyde and acrolein to a Diels-Alder reaction to obtain 6-methyl-1,3-cyclohexene-1-carboxaldehyde Diels-Alder reaction step
  • a step of subjecting 6-methyl-1,3-cyclohexene-1-carboxaldehyde to a Tishchenko reaction to obtain 6-methyl-3-cyclohexenylmethyl (6'-methyl-3'-cyclohexenyl) carboxylate (Tishchenko reaction step)
  • Diels-Alder reaction step a step of subjecting 6-methyl-1,3-cyclohexene-1-carboxaldehyde to a Tishchenko reaction to obtain 6-methyl-3-cyclohexenylmethyl (6'-methyl-3'-cyclohexenyl) carboxylate
  • Epoxidation Step is a step of obtaining a reaction product by reacting 6-methyl-3-cyclohexenylmethyl(6'-methyl-3'-cyclohexenyl)carboxylate represented by the following formula (A) with an organic peracid. In this step, a reaction product containing the compound represented by the above formula (1) is obtained.
  • organic peracids examples include performic acid, peracetic acid, perpropionic acid, m-chloroperbenzoic acid, trifluoroperacetic acid, and perbenzoic acid. Only one type of the organic peracids may be used, or two or more types may be used.
  • the amount of organic peracid used is, for example, 0.5 to 3 moles per mole of 6-methyl-3-cyclohexenylmethyl (6'-methyl-3'-cyclohexenyl) carboxylate.
  • the epoxidation reaction can be carried out in the presence of a solvent.
  • the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, isopropylbenzene, diethylbenzene, and p-cymene; alicyclic hydrocarbons such as cyclohexane and decalin; aliphatic hydrocarbons such as n-hexane, heptane, octane, nonane, and decane; alcohols such as cyclohexanol, hexanol, heptanol, octanol, nonanol, and furfuryl alcohol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; esters such as ethyl acetate, n-amyl acetate, cyclohexyl acetate, isoamy
  • the amount of solvent used is, for example, about 0.2 to 10 times the mass of 6-methyl-3-cyclohexenylmethyl (6'-methyl-3'-cyclohexenyl) carboxylate.
  • stabilizers for organic peracids e.g., ammonium hydrogen phosphate, potassium pyrophosphate, 2-ethylhexyl tripolyphosphate, etc.
  • polymerization inhibitors e.g., hydroquinone, piperidine, ethanolamine, phenothiazine, etc.
  • the reaction temperature for the epoxidation reaction is, for example, 0 to 70°C.
  • the reaction atmosphere is not particularly limited as long as it does not inhibit the reaction, and may be, for example, an air atmosphere, a nitrogen atmosphere, an argon atmosphere, etc.
  • the water-washing step is a step of removing, by washing with water, organic peracids and organic acids which are decomposition products thereof, contained in the reaction product obtained through the epoxidation step.
  • the amount of water used is, for example, about 0.1 to 3 times (v/v) the reaction product.
  • an equilibrium extractor such as a mixer-settler type, an extraction tower, or a centrifugal extractor can be used.
  • the low-boiling point removal step is a step of distilling off components (e.g., solvent, water, etc.) contained in the reaction product and having a boiling point lower than that of the compound represented by formula (1). By subjecting the reaction product to this step, the content of compounds having a molecular weight of 100 or less that are mixed into the epoxy compound product can be reduced to an extremely low level.
  • components e.g., solvent, water, etc.
  • a thin film evaporator or distillation column can be used for distillation.
  • Distillation is preferably carried out under conditions of a heating temperature in the range of 50 to 200°C and a pressure in the range of 1 to 760 torr. Distillation can also be carried out in two stages by changing the pressure and temperature.
  • a polymerization inhibitor in order to suppress the ring-opening polymerization reaction of the compound represented by formula (1) above.
  • the amount of polymerization inhibitor added varies slightly depending on the type and distillation temperature, but it is preferable that the amount is in the range of, for example, 1 to 10,000 ppm by mass (particularly, 10 to 2,000 ppm by mass) relative to the reaction product.
  • the high-boiling component removal step is a step of distilling off components (e.g., solvent, water, etc.) contained in the reaction product and having a higher boiling point than the compound represented by formula (1) by thin-film evaporation.
  • the high-boiling component removal step is a step of evaporating and distilling off the compound represented by formula (1) from a mixture of the compound represented by formula (1) and components having a higher boiling point than the compound represented by formula (1), which is the bottoms obtained after the low-boiling component removal step.
  • the compound represented by formula (a) is inhibited from being produced as a by-product by reaction of the organic acid which is a decomposition product of the organic peracid with the by-product compound represented by formula (a) to produce a compound represented by formula (c) or a compound represented by formula (d).
  • the compound represented by formula (b) is inhibited from being produced as a by-product by reaction of the organic acid which is a decomposition product of the organic peracid with the remaining unreacted 6-methyl-3-cyclohexenylmethyl(6'-methyl-3'-cyclohexenyl)carboxylate.
  • distillation tower for example, a packed tower or a plate tower can be used.
  • the actual number of stages of the distillation tower is, for example, 14 or more stages, and is preferably 14 to 100 stages, and particularly preferably 14 to 50 stages, in that it is possible to suppress the contamination of the compounds represented by formulas (a) to (d) and further improve the purity of the product.
  • a thin film evaporator can be used for distillation.
  • the distillation is preferably performed under conditions of a heating temperature of 250°C or less (preferably 230°C or less) and a pressure of 3 torr or more (preferably 0.7 torr or less) in order to prevent the compound represented by formula (1) from decomposing and increasing the degree of coloration, and the epoxy group of the compound represented by formula (1) from ring-opening polymerization and gelling.
  • the distillation temperature is preferably 170°C or more, more preferably 180°C or more.
  • the pressure is preferably 0.01 torr or more from the viewpoint of increasing the purity of the epoxy compound product, and may be 0.02 torr or more.
  • the pressure is preferably 0.5 Torr or less, more preferably 0.2 Torr or less, even more preferably 0.16 Torr or less, even more preferably 0.1 Torr or less, and particularly preferably 0.04 Torr or less, in order to further prevent the by-production of the compounds represented by formulas (a) to (d).
  • the wiper rotation speed is preferably 100 to 800 rpm, and more preferably 200 to 600 rpm. If the wiper rotation speed is too high, the energy cost tends to be high, and conversely, if it is too low, the compounds represented by formulas (a) to (d) tend to be more likely to be mixed into the product.
  • the compound represented by the above formula (1) has a higher boiling point than 3,4-epoxycyclohexylmethyl (3',4'-epoxy) cyclohexane carboxylate, and therefore needs to be distilled at a relatively high temperature. For this reason, in the high boiling component removal step, the reaction that produces the compounds represented by the formulas (a) to (d) is more likely to proceed, and as a result, the purity of the obtained epoxy compound product is likely to decrease.
  • the compound represented by formula (1) can be efficiently volatilized without raising the heating temperature too high, and the reaction that produces the compounds represented by formulas (a) to (d) in the high boiling point removal step can be suppressed, resulting in a high-purity epoxy compound product.
  • the pressure in the high boiling point removal step an even higher purity epoxy compound product can be obtained.
  • the compound represented by the formula (1) is a curable compound, and the above-mentioned epoxy compound product can be used to obtain a curable composition.
  • the above-mentioned curable composition contains the above-mentioned epoxy compound product.
  • the curable composition contains at least the compound represented by formula (1) contained in the epoxy compound product as a curable compound.
  • the curable composition may contain other curable compounds other than the compound represented by formula (1).
  • the other curable compounds may be one type or two or more types.
  • the other curable compounds include, for example, epoxy compounds other than the compound represented by formula (1) above, compounds having one or more oxetane groups in the molecule (sometimes referred to as “oxetane compounds”), and compounds having one or more vinyl ether groups in the molecule (sometimes referred to as “vinyl ether compounds”).
  • the curable composition may contain the other epoxy compounds and/or oxetane compounds as the other compounds.
  • the other epoxy compounds mentioned above are compounds having one or more epoxy groups (oxiranyl groups) in the molecule.
  • the other epoxy compounds mentioned above are preferably compounds having two or more epoxy groups (preferably 2 to 6, more preferably 2 to 4) in the molecule.
  • epoxy compounds mentioned above include alicyclic epoxy compounds, aromatic epoxy compounds, and aliphatic epoxy compounds.
  • the above-mentioned alicyclic epoxy compounds include known or conventional compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, and are not particularly limited.
  • they include (I) compounds having an epoxy group (called an "alicyclic epoxy group") composed of two adjacent carbon atoms and an oxygen atom that constitute an alicyclic ring in the molecule; (II) compounds in which an epoxy group is directly bonded to an alicyclic ring by a single bond; and (III) compounds having an alicyclic ring and a glycidyl ether group in the molecule (glycidyl ether type epoxy compounds).
  • the above-mentioned (I) compound having an alicyclic epoxy group in the molecule includes a compound represented by the following formula (i).
  • Y represents a single bond or a linking group (a divalent group having one or more atoms).
  • the linking group include a divalent hydrocarbon group, an alkenylene group in which some or all of the carbon-carbon double bonds have been epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and groups in which multiple of these are linked together.
  • a substituent such as an alkyl group may be bonded to one or more of the carbon atoms constituting the cyclohexane ring (cyclohexene oxide group) in formula (i).
  • the divalent hydrocarbon group may be a linear or branched alkylene group having 1 to 18 carbon atoms, or a divalent alicyclic hydrocarbon group.
  • Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.
  • Examples of the divalent alicyclic hydrocarbon group may be a divalent cycloalkylene group (including a cycloalkylidene group) such as a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, or a cyclohexylidene group.
  • a divalent cycloalkylene group including a cycloalkylidene group
  • a divalent cycloalkylene group such as a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, or a cyclohexylidene group
  • alkenylene group in the alkenylene group in which some or all of the carbon-carbon double bonds have been epoxidized includes, for example, straight-chain or branched alkenylene groups having 2 to 8 carbon atoms, such as vinylene, propenylene, 1-butenylene, 2-butenylene, butadienylene, pentenylene, hexenylene, heptenylene, and octenylene.
  • the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds have been epoxidized, and more preferably an alkenylene group in which all of the carbon-carbon double bonds have been epoxidized and have 2 to 4 carbon atoms.
  • alicyclic epoxy compound represented by formula (i) above include (3,4,3',4'-diepoxy)bicyclohexyl and compounds represented by formulas (i-1) to (i-9) below.
  • l and m each represent an integer of 1 to 30.
  • R' is an alkylene group having 1 to 8 carbon atoms, and among these, a linear or branched alkylene group having 1 to 3 carbon atoms, such as a methylene group, an ethylene group, a propylene group, or an isopropylene group, is preferred.
  • n1 to n6 each represent an integer of 1 to 30.
  • other examples of the alicyclic epoxy compound represented by the above formula (i) include 2,2-bis(3,4-epoxycyclohexyl)propane, 1,2-bis(3,4-epoxycyclohexan-1-yl)ethane, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexan-1-yl)ethane, and bis(3,4-epoxycyclohexylmethyl)ether.
  • the above-mentioned (I) compound having an alicyclic epoxy group in the molecule includes an epoxy-modified siloxane.
  • the above-mentioned epoxy-modified siloxane includes, for example, a linear or cyclic polyorganosiloxane having a structural unit represented by the following formula (i'):
  • R3 represents a substituent containing a group represented by the following formula (1a) or a substituent containing a group represented by the following formula (1b), and R4 represents an alkyl group or an alkoxy group.
  • R 1a and R 1b are the same or different and each represents a linear or branched alkylene group, such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, or a decamethylene group, which is a linear or branched alkylene group having 1 to 10 carbon atoms.
  • a linear or branched alkylene group such as a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, or a decamethylene group, which is a linear or branched alkylene group having 1 to 10 carbon atoms.
  • the epoxy equivalent of the above epoxy-modified siloxane is, for example, 100 to 400, preferably 150 to 300.
  • epoxy-modified siloxane for example, a commercially available product such as the compound represented by the following formula (i'-1) (product name "KR-470", manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.
  • the above (II) compound having an epoxy group directly bonded to an alicyclic ring via a single bond includes, for example, a compound represented by the following formula (ii).
  • R" is a group (p-valent organic group) obtained by removing p hydroxyl groups (-OH) from the structural formula of p-valent alcohol, and p and n each represent a natural number.
  • p-valent alcohols [R"(OH)p] include polyhydric alcohols (alcohols having 1 to 15 carbon atoms, etc.) such as 2,2-bis(hydroxymethyl)-1-butanol.
  • p is preferably 1 to 6
  • n is preferably 1 to 30.
  • the n in each group in ( ) (in the outer parentheses) may be the same or different.
  • Examples of the above (III) compounds having an alicyclic ring and a glycidyl ether group in the molecule include, for example, glycidyl ethers of alicyclic alcohols (particularly, alicyclic polyhydric alcohols).
  • compounds obtained by hydrogenating bisphenol A type epoxy compounds such as 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane and 2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane (hydrogenated bisphenol A type epoxy compounds); bis[o,o-(2,3-epoxypropoxy)cyclohexyl]methane, bis[o,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[p,p-(2,3-epoxypropoxy)cyclohexyl]methane, bis[3,5-dimethyl-4-( Examples include hydrogenated compounds of bisphenol F type epoxy compounds such as [2,3-epoxypropoxy]cyclohexyl]methane (hydrogenated bisphenol F type epoxy compounds); hydrogenated biphenol type epoxy compounds; hydrogenated phenol novolac type epoxy compounds; hydrogenated cresol novolac type epoxy compounds
  • the aromatic epoxy compound is a compound having one or more aromatic rings (aromatic hydrocarbon rings or aromatic heterocycles) and one or more epoxy groups in the molecule.
  • aromatic epoxy compounds compounds in which a glycidoxy group is bonded to one or more carbon atoms constituting an aromatic ring (particularly an aromatic hydrocarbon ring) having carbon atoms (aromatic glycidyl ether epoxy compounds) are preferred.
  • the above-mentioned aromatic epoxy compounds include, for example, epi-bis-type glycidyl ether type epoxy resins obtained by a condensation reaction between bisphenols [e.g., bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc.] and epihalohydrin; high molecular weight epi-bis-type glycidyl ether type epoxy resins obtained by further addition reaction of these epi-bis-type glycidyl ether type epoxy resins with the above-mentioned bisphenols; phenols [e.g., phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol, etc.]; Novolak alkyl type glycidyl ether type epoxy resins obtained by condensing polyhydric alcohols obtained by condensing polyhydric alcohols [e.g., formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldeh
  • aliphatic epoxy compounds include glycidyl ethers of alcohols not having a q-valent cyclic structure (q is a natural number); glycidyl esters of mono- or polyvalent carboxylic acids [e.g., acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.]; epoxidized products of oils and fats having double bonds, such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; epoxidized products of polyolefins (including polyalkadienes), such as epoxidized polybutadiene, etc.
  • glycidyl esters of mono- or polyvalent carboxylic acids e.g., acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid,
  • Examples of the q-valent alcohols that do not have a cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, and 1-butanol; dihydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; and trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol.
  • the q-valent alcohol may be polyether polyol, polyester polyol, poly
  • oxetane compounds include known or conventional compounds having one or more oxetane rings in the molecule, and are not particularly limited thereto.
  • the vinyl ether compound may be any known or conventional compound having one or more vinyl ether groups in the molecule, and is not particularly limited.
  • the vinyl ether compound include, but are not limited to, 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,6-hexanediol divinyl ether, 1 ,8-octanediol divinyl ether, 1,4-cyclohexane
  • the proportion of the compound represented by the above formula (1) in the total amount (100% by mass) of the curable compounds contained in the curable composition is, for example, 50% by mass or more (e.g., 50 to 100% by mass), preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.
  • the curable composition preferably contains, in addition to the curable compound, one or more selected from the group consisting of a curing agent, a curing accelerator, and a curing catalyst.
  • the curable composition preferably contains a curing agent and/or a curing catalyst.
  • the total content of the curable compound, curing agent and/or curing accelerator in the total amount (100 mass%) of the curable composition is, for example, 60 mass% or more, preferably 70 mass% or more, more preferably 80 mass% or more, even more preferably 90 mass% or more, and particularly preferably 95 mass% or more.
  • the total content of the curable compound and the curing catalyst in the total amount (100% by mass) of the curable composition is, for example, 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
  • the content of compounds other than the curable compound, curing agent, curing accelerator, and curing catalyst relative to the total amount (100 mass%) of the curable composition is, for example, 50 mass% or less, and preferably 40 mass% or less.
  • the curing agent for example, known or commonly used curing agents for epoxy resins such as acid anhydrides (acid anhydride-based curing agents), amines (amine-based curing agents), polyamide resins, imidazoles (imidazole-based curing agents), polymercaptans (polymercaptan-based curing agents), phenols (phenol-based curing agents), polycarboxylic acids, dicyandiamides, organic acid hydrazides, etc.
  • the curing agents may be used alone or in combination of two or more kinds.
  • Examples of the above acid anhydrides include methyltetrahydrophthalic anhydride (4-methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.), methylhexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, etc.), dodecenyl succinic anhydride, methyl end methylene tetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, nadic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, 4-(4-methyl-3-pentenyl)t
  • acid anhydrides that are liquid at 25°C [e.g., methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, methylendmethylenetetrahydrophthalic anhydride, etc.] are preferred.
  • the above amines include, for example, aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, and polypropylenetriamine; menthenediamine, isophoronediamine, bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, N-aminoethylpiperazine, 3,9-bis(3-aminopropyl)-3,4,8 , 10-tetraoxaspiro[5,5]undecane and other alicyclic polyamines; m-phenylenediamine, p-phenylenediamine, tolylene-2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine, 3,5-
  • polyamide resins examples include polyamide resins that have either or both of a primary amino group and a secondary amino group in the molecule.
  • the above imidazoles include, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- Examples include 2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-s-triazine, and 2,4-diamino-6-[2-eth
  • polymercaptans examples include liquid polymercaptan and polysulfide resin.
  • phenols examples include novolac-type phenolic resins, novolac-type cresol resins, p-xylylene-modified phenolic resins, aralkyl resins such as p-xylylene and m-xylylene-modified phenolic resins, terpene-modified phenolic resins, dicyclopentadiene-modified phenolic resins, and triphenolpropane.
  • polycarboxylic acids examples include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and carboxyl group-containing polyesters.
  • acid anhydrides as a curing agent, from the viewpoint of the heat resistance and transparency of the resulting cured product, acid anhydrides (acid anhydride-based curing agents) are preferable, and for example, commercially available products such as "RIKACID MH-700” and “RIKACID MH-700F” (both manufactured by New Japan Chemical Co., Ltd.) and “HN-5500” (manufactured by Hitachi Chemical Co., Ltd.) can be used.
  • the content (mixture amount) of the curing agent is preferably 50 to 200 parts by mass, more preferably 80 to 150 parts by mass, per 100 parts by mass of the total amount of the epoxy compounds contained in the curable composition. More specifically, when an acid anhydride is used as the curing agent, it is preferable to use it in a ratio of 0.5 to 1.5 equivalents per equivalent of epoxy groups in all the epoxy compounds contained in the curable composition.
  • the content of the curing agent is 50 parts by mass or more, curing can be sufficiently advanced, and the toughness of the obtained cured product tends to be improved.
  • the content of the curing agent is 200 parts by mass or less, coloring is further suppressed, and a cured product with excellent hue tends to be obtained.
  • the composition contains a curing agent
  • the composition further contains a curing accelerator.
  • the curing accelerator has an effect of accelerating the reaction rate when a compound having an epoxy group (oxiranyl group) reacts with a curing agent.
  • the above-mentioned curing accelerators include, for example, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU) or a salt thereof (e.g., phenol salt, octylate salt, p-toluenesulfonate salt, formate salt, tetraphenylborate salt, etc.), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) or a salt thereof (e.g., phenol salt, octylate salt, p-toluenesulfonate salt, formate salt, tetraphenylborate salt, etc.); benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol.
  • DBU 1,8-diazabicyclo[5.4.0]undecene-7
  • a salt thereof e.g., phenol salt, octylate salt, p-toluene
  • tertiary amines such as N,N-dimethylcyclohexylamine; imidazoles such as 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole; phosphate esters; phosphines such as triphenylphosphine, tris(dimethoxy)phosphine; phosphonium compounds such as tetraphenylphosphonium tetra(p-tolyl)borate; organic metal salts such as zinc octylate, tin octylate, zinc stearate; metal chelates such as aluminum acetylacetone complex.
  • the above curing accelerators may be used alone or in combination of two or more.
  • curing accelerator for example, commercially available products such as those under the trade names "U-CAT SA 506", “U-CAT SA 102”, “U-CAT 5003", “U-CAT 18X”, and “U-CAT 12XD” (developed products) (all manufactured by San-Apro Co., Ltd.); those under the trade names “TPP-K” and “TPP-MK” (both manufactured by Hokko Chemical Industry Co., Ltd.); and those under the trade name "PX-4ET” (manufactured by Nippon Chemical Industry Co., Ltd.) can be used.
  • the content (mixture amount) of the curing accelerator is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 3 parts by mass, and even more preferably 0.03 to 3 parts by mass, per 100 parts by mass of the curing agent. If the content of the curing accelerator is 0.01 parts by mass or more, a more efficient curing acceleration effect tends to be obtained. On the other hand, if the content of the curing accelerator is 5 parts by mass or less, coloring is further suppressed, and a cured product with excellent hue tends to be obtained.
  • the curable composition may contain a curing catalyst instead of a curing agent.
  • the curing catalyst has the function of initiating and/or accelerating the curing reaction (polymerization reaction) of a cationic curable compound such as the compound represented by the formula (1) above, thereby curing the curable composition.
  • the curing catalyst include cationic polymerization initiators (photocationic polymerization initiators, thermal cationic polymerization initiators, etc.) that generate cationic species by applying light irradiation or heat treatment, and initiate polymerization, Lewis acid-amine complexes, Bronsted acid salts, imidazoles, etc.
  • the curing catalyst may be used alone or in combination of two or more.
  • photocationic polymerization initiator examples include hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, and the like.
  • examples of the photocationic polymerization initiator include sulfonium salts (particularly triarylsulfonium salts) such as triarylsulfonium hexafluorophosphate (e.g., p-phenylthiophenyldiphenylsulfonium hexafluorophosphate) and triarylsulfonium hexafluoroantimonate; iodonium salts such as diaryliodonium hexafluorophosphate, diaryliodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, and iodonium [4-(4-methylphenyl-2-methylpropyl)phenyl]hexafluorophosphate; phosphonium salts such as tetrafluorophosphonium hexafluorophosphate; and
  • photocationic polymerization initiator for example, commercially available products such as “UVACURE1590” (manufactured by Daicel Allnex Co., Ltd.); “CD-1010”, “CD-1011”, and “CD-1012” (all manufactured by Sartomer Corporation, USA); “Irgacure 264” (manufactured by BASF); and “CIT-1682” (manufactured by Nippon Soda Co., Ltd.) can be preferably used.
  • the cationic polymerization initiator may, for example, be an aryl diazonium salt, an aryl iodonium salt, an aryl sulfonium salt, or an allene ion complex.
  • Commercially available products such as “PP-33”, “CP-66”, and “CP-77” (all manufactured by ADEKA CORPORATION); "FC-509” (manufactured by 3M); "UVE1014" (manufactured by G.E.); "San-Aid SI-60L”, “San-Aid SI-80L”, “San-Aid SI-100L”, “San-Aid SI-110L”, and “San-Aid SI-150L” (all manufactured by Sanshin Chemical Industry Co., Ltd.); and "CG-24-61” (manufactured by BASF) are preferably used.
  • Lewis acid-amine complex examples include BF3.n - hexylamine, BF3.monoethylamine , BF3.benzylamine , BF3.diethylamine , BF3.piperidine , BF3.triethylamine , BF3.aniline , BF4.n -hexylamine, BF4.monoethylamine , BF4.benzylamine , BF4.diethylamine , BF4.piperidine, BF4.triethylamine , BF4.aniline, PF5.ethylamine , PF5.isopropylamine, PF5.butylamine , PF5.laurylamine , PF5.benzylamine , and AsF5.laurylamine .
  • Bronsted acid salts examples include aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts, and phosphonium salts.
  • the above imidazoles include, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- Examples include 2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-s-triazine, and 2,4-diamino-6-[2-eth
  • the content (mixture amount) of the curing catalyst is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 4 parts by mass, and even more preferably 0.03 to 3 parts by mass, relative to 100 parts by mass of the cationic curable compound contained in the curable composition.
  • content of the curing catalyst is within the above range, the curing speed of the curable composition increases, and the heat resistance and transparency of the cured product tend to be improved in a balanced manner.
  • the curable composition may contain additives, if necessary, in addition to the above-mentioned components.
  • additives include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin; defoamers, leveling agents, silane coupling agents, surfactants, inorganic fillers, flame retardants, colorants, ion adsorbents, pigments, fluorescent materials, and mold release agents. Only one type of the additives may be used, or two or more types may be used.
  • the curable composition can be prepared by stirring and mixing the above-mentioned components in a heated state as necessary.
  • stirring and mixing known or conventional stirring and mixing means can be used, such as various mixers such as dissolvers and homogenizers, kneaders, roll mills, bead mills, and self-revolving stirrers. After stirring and mixing, the mixture may be degassed under vacuum.
  • the ratio of the compound represented by formula (1) to the total amount (100 mass%) of the compound represented by formula (1), the compound represented by formula (a), the compound represented by formula (b), the compound represented by formula (c), and the compound represented by formula (d) in the curable composition is 90 mass% or more, preferably 91 mass% or more, more preferably 94 mass% or more, and even more preferably 96 mass% or more.
  • the above ratio can be calculated from the peak area ratio obtained by GC-MS.
  • the total proportion of the compound represented by formula (a), the compound represented by formula (b), the compound represented by formula (c), and the compound represented by formula (d) relative to the total amount (100 mass%) of the compound represented by formula (1), the compound represented by formula (a), the compound represented by formula (b), the compound represented by formula (c), and the compound represented by formula (d) is 10 mass% or less, preferably 9 mass% or less, more preferably 6 mass% or less, and even more preferably 4 mass% or less.
  • the above proportion can be calculated from the peak area proportion obtained by GC-MS.
  • the curable composition has fast curing properties, and the curing time (or gel time) at 120°C is, for example, 1100 seconds or less, preferably 1050 seconds or less.
  • the curing time (or gel time) at 80°C is, for example, 5000 seconds or less, preferably 4000 seconds or less, more preferably 3000 seconds or less.
  • the heating temperature (curing temperature) during curing is preferably 45 to 200°C, more preferably 100 to 190°C, and even more preferably 100 to 180°C.
  • the heating time (or curing time) is preferably 30 to 600 minutes, and more preferably 45 to 540 minutes. If the heating temperature or heating time is below the above range, curing will be insufficient, and conversely, if it exceeds the above range, decomposition of the resin components may occur, so neither is preferable.
  • the curing conditions depend on various conditions, but can be appropriately adjusted, for example, by shortening the heating time when the heating temperature is high, or lengthening the heating time when the heating temperature is low.
  • the curable composition can be cured to obtain a cured product having excellent transparency and heat resistance.
  • the above cured product has excellent transparency, and its light transmittance (3 mm thickness) of light with a wavelength of 450 nm is preferably 80% or more, more preferably 85% or more, even more preferably 88% or more, and particularly preferably 90% or more. Since the above curable composition forms a cured product with excellent transparency, when used as a sealant for optical semiconductor elements in an optical semiconductor device or as a die attachment paste agent, the luminous intensity emitted from the optical semiconductor device tends to be higher.
  • the above cured product has excellent heat resistance, and its glass transition temperature (Tg) is preferably 170°C or higher, more preferably 175°C or higher, even more preferably 180°C or higher, even more preferably 190°C or higher, and particularly preferably 200°C or higher.
  • Tg glass transition temperature
  • the cured product has excellent heat resistance, and its 5% weight loss temperature (Td5) is preferably 325°C or higher, more preferably 330°C or higher, and even more preferably 335°C or higher.
  • the 10% weight loss temperature (Td10) of the cured product is preferably 355°C or higher, and more preferably 360°C or higher.
  • the cure shrinkage of the cured product is preferably 1.5% or less, more preferably 1.2% or less, and even more preferably 1.1% or less.
  • the cure shrinkage is calculated from the density change based on the following formula by measuring the density of the curable composition before curing and the cured product after curing.
  • Volumetric shrinkage rate r ⁇ (ds-dl)/dl ⁇ x 100 dl: specific gravity of the liquid before hardening. Measured using a density and specific gravity meter "DA-640" (manufactured by Kyoto Electronics Manufacturing Co., Ltd. ds: Specific gravity of solid after hardening, measured by solid specific gravity measurement method.
  • curable composition can be used for various applications, such as sealants, adhesives, coating agents, electrical insulating materials, laminates, inks, sealants, resists, composite materials, transparent substrates, transparent sheets, transparent films, optical elements, optical lenses, photolithography, electronic paper, touch panels, solar cell substrates, optical waveguides, light guide plates, and holographic memories.
  • the encapsulant includes the curable composition.
  • the encapsulant can be preferably used for encapsulating an optical semiconductor (optical semiconductor element) in an optical semiconductor device.
  • the content of the curable composition relative to the total amount (100% by mass) of the sealant is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more.
  • the sealant may consist of only the curable composition.
  • the adhesive contains the curable composition.
  • the adhesive can be used in various applications that require excellent transparency, heat resistance, and resistance to curing shrinkage, such as applications for adhering and fixing a member or the like to an adherend, specifically, a die attachment paste for adhering and fixing an optical semiconductor element to a metal electrode in an optical semiconductor device; a lens adhesive for fixing a lens of a camera or the like to an adherend or bonding lenses together; and an optical film adhesive for fixing an optical film (e.g., a polarizer, a polarizer protective film, a retardation film, etc.) to an adherend or bonding optical films together or an optical film to another film.
  • an optical film e.g., a polarizer, a polarizer protective film, a retardation film, etc.
  • the above adhesive can be particularly preferably used as a die attachment paste (or die bond agent).
  • a die attachment paste or die bond agent.
  • the content of the curable composition relative to the total amount (100% by mass) of the adhesive is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more.
  • the adhesive may consist of only the curable composition.
  • the coating agent includes the curable composition.
  • the coating agent can be used in various applications that require excellent handling properties, transparency, and heat resistance.
  • the content of the curable composition relative to the total amount of the coating agent (100% by mass) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more.
  • the coating agent may consist of only the curable composition.
  • the cured product can be used to obtain an optical member.
  • the optical member includes a cured product of the curable composition.
  • Examples of the optical member include an optical semiconductor device in which an optical semiconductor element is sealed by the cured product, an optical semiconductor device in which an optical semiconductor element is bonded to an electrode by the cured product, and an optical semiconductor device in which an optical semiconductor element is bonded to an electrode by the cured product and the optical semiconductor element is sealed by the cured product.
  • the optical member has a configuration in which it is sealed and bonded by the cured product, and therefore has excellent heat resistance and high light extraction efficiency.
  • Example 1 A 20 L SUS316 jacketed reactor equipped with a stirrer was charged with 5,000 g of 6-methyl-3-cyclohexenylmethyl (6'-methyl-3'-cyclohexenyl) carboxylate, and then heated to an internal temperature of 25°C. 13,790 g of a 30% ethyl acetate solution of peracetic acid was added dropwise over 6 hours, and the mixture was aged for 3 hours. The internal temperature was maintained at 30°C during the dropwise addition and aging. In this way, 18,790 g of a reaction crude liquid containing 3,4-epoxy-6-methyl-cyclohexylmethyl (3',4'-epoxy-6'-methyl) cyclohexane carboxylate was obtained.
  • Example 2 An alicyclic epoxy compound product 2 of Example 2 was obtained in the same manner as in Example 1, except that in the high boiling point removal step, the pressure was changed to 0.075 to 0.15 Torr.
  • Example 3 Alicyclic epoxy compound product 3 of Example 3 was obtained in the same manner as in Example 1, except that in the high boiling point removal step, the pressure was changed to 0.030 to 0.038 Torr.
  • Comparative Example 1 An alicyclic epoxy compound product 4 of Comparative Example 1 was obtained in the same manner as in Example 1, except that the high boiling point removal step was not carried out.
  • the peak area was calculated by dividing the peak area by a perpendicular line from the valley of the peak to the baseline.
  • the GPC device and various conditions used are as follows. Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation) Detector: Differential refractometer (RI detector) Precolumn: TSKGUARD COLUMN SUPER HZ-L 4.6mm x 20mm Column: Sample side TSK-GEL SUPER HZM-N 4.6mm x 150mm x 4 Reference side TSK-GEL SUPER HZM-N 6.0mm x 150mm x 1 + TSK-GEL SUPER H-RC 6.0mm x 150mm Thermostatic chamber temperature: 40°C Mobile phase: THF Mobile phase flow rate: 0.35 ml/min Sample injection volume: 10 ⁇ l Data collection time: 10 to 26 minutes after sample injection
  • compound (a) is a compound having a structure obtained by removing methyl groups from two epoxycyclohexyl groups of the compound represented by the above formula (a)
  • compound (b) is a compound having a structure obtained by removing methyl groups from two epoxycyclohexyl groups of the compound represented by the above formula (b)
  • compound (c) is a compound having a structure obtained by removing methyl groups from two epoxycyclohexyl groups of the compound represented by the above formula (c)
  • compound (d) is a compound having a structure obtained by removing methyl groups from two epoxycyclohexyl groups of the compound represented by the above formula (d).
  • Measurement device Product name "Agilent 7890GC5977B MSD", manufactured by Agilent Technologies, Inc.
  • Column packing material (5% phenyl)methylsiloxane
  • Column size length 15 m ⁇ inner diameter 0.53 mm ⁇ ⁇ film thickness 1.5 ⁇ m
  • Detector FID
  • the hue was evaluated by determining the Hazen color number APHA using a spectroscopic colorimeter and turbidity meter (trade name "TZ6000", manufactured by Nippon Denshoku Industries Co., Ltd.) and a glass cell (optical path length 33 x cell width 20 x height 55). A value of 105 or less is considered good, and a value of 15 or less is considered excellent.
  • TZ6000 spectroscopic colorimeter and turbidity meter
  • Viscosity The viscosity of the alicyclic epoxy compound product at 25°C was measured using a digital viscometer (model number "DVU-E II type", manufactured by Tokimec Co., Ltd.) under the following conditions: rotor: standard 1°34' x R24, temperature: 25°C, rotation speed: 0.5 to 10 rpm. A viscosity of 1300 mPa ⁇ s or less is judged as good, and a viscosity of 1000 mPa ⁇ s or less is judged as excellent.
  • Example 4 0.6 parts by mass of a thermal cationic catalyst "SAN-AID SI-100L” (product name, manufactured by Sanshin Chemical Industry Co., Ltd.) was blended with 100 parts by mass of the alicyclic epoxy compound product of each example, and the mixture was stirred using a planetary stirring device (product name "Awatori Rentaro AR-250", manufactured by Thinky Corporation), and further degassed to obtain each curable composition.
  • SAN-AID SI-100L product name, manufactured by Sanshin Chemical Industry Co., Ltd.
  • Example 5 The alicyclic epoxy compound product of each example was mixed with an acid anhydride curing agent (trade name "RIKACID MH-700” manufactured by New Japan Chemical Co., Ltd.) and a curing accelerator (trade name "PX-4MP” manufactured by Nippon Chemical Industry Co., Ltd.) such that the ratio of the epoxy equivalent of the compound represented by the formula (1) in the alicyclic epoxy compound product to the acid anhydride equivalent was 100:90, and the mixture was stirred using a planetary stirring device (trade name "Awatori Rentaro AR-250” manufactured by Thinky Corporation), and further degassed to obtain each curable composition.
  • an acid anhydride curing agent trade name "RIKACID MH-700” manufactured by New Japan Chemical Co., Ltd.
  • a curing accelerator trade name "PX-4MP” manufactured by Nippon Chemical Industry Co., Ltd.
  • Example 4 1100 seconds or less was judged as good, and 1050 seconds or less was judged as excellent. In Example 5, 5000 seconds or less was judged as good, and 3000 seconds or less was judged as excellent.
  • Example 6 Each of the curable compositions obtained in Examples 4 and 5 was filled into a mold and heated in a resin curing oven at 120° C. for 5 hours to obtain each cured product.
  • Example 6 Light transmittance For each of the cured products (thickness 3 mm) obtained in Example 6, the light transmittance (thickness direction) of light with a wavelength of 450 nm was measured using a spectrophotometer (product name "UV-2450", 10 mm square quartz cell, thickness 10 mm, manufactured by Shimadzu Corporation). In Example 4, a value of 80% or more was judged as good, and a value of 85% or more was judged as excellent. In Example 5, a value of 88% or more was judged as good, and a value of 90% or more was judged as excellent.
  • a spectrophotometer product name "UV-2450", 10 mm square quartz cell, thickness 10 mm, manufactured by Shimadzu Corporation.
  • Example 9 Glass transition temperature (Tg) The glass transition temperature of each of the cured products obtained in Example 6 was determined under the following conditions. In Example 4, a glass transition temperature of 175° C. or higher was judged as good, and a glass transition temperature of 200° C. or higher was judged as excellent. In Example 5, a glass transition temperature of 180° C. or higher was judged as good, and a glass transition temperature of 190° C. or higher was judged as excellent. Sample: Length 4mm x Width 5mm x Thickness 10mm Measurement device: Thermomechanical measurement device (TMA), product name "TMA/SS6000", manufactured by Seiko Instruments Inc. Measurement mode: compression (penetration), constant load measurement Measurement temperature: from 25°C to 300°C Heating rate: 5°C/min
  • the alicyclic epoxy compound products of the examples were evaluated as having low viscosity, good color, and excellent transparency compared to products with lower purity.
  • the cured products were also evaluated as having high light transmittance, excellent transparency, and high retention, as well as high Tg and excellent heat resistance.
  • the alicyclic epoxy compound products of the examples were evaluated as having less cure shrinkage compared to other alicyclic epoxy compound products.
  • Example 7 100 parts by mass of the alicyclic epoxy compound product 1 obtained in Example 1 was mixed with 2 parts by mass of a thermal cationic catalyst (product name "CPI-210S", manufactured by San-Apro Co., Ltd.) as a curing catalyst, and the mixture was stirred using a planetary stirring device (product name "Awatori Rentaro AR-250", manufactured by Thinky Corporation), and further degassed to obtain a curable composition.
  • the curable composition was then filled into a mold, irradiated with ultraviolet light at an intensity of 100 mW/ cm2 for 30 seconds, and then heated in a resin curing oven at 150°C for 30 minutes to obtain a cured product.
  • Examples 8 to 16 Curable compositions and cured products were prepared in the same manner as in Example 7, except that the components and amounts thereof were as shown in Table 2.
  • curability The curability of the curable compositions obtained in Examples 8 to 16 was measured using a device: SII's DSC6220. Specifically, a light source wavelength of 365 nm was irradiated at 30° C. for 30 seconds at 100 mW, and the exothermic peak intensity was calculated. The higher the peak intensity, the better the curability.
  • Low-boiling point removal step A step of removing low-boiling points from the reaction product.
  • High-boiling point removal step A step of removing high-boiling points from the reaction product by thin-film evapor

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  • Health & Medical Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2890194A (en) 1956-05-24 1959-06-09 Union Carbide Corp Compositions of epoxides and polycarboxylic acid compounds
US2999827A (en) * 1959-01-21 1961-09-12 Union Carbide Corp Epoxy coating compositions
WO2005090325A1 (ja) * 2004-03-18 2005-09-29 Daicel Chemical Industries, Ltd. 高純度脂環式 エポキシ化合物、その製造方法、硬化性エポキシ樹脂組成物、その硬化物、および用途
WO2006073093A1 (ja) * 2005-01-07 2006-07-13 Daicel Chemical Industries, Ltd. 高純度脂環式ジエポキシ化合物およびその製造方法
WO2019138988A1 (ja) 2018-01-12 2019-07-18 株式会社ダイセル 脂環式エポキシ化合物製品
WO2020213526A1 (ja) * 2019-04-19 2020-10-22 株式会社ダイセル 脂環式エポキシ化合物製品
JP2022177527A (ja) 2021-05-18 2022-12-01 ソニーセミコンダクタソリューションズ株式会社 固体撮像装置及び固体撮像装置の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019138988A (ja) 2018-02-08 2019-08-22 キヤノン株式会社 情報処理システム、情報処理方法、及びプログラム
KR102890194B1 (ko) 2022-12-20 2025-11-26 이화여자대학교 산학협력단 대체 단백질의 물성 조절용 섬유형 첨가제, 대체 단백질, 식품 및 대체 단백질의 제조방법

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2890194A (en) 1956-05-24 1959-06-09 Union Carbide Corp Compositions of epoxides and polycarboxylic acid compounds
US2999827A (en) * 1959-01-21 1961-09-12 Union Carbide Corp Epoxy coating compositions
WO2005090325A1 (ja) * 2004-03-18 2005-09-29 Daicel Chemical Industries, Ltd. 高純度脂環式 エポキシ化合物、その製造方法、硬化性エポキシ樹脂組成物、その硬化物、および用途
WO2006073093A1 (ja) * 2005-01-07 2006-07-13 Daicel Chemical Industries, Ltd. 高純度脂環式ジエポキシ化合物およびその製造方法
WO2019138988A1 (ja) 2018-01-12 2019-07-18 株式会社ダイセル 脂環式エポキシ化合物製品
WO2020213526A1 (ja) * 2019-04-19 2020-10-22 株式会社ダイセル 脂環式エポキシ化合物製品
JP2022177527A (ja) 2021-05-18 2022-12-01 ソニーセミコンダクタソリューションズ株式会社 固体撮像装置及び固体撮像装置の製造方法

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