CN113710719A - Epoxy resin and method for producing same - Google Patents

Epoxy resin and method for producing same Download PDF

Info

Publication number
CN113710719A
CN113710719A CN202080022416.7A CN202080022416A CN113710719A CN 113710719 A CN113710719 A CN 113710719A CN 202080022416 A CN202080022416 A CN 202080022416A CN 113710719 A CN113710719 A CN 113710719A
Authority
CN
China
Prior art keywords
formula
compound
epoxy resin
reaction
producing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202080022416.7A
Other languages
Chinese (zh)
Other versions
CN113710719B (en
Inventor
阿须间夕纪
浦野航
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Publication of CN113710719A publication Critical patent/CN113710719A/en
Application granted granted Critical
Publication of CN113710719B publication Critical patent/CN113710719B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
    • C07C303/30—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reactions not involving the formation of esterified sulfo groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • 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
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/28—Ethers with hydroxy compounds containing oxirane rings
    • C07D303/30—Ethers of oxirane-containing polyhydroxy compounds in which all hydroxyl radicals are etherified 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
    • C08G59/02—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
    • 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
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention relates to an epoxy resin containing 3,3 '-diglycidyl biphenyl-4, 4' -diglycidyl ether (formula (1)), and aims to provide a novel epoxy resin which can be handled as a solid in a normal state and is excellent in elastic modulus and shear adhesion strength. The epoxy resin is characterized by containing 3,3 '-diglycidyl biphenyl-4, 4' -diglycidyl ether represented by the following formula (1), and containing a component having a standard polystyrene equivalent molecular weight of not less than 9% by area and not more than 25% by area as measured by an RI detector in GPC, of not less than 60.8. [ formula (1) ].

Description

Epoxy resin and method for producing same
Technical Field
The present invention relates to an epoxy resin and a method for producing the same.
Background
The epoxy resin is a thermosetting synthetic resin having a reactive epoxy group at the end. Epoxy resins are widely used as high-performance, multifunctional resins because they are three-dimensional cured products that are not melt-insoluble when reacted with a curing agent, and can be used in accordance with various performance requirements by mixing various modifiers such as fillers, toughening agents, and diluents.
For example, patent document 1 (jp 2015-166335 a) discloses a method for producing an epoxy compound, which is characterized by reacting a carbon-carbon double bond of a compound having a carbon-carbon double bond with hydrogen peroxide in the presence of an onium salt having 4 or more acyloxy groups having 1 to 4 carbon atoms or 1 or more benzyloxy groups, and the onium salt having 20 or more total carbon atoms, and at least one of a tungsten compound and a molybdenum compound to epoxidize the compound.
Further, as an epoxy resin, a polyfunctional epoxy resin obtained by epoxidizing 3,3 '-diallylbiphenyl-4, 4' -diglycidyl ether (the following formula (4)) is known. For example, patent document 2 (japanese patent No. 2539648) discloses 3,3 '-diglycidyl biphenyl-4, 4' -diglycidyl ether (formula (1) below) as a polyfunctional epoxy resin obtained by epoxidizing a diallyl diglycidyl ether intermediate. Specifically, as a method for producing 3,3 '-diglycidyl biphenyl-4, 4' -diglycidyl ether (the following formula (1)), the following method is disclosed: 3,3 '-Diglycidylbiphenyl-4, 4' -diglycidyl ether (formula (4) below) in chloroform and sodium acetate were introduced into a sulfonation flask, peracetic acid was added dropwise at room temperature over about 2 hours, and after the completion of the dropwise addition, the reaction mixture was stirred, chloroform was then added, washed with water several times until the organic phase was neutral, dried, filtered, and then concentrated under vacuum, whereby 3,3 '-diglycidyl biphenyl-4, 4' -diglycidyl ether (formula (1) below) was obtained.
Formula (1)
Figure BDA0003268561770000021
Formula (4)
Figure BDA0003268561770000022
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2015-166335
Patent document 2: japanese patent No. 2539648
Disclosure of Invention
Problems to be solved by the invention
The 3,3 '-diglycidyl biphenyl-4, 4' -diglycidyl ether (formula (1) above) disclosed in patent document 2 has the following characteristics: not only has 4 epoxy groups in 1 molecule and is excellent in heat resistance, but also has low viscosity and excellent moldability despite multifunctionalization. However, the epoxy resin obtained by the manufacturing method disclosed in patent document 2 is liquid at normal temperature, and therefore, there are problems such as difficulty in industrial operation and an excessive industrial burden.
Accordingly, the present invention relates to an epoxy resin containing 3,3 '-diglycidyl biphenyl-4, 4' -diglycidyl ether (formula (1)), and an object of the present invention is to provide a novel epoxy resin which can be handled easily as a solid and is further excellent in elastic modulus and shear adhesion strength, and a method for producing the same.
Technical scheme for solving problems
The present invention provides an epoxy resin containing 3,3 '-diglycidyl biphenyl-4, 4' -diglycidyl ether represented by the following formula (1) (also referred to as a "compound of formula (1)), wherein the epoxy resin contains a component having a standard polystyrene equivalent molecular weight of not less than 9% by area and not more than 25% by area as measured by a RI detector in gel permeation chromatography (referred to as" GPC ").
The present invention also provides an epoxy resin containing a compound represented by the following formula (5),
the epoxy resin contains a component having a standard polystyrene equivalent molecular weight of 9 to 25% by area of 60.8 or more as measured by a RI detector in gel permeation chromatography (referred to as "GPC").
The present invention further proposes that the component having a standard polystyrene equivalent molecular weight of 60.8 or more in GPC in the epoxy resin is a compound having 2 or more biphenyl skeletons.
The present invention also provides an epoxy resin composition comprising the epoxy resin, and containing an epoxy curing agent in a proportion of 0.80 equivalent or more and 1.03 equivalent or less of functional group equivalent to the epoxy resin.
The invention further provides a cured product which is formed by curing the epoxy resin composition.
The present invention also provides a method for producing an epoxy resin, comprising the steps of: a step of obtaining an epoxy resin by performing a reaction of converting a compound represented by the following formula (2) (also referred to as a "compound of formula (2)") into a compound represented by the following formula (3) (also referred to as a "compound of formula (3)"), then performing a reaction of converting the compound of formula (3) into a compound represented by the following formula (4) (also referred to as a "compound of formula (4)"), and then performing a reaction of converting the compound of formula (4) into a compound of formula (1) represented by the following formula (1), wherein in the method for producing an epoxy resin, a content ratio of a component having a standard polystyrene equivalent molecular weight of 60.8 or more in the epoxy resin is 9 area% or more and 25 area% or less as measured by using an RI detector in GPC.
Formula (1)
Figure BDA0003268561770000041
Formula (2)
Figure BDA0003268561770000042
Formula (3)
Figure BDA0003268561770000043
Formula (4)
Figure BDA0003268561770000044
The present invention further provides a method for producing an epoxy resin, wherein the following reaction is performed: subjecting the compound of formula (2) to claisen rearrangement in the presence of a basic compound to convert into the compound of formula (3).
The present invention further provides a method for producing an epoxy resin, wherein the basic compound is added to the compound of formula (2) in a proportion of 1.0 mol or more and 100 mol or less relative to 1.0 mol of the compound, and the mixture is reacted.
The present invention further provides a method for producing an epoxy resin, wherein the basic compound is an aniline compound.
The present invention further provides a method for producing an epoxy resin, characterized in that, in the method for producing an epoxy resin, purification for separating and removing components other than the compound of the formula (3) is performed after the reaction for converting the compound of the formula (2) into the compound of the formula (3) is performed and before the reaction for converting the compound of the formula (3) into the compound of the formula (4) is performed.
The present invention further provides a method for producing an epoxy resin, wherein in the method for producing an epoxy resin, after the reaction for converting the compound of formula (3) into the compound of formula (4) is performed and before the reaction for converting the compound of formula (4) into the compound of formula (1), the method is characterized in that the method is performed by separating and removing components other than the compound of formula (4).
The present invention further provides a method for producing an epoxy resin, wherein the method for producing an epoxy resin is characterized in that, after a reaction for converting the compound of formula (4) into the compound of formula (1), purification for separating and removing components other than the compound of formula (1) is performed.
The present invention further provides a method for producing an epoxy resin, wherein the purification is performed by crystallization.
The present invention also provides a method for producing an epoxy resin, comprising the steps of: a step of obtaining an epoxy resin by carrying out a reaction of converting a compound represented by the following formula (6) (also referred to as "compound of formula (6)") into a compound represented by the following formula (7) (also referred to as "compound of formula (7)"), then carrying out a reaction of converting the compound of formula (7) into a compound represented by the following formula (8) (also referred to as "compound of formula (8)"), then carrying out a reaction of converting the compound of formula (8) into a compound of formula (5) represented by the following formula (5),
in the method for producing an epoxy resin, the content of a component having a standard polystyrene equivalent molecular weight of 60.8 or more in the epoxy resin is 9 to 25 area% when measured by an RI detector in GPC.
[ formula (5) ]
Figure BDA0003268561770000061
X in the formula (5) is-SO2-、-O-、-CO-、-C(CF3)2-, -S-or a divalent linking group selected from a hydrocarbon group having 1 to 20 carbon atoms.
[ formula (6) ]
Figure BDA0003268561770000062
X in the formula (6) is-SO2-、-O-、-CO-、-C(CF3)2-, -S-or a divalent linking group selected from a hydrocarbon group having 1 to 20 carbon atoms.
[ formula (7) ]
Figure BDA0003268561770000071
X in the formula (7) is-SO2-、-O-、-CO-、-C(CF3)2-, -S-or a divalent linking group selected from a hydrocarbon group having 1 to 20 carbon atoms.
[ formula (8) ]
Figure BDA0003268561770000072
X in the formula (8) is-SO2-、-O-、-CO-、-C(CF3)2-, -S-or a divalent linking group selected from a hydrocarbon group having 1 to 20 carbon atoms.
The present invention further provides a method for producing an epoxy resin, wherein the following reaction is performed: subjecting the compound of formula (6) to claisen rearrangement in the presence of a basic compound to convert into the compound of formula (7).
The present invention further provides a method for producing an epoxy resin, wherein the basic compound is added to the compound of formula (6) in a proportion of 1.0 mol or more and 100 mol or less relative to 1.0 mol of the compound, and the mixture is reacted.
The present invention further provides a method for producing an epoxy resin, wherein the basic compound is an aniline compound.
The present invention further provides a method for producing an epoxy resin, wherein in the method for producing an epoxy resin, purification for separating and removing components other than the compound of the formula (7) is performed after the reaction for converting the compound of the formula (6) into the compound of the formula (7) is performed and before the reaction for converting the compound of the formula (7) into the compound of the formula (8) is performed.
The present invention further provides a method for producing an epoxy resin, wherein in the method for producing an epoxy resin, purification for separating and removing components other than the compound of formula (8) is performed after the reaction for converting the compound of formula (7) into the compound of formula (8) is performed and before the reaction for converting the compound of formula (8) into the compound of formula (5) is performed.
The present invention further provides a method for producing an epoxy resin, wherein the method for producing an epoxy resin is characterized in that, after a reaction for converting the compound of formula (8) into the compound of formula (5), purification for separating and removing components other than the compound of formula (5) is performed.
The present invention further provides a method for producing an epoxy resin, wherein the purification is performed by crystallization in the method for producing an epoxy resin.
Effects of the invention
The epoxy resin proposed by the present invention and the epoxy resin obtained by the manufacturing method proposed by the present invention can maintain characteristics such as excellent heat resistance and moldability because the epoxy resin contains 3,3 '-diglycidyl biphenyl-4, 4' -diglycidyl ether represented by the above formula (1), i.e., the compound of the formula (1).
Further, the epoxy resin proposed by the present invention and the epoxy resin obtained by the manufacturing method proposed by the present invention can maintain characteristics such as excellent heat resistance and moldability since they are epoxy resins containing the above-described compound of formula (5).
The epoxy resin proposed by the present invention and the epoxy resin obtained by the production method proposed by the present invention can be handled as a solid, and are excellent in elastic modulus and shear adhesion strength, so that they are industrially easy to handle and suitable for industrial use.
Drawings
FIG. 1 is a process diagram showing an example of a method for producing an epoxy resin according to an example of the embodiment of the present invention.
FIG. 2 is a diagram showing the structural formula of a compound contained in an oligomer component X described later.
Detailed Description
< the present epoxy resin >
An epoxy resin according to an example of the embodiment of the present invention (referred to as "present epoxy resin") is an epoxy resin containing a compound represented by the following formula (1), and is an epoxy resin containing a component having a predetermined molecular weight (referred to as "oligomer component X") at a predetermined ratio.
The epoxy resin is an epoxy resin containing a compound having a molar molecular weight of 410, and is in an uncured state in which the epoxy resin is not substantially crosslinked, that is, not intentionally crosslinked.
Formula (1)
Figure BDA0003268561770000091
(oligomer component X)
The epoxy resin preferably contains 9% by area or more of a component having a standard polystyrene equivalent molecular weight of 60.8 or more (referred to as "oligomer component X") as measured by an RI detector in GPC, more preferably 10% by area or more, particularly preferably 15% by area or more, and on the other hand preferably 25% by area or less, more preferably 20% by area or less, particularly preferably 18% by area or less.
If the area ratio of the oligomer component X in the present epoxy resin is 9 area% or more, the energy necessary for melting can be reduced, and if it is 25 area% or less, the present epoxy resin can be made solid at room temperature, and further, the elastic modulus and shear adhesion strength can be made excellent.
The oligomer component X is a compound having 2 or more biphenyl skeletons, and may be composed of 2 or more compounds having 2 or more biphenyl skeletons.
The oligomer component X is not particularly limited if it is a compound having 2 or more biphenyl skeletons, but is preferably a component composed of at least one of compounds having molar molecular weights 819, 805, and 765, and more preferably a compound having a molar molecular weight 833 or 847.
The compound having the estimated molar mass 847 is a compound produced when N, N-diethylaniline is used in the claisen rearrangement step, and the compound having the estimated molar mass 833 is a compound produced when N, N-dimethylaniline is used.
Examples of the compound contained in the oligomer component X include compounds having a chemical structure shown in fig. 2. It is noted that some or all of the double bonds in the structural formula shown in FIG. 2 may be converted to epoxy groups by oxidation, and preferably all may be converted to epoxy groups.
(melting Point)
The melting point of the epoxy resin obtained from the DSC curve is preferably 50 ℃ or higher, more preferably 60 ℃ or higher. The upper limit is about 100 ℃.
The melting point of the present epoxy resin obtained from a DSC curve is preferably 50 ℃ or higher, since the epoxy resin is in a solid state at ordinary temperature, and therefore, the epoxy resin is excellent in industrial workability. Further, if it is 100 ℃ or lower, it is preferable because it can be dissolved without requiring a large amount of energy and it is easy to keep the liquid state in the step of preparing the epoxy resin composition before curing.
In order to adjust the melting point of the present epoxy resin to 50 ℃ or higher as determined from the DSC curve, the above-mentioned area ratio of the oligomer component X in the present epoxy resin may be 9 area% or more and 25 area% or less, as described above.
< the present production method >
Next, a description will be given of a production method according to a preferred example (referred to as "the present production method") as a production method of the present epoxy resin. However, the method for producing the epoxy resin is not limited to the following method.
The method for producing an epoxy resin is characterized by comprising the steps of: the present invention provides a method for producing an epoxy resin, which comprises the steps of carrying out a reaction for converting a compound of formula (2) into a compound of formula (3) (this reaction step is referred to as "step a"), then carrying out a reaction for converting a compound of formula (3) into a compound of formula (4) (this reaction step is referred to as "step B"), and then carrying out a reaction for converting a compound of formula (4) into a compound of formula (1) (this reaction step is referred to as "step C"), wherein the content ratio of oligomer component X in the epoxy resin, for example, the present epoxy resin, is controlled to be 9 to 25 area% as measured by an RI detector.
Formula (2)
Figure BDA0003268561770000111
Formula (3)
Figure BDA0003268561770000112
Formula (4)
Figure BDA0003268561770000113
Formula (1)
Figure BDA0003268561770000114
In the present manufacturing method, the step a, the step B, and the step C may be performed continuously by an apparatus in which conveying apparatuses are connected to each other, or may be performed at intervals in different apparatuses.
In addition, if the manufacturing method includes the step a, the step B, and the step C, other steps, other processes, and the like may be appropriately inserted.
(Process A)
The step a, which is a reaction method for converting the compound of the formula (2) into the compound of the formula (3), may be performed by a claisen rearrangement reaction.
The claisen rearrangement reaction is affected by the solvent and additives used, but the reaction can be usually carried out by heating to a temperature of 100 to 300 ℃. The reaction is preferably heated to a temperature of 150 ℃ or higher from the viewpoint of shortening the reaction time, and is preferably heated to a temperature of 250 ℃ or lower from the viewpoint of suppressing side reactions under high temperature conditions. Among them, heating to a temperature of 170 ℃ or higher or 220 ℃ or lower is particularly preferable.
The solvent is not necessarily required in this step, but may be used. From the viewpoint of process safety, it is preferable to use a solvent because there is an advantage that the increase in the internal temperature can be suppressed by absorbing the reaction heat of the claisen rearrangement reaction by the latent heat of evaporation of the solvent.
The solvent used in the present step is not particularly limited if it has a boiling point higher than the reaction temperature, is stable at the reaction temperature, and is inert to the compound of the formula (2) or the compound of the formula (3), and specifically includes aromatic hydrocarbons such as toluene, xylene, mesitylene, anisole, and the like; aliphatic chain hydrocarbons such as octane, nonane, decane, undecane, and dodecane; aliphatic cyclic hydrocarbons such as cyclooctane, ethylcyclohexane, decalin, and the like; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; dimethyl sulfoxide; and mixtures of these solvents.
The compound of formula (2) can be obtained by any method. Commercially available products can be obtained, and when the synthesis is performed, the synthesis can be performed by reacting biphenol with allyl halide such as allyl chloride or allyl bromide in the presence of a base.
(Process B)
The step B, which is a reaction step for converting the compound of the formula (3) into the compound of the formula (4), can be carried out by a method known as glycidation.
For example, it can be carried out by reacting an epihalohydrin in the presence of a base. Alternatively, the addition may be carried out by adding an epihalohydrin in the presence of an acid catalyst, followed by dehalogenation and hydrogenation using a base.
Examples of the epihalohydrin include epichlorohydrin and epibromohydrin. Epichlorohydrin is preferred from the viewpoint of easy availability on an industrial scale.
The amount of the epihalohydrin used is preferably 1 to 100 equivalents based on the compound of the formula (3). Among them, 5 equivalents or more is preferable from the viewpoint of improving the reaction selectivity, and 50 equivalents or less is preferable from the viewpoint of improving the productivity per batch. Among them, more preferably 10 equivalents or more and 40 equivalents or less, and particularly preferably 20 equivalents or more and 35 equivalents or less.
The reaction temperature is usually a temperature of-50 to 200 ℃. From the viewpoint of shortening the reaction time, it is preferably 0 ℃ or higher, and from the viewpoint of suppressing side reactions under high temperature conditions, it is preferably 150 ℃ or lower. Among them, heating to a temperature of 40 ℃ or higher or 100 ℃ or lower is particularly preferable.
Examples of the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide and barium hydroxide. Among them, potassium hydroxide and sodium hydroxide are preferable from the viewpoint of reaction efficiency.
The amount of the base used is preferably 1 to 20 equivalents based on the compound of the formula (3). Among them, from the viewpoint of improvement in yield, 1.5 equivalents or more is preferable, and in order to avoid complication of removal, 5 equivalents or less is preferable. Among them, 1.8 equivalents or more and 2.5 equivalents or less are particularly preferable.
The base may be used as it is in a solid state, but is preferably used in a solution state from the viewpoint of improving reactivity.
As the catalyst, quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide; tertiary amines such as benzyldimethylamine and 2,4,6- (trisdimethylaminomethyl) phenol; imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole; phosphonium salts such as ethyltriphenylphosphonium iodide; phosphines such as triphenylphosphine, etc.
As the solvent, epihalohydrin may be used as the solvent, and alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, and tert-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and 2-pentanone; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; aromatic compounds such as benzene, xylene, and toluene; aromatic alcohols such as benzyl alcohol; glycol ether acetates such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; ethers such as 1, 3-dioxane, 1, 4-dioxane, diethyl ether, and tetrahydrofuran; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; dimethylsulfoxide, water, etc. These may be used alone or in combination of two or more. As described above, in view of reaction efficiency, it is preferable to use a solvent in which a base is easily dissolved, and therefore, alcohols, ketones, glycol ethers, glycol ether acetates, ethers, amides, and water are preferable, and alcohols and water are preferable among them.
(Process C)
The step C, i.e., the reaction step of converting the compound of formula (4) into the compound of formula (1), can be carried out by any method.
As an example of the arbitrary method, for example, the following method can be given: phosphoric acids or phosphonic acids are oxidized in the presence of an onium salt as a phase transfer catalyst and at least one of a tungsten compound and a molybdenum compound as a catalyst composition using hydrogen peroxide as an oxidizing agent.
Further, a method of oxidation using a peroxy acid such as peracetic acid or m-chloroperoxybenzoic acid is exemplified.
Further, there is a method of reacting hydrogen peroxide with an organic nitrile compound in the presence of a carbonate, a bicarbonate or the like of an alkali metal.
Among them, for the reason that it is excellent in safety without using an excessive amount of an oxidizing agent, the following method is preferable: the oxidation is carried out by using hydrogen peroxide as an oxidizing agent in the presence of an onium salt as a phase transfer catalyst and at least one of a tungsten compound and a molybdenum compound as a catalyst composition.
Examples of the phosphoric acids include inorganic phosphoric acids such as phosphoric acid, polyphosphoric acid, and pyrophosphoric acid; inorganic phosphates such as sodium phosphate, potassium phosphate, ammonium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, ammonium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and calcium dihydrogen phosphate; phosphoric acid esters such as monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, triethyl phosphate, and triphenyl phosphate; and the like. The phosphonic acids include aminomethylphosphonic acid and phenylphosphonic acid. For reasons of low cost, phosphoric acids are preferred, with inorganic phosphoric acids being preferred, and phosphoric acid being particularly preferred, from the viewpoint of reactivity.
The onium salt of the phase transfer catalyst is a salt of an onium ion and an anion, and examples of the onium ion include tetraalkylammonium ions, trialkylphenylammonium ions, trialkylbenzylammonium ions, pyridinium ions, and phosphonium ions. In addition, onium salts disclosed in WO2013147092, Japanese Kokai publication 2015-166335 can also be used. Among them, from the viewpoint of reaction efficiency, it is preferable to use an onium ion having 20 or more carbon atoms. Further, the onium salts disclosed in WO2013147092, Japanese Kokai publication 2015-166335 are preferable because they can be converted into water-soluble substances by simple subsequent treatments such as hydrolysis after the reaction is completed, and can be efficiently removed from the catalyst composition.
The above-mentioned anionic species is not particularly limited. Examples thereof include monovalent anions such as hydrogen sulfate, monomethyl sulfate, halogen ions, nitrate, acetate, hydrogen carbonate, dihydrogen phosphate, sulfonate, carboxylate, hydroxide, etc., and divalent anions such as hydrogen phosphate, sulfate, etc., and monovalent anions are preferable from the viewpoint of easy availability and adjustment. From the viewpoint that side reactions can be suppressed, monomethyl sulfate, hydrogen sulfate, acetate, dihydrogen phosphate, or hydroxide is preferable.
The onium ion and the anion species may be used singly or in combination of two or more kinds as appropriate.
Examples of the tungsten compounds and molybdenum compounds include tungstic acid; tungstates such as sodium tungstate, potassium tungstate, calcium tungstate, and ammonium tungstate; hydrates of the above tungstates; phosphotungstic acids such as 12-phosphotungstic acid and 18-phosphotungstic acid; silicotungstic acids such as 12-silicotungstic acid; borotungstic acids such as 12-borotungstic acid; a metal tungsten; molybdic acids such as molybdic acid; molybdates such as sodium molybdate, potassium molybdate, ammonium molybdate and the like; hydrates of the above molybdates or hydrates thereof. Tungstic acid, tungstate are preferred from the viewpoint of improving the catalyst activity, and tungstic acid, sodium tungstate, calcium tungstate or their hydrates are preferred from the viewpoint of easy availability.
The hydrogen peroxide may be used in a 35 mass% aqueous solution, a 45 mass% aqueous solution, or a 60 mass% aqueous solution, which can be obtained in general. For reasons of easy availability, a 35 mass% aqueous solution is preferred.
The hydrogen peroxide concentration in the reaction solution is not particularly limited, but is usually in the range of 0.1 to 30% by mass, and is preferably kept at 1% by mass or more from the viewpoint of reaction efficiency, and is preferably kept at 20% by mass or less from the viewpoint of safety. Among these, it is preferable to further maintain 2 mass% or more or 15 mass% or less.
As the solvent, if it is inert with respect to the compound of the formula (4) or the compound of the formula (1), the active catalyst, and hydrogen peroxide to be used, an appropriate solvent can be used. Specific examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane, octane and dodecane; alcohols such as methanol, ethanol, isopropanol, butanol, hexanol, and cyclohexanol; halogen-based solvents such as chloroform, dichloromethane, and dichloroethane; ethers such as tetrahydrofuran and dioxane; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ester compounds such as nitriles including acetonitrile and butyronitrile, ethyl acetate, butyl acetate, and methyl formate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; ureas such as N, N' -dimethylimidazolidinone; and mixtures of these solvents. From the viewpoint of reaction efficiency and the ease of separation of the target product and the catalyst component, it is preferable to use a solvent that forms a biphasic system without mixing with water, and therefore aromatic hydrocarbons, aliphatic hydrocarbons, halogen-based solvents, water-insoluble ketones, and ester compounds are preferable, and aromatic hydrocarbons having high solubility of the above formula (4) as a reaction raw material, which are stable to the oxidation reaction, are more preferable.
(the present production method)
In the present production method, the specific method of the method of making the content ratio of the oligomer component X in the present epoxy resin to be 9 area% or more and 25 area% or less as measured by an RI detector is not particularly limited. For example, the present invention can be implemented by the following production methods 1 to 4. But is not limited to these methods.
(production method example 1)
As an example of a method for adjusting the content ratio of the oligomer component X in the epoxy resin to 9% by area or more and 25% by area or less as measured by an RI detector, the following method can be given: in the step a, the compound of the formula (2) is subjected to claisen rearrangement reaction in the presence of a basic compound to convert the compound into a compound of the formula (3).
The claisen rearrangement allows the reaction to proceed only by heating, and thus the reaction can proceed without adding an alkali compound. However, by carrying out the claisen rearrangement reaction in the presence of a basic compound to produce the compound of the formula (3), the production of components other than the compound of the formula (3) can be suppressed, and the content of the oligomer component X in the epoxy resin can be finally made to be within the above-specified range.
The basic compound may be any compound which does not have a polymerizable functional group in the molecule and does not volatilize at the reaction temperature. Examples thereof include aliphatic linear amines such as diethylenetriamine and triethylenetetramine; aliphatic amines having a benzene ring such as benzylamine, m-xylylenediamine, p-xylylenediamine, N-methylbenzylamine, N-ethylbenzylamine, N-isopropylbenzylamine, 1-phenylethylamine, dibenzylamine, and N, N-dimethylbenzylamine; anilines such as aniline, N-methylaniline, N-ethylaniline, N-isopropylaniline, N-dimethylaniline, N-diethylaniline and N, N-dipropylaniline; alicyclic amines such as piperidines and morpholines; heterocyclic amines such as pyridines, pyrroles, indoles, quinolines, imidazoles, carbazoles and the like.
Among them, anilines which are inexpensive and easily separated from the product are preferable, and among them, N-dimethylaniline, N-diethylaniline and N, N-dipropylaniline which have low reactivity with the allyl group contained in the compound of the formula (2) and the compound of the formula (3) and are less likely to cause side reactions are particularly preferable.
The basic compound is preferably added in a proportion of 0.5 mol or more and 100 mol or less, particularly preferably 0.8 mol or more, particularly preferably 1.0 mol or more, based on 1.0 mol of the compound of the formula (2), and preferably 20 mol or less, particularly preferably 5 mol or less, from the viewpoint of cost.
(production method example 2)
Another example of the method in which the content ratio of the oligomer component X in the epoxy resin is 9 area% or more and 25 area% or less as measured by an RI detector is as follows: in a stage after the reaction for converting the compound of formula (2) into the compound of formula (3) and before the reaction for converting the compound of formula (3) into the compound of formula (4), the content ratio of the oligomer component X in the epoxy resin is controlled within a predetermined numerical range by performing purification for separating and removing components other than the compound of formula (3).
(production method example 3)
As another example of the method in which the content ratio of the oligomer component X in the epoxy resin is 9 area% or more and 25 area% or less as measured by an RI detector, the following method can be given: in a stage after the reaction for converting the compound of formula (3) into the compound of formula (4) and before the reaction for converting the compound of formula (4) into the compound of formula (1), the content ratio of the oligomer component X in the epoxy resin is controlled within a predetermined numerical range by performing purification for separating and removing components other than the compound of formula (4).
(production method example 4)
Still another example of the method for determining the content ratio of the oligomer component X in the epoxy resin to be 9 area% or more and 25 area% or less as measured by an RI detector is as follows: after the reaction for converting the compound of formula (4) into the compound of formula (1), the epoxy resin is purified by separating and removing components other than the compound of formula (1) so that the content ratio of the oligomer component X in the epoxy resin falls within a predetermined numerical range.
(specific method of purification)
In the above production methods examples 2 to 4, a known purification method can be suitably used as a specific method for separating and removing each component. For example, crystallization, suspension washing, liquid separation, adsorption, column chromatography, distillation, etc. These purification methods may be appropriately combined. The crystallization method, the suspension washing method, the liquid separation method, and the distillation method are preferable from the viewpoint of a small burden on the production process, and the crystallization method is particularly preferable from the viewpoint of a good purification efficiency.
Crystallization is an example of a chemical separation technique, and is a technique of crystallizing a target component from a solution by cooling or heating to selectively separate the target component by utilizing the temperature dependence of solubility.
As a purification method using crystallization, any of the following methods and the like can be used: a method of precipitating the solvent while distilling the solvent under reduced pressure, a method of precipitating the solvent while cooling the solvent by utilizing a difference in solubility without distilling the solvent, a method of dissolving the solvent in a benign solvent and then precipitating the solvent by adding a poor solvent, and the like. The precipitated solid matter can be recovered by filtration and dried to obtain the target product.
As the solvent used for crystallization, a suitable solvent is preferably selected in accordance with the solubility of the compound, and a plurality of solvents may be used in combination.
Among them, examples of the solvent include aliphatic hydrocarbons such as hexane, heptane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as methyl acetate, ethyl acetate, isopropyl acetate, etc.; nitriles such as acetonitrile; chain or cyclic ethers such as diisopropyl ether, 1, 2-dimethoxyethane, tetrahydrofuran, and dioxane; alcohols such as methanol, ethanol, 2-propanol, and n-butanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; aprotic polar solvents such as N, N' -dimethylformamide, N-methylpyrrolidone, and dimethylsulfoxide; and (3) water.
As the purification method using suspension washing, a poor solvent is preferably used. Preferred examples of the poor solvent include high-polarity solvents such as methanol, ethylene glycol, and water, and conversely, low-polarity aliphatic hydrocarbons such as hexane, heptane, and cyclohexane.
After the suspension washing is completed, the solid matter can be recovered by filtration and dried to obtain the target product.
In the purification by liquid separation, there are a case where water and an insoluble or scarcely soluble organic solvent are combined and a case where a plurality of mutually immiscible organic solvents are combined. Examples of the combination of water and an insoluble or poorly soluble organic solvent include a combination of an organic solvent such as ethyl acetate or toluene and water.
Examples of the adsorbent used in the adsorption method include activated carbon, activated clay, molecular sieves, activated alumina, zeolite, ion exchange resins, and the like. The adsorbent is removed by filtration after being added to the solution containing the compound, and may be used by being packed in a column.
The above-mentioned production methods 1 to 4 may be carried out individually or in combination of two or more of the production methods 1 to 4. Among them, it is particularly preferable to produce the epoxy resin containing the compound of formula (1) in high yield by only production method example 1, in order to avoid the loss due to the crystallization operation.
In the crystallization in production method example 2, it is preferable to heat and dissolve the crystals in a benign solvent such as toluene or ethyl acetate, and to collect crystals precipitated in the cooling process by filtration, for example.
In the crystallization in production method example 3 or production method example 4, it is preferable to add an alcohol such as methanol, ethanol, 2-propanol, or n-butanol, heat the mixture, stand the mixture, remove a lower layer separated from the alcohol solution by liquid separation, cool the remaining upper layer, and collect crystals precipitated in the cooling process by filtration.
< present epoxy resin composition >
Next, an epoxy resin composition containing the present epoxy resin and an epoxy cured product (referred to as "the present epoxy resin composition") will be described.
The present epoxy resin composition is a composition containing the present epoxy resin, an epoxy curing agent and other components, and is an uncured epoxy resin composition which is not substantially crosslinked, that is, is not intentionally crosslinked.
The epoxy resin composition preferably contains an epoxy curing agent in a proportion of 0.80 equivalent to 1.03 equivalent to the functional group equivalent of the epoxy resin.
In general, when a curing agent is mixed with an epoxy resin, the epoxy curing agent is usually mixed in a ratio of 1:1 in terms of functional group equivalent to that of the epoxy resin.
On the other hand, in the present epoxy resin composition, by containing the epoxy curing agent in a proportion of 1.03 equivalents or less, in particular 1.00 equivalents or less, relative to the functional group equivalent of the present epoxy resin, the conductivity of the extract water can be reduced, and the pH can be brought into a neutral range. The present epoxy resin contains the compound of the formula (1) as a main component, but since the compound of the formula (1) has epoxy groups in 1 molecule at a high density, the curing rate is lower than that of a general epoxy resin, and unreacted functional groups tend to remain in a cured product. Therefore, it is considered that by reducing the equivalent weight of the curing agent, unreacted functional groups called sources of ionic components can be reduced, the conductivity of the extract water is lowered, and further, the pH approaches the neutral range. This makes it possible to provide a material having an excellent corrosion-inhibiting effect for use in applications such as semiconductor packaging materials.
On the other hand, by containing 0.80 equivalent or more of an epoxy curing agent to the functional group equivalent of the present epoxy resin, the occurrence of curing failure can be prevented, and the deterioration of various physical properties caused by the curing failure can be suppressed.
From the above-described viewpoint, when the curing agent is mixed with the present epoxy resin, the curing agent is preferably contained in a proportion of 0.80 equivalent or more and 1.03 equivalent or less, more preferably 0.85 or more and 1.00 or less, still more preferably 0.87 or more and 0.98 or less, and still more preferably 0.90 or more and 0.96 or less, of the functional group equivalents to the present epoxy resin.
As the epoxy curing agent, a known curing agent can be used. Specific examples thereof include phenol-based curing agents, ester-based curing agents, benzoxazine-based curing agents, acid anhydride-based curing agents, primary and secondary amine-based curing agents, thiol-based curing agents, amide-based curing agents, blocked isocyanate-based curing agents, tertiary amine-based curing agents, imidazole-based curing agents, lewis acid-amine complexes, and the like. Further, a phenoxy resin may be used as a curing agent.
(other Components)
The epoxy resin composition may contain, in addition to the epoxy resin and the curing agent, other epoxy resins, curing accelerators, fillers, mold release agents, other additives, solvents, and the like as required.
The content of the epoxy resin is usually 0.1% by mass or more, preferably 1% by mass or more, and particularly preferably 10% by mass or more, based on the total solid phase components contained in the epoxy resin composition. The content is usually 95% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less.
Examples of the "other epoxy resin" include various epoxy resins such as bisphenol a type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, and the like.
Examples of the "curing accelerator" include imidazole-based curing accelerators, tertiary amine-based curing accelerators, organic phosphine-based curing accelerators, phosphonium salt-based curing accelerators, tetraphenylboron salt-based curing accelerators, metal-based curing accelerators, organic acid dihydrazides, and halogenated boron amine complexes.
Examples of the "filler" include insulating fillers such as alumina, aluminum nitride, boron nitride, silicon nitride, and silica when an inexpensive insulating composition is desired.
Examples of the "release agent" include stearic acid, palmitic acid, zinc stearate, and calcium stearate.
The epoxy resin composition may contain a solvent for the purpose of adjusting the viscosity during processing and improving the workability during curing.
Examples of such solvents include ketones such as acetone, Methyl Ethyl Ketone (MEK), methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate; ethers such as ethylene glycol monomethyl ether; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; alcohols such as methanol, ethanol, and isopropanol; alkanes such as hexane and cyclohexane; aromatic compounds such as toluene and xylene.
In addition, the epoxy resin composition may contain a coupling agent, an ultraviolet screening agent, an antioxidant, a light stabilizer, a plasticizer, a flux, a flame retardant, a colorant, a dispersant, an emulsifier, a low-elasticizer, a diluent, an antifoaming agent, an ion scavenger, and the like as appropriate.
< the present cured product >
By curing the present epoxy resin composition, a cured product (referred to as "the present cured product") can be obtained.
The curing method and conditions are not particularly limited. However, thermosetting is preferable from the viewpoint of easy molding.
(glass transition temperature)
The glass transition temperature (Tg) of the cured product is usually 150 ℃ or higher, and when used as a sealing material for a semiconductor driven under high temperature conditions such as a power device, it is more preferably 180 ℃ or higher, and particularly preferably 200 ℃ or higher.
(storage modulus of elasticity (E'))
The storage elastic modulus (E') of the cured product at 250 ℃ varies depending on the type of the curing agent used, but is usually 10MPa to 10 GPa.
When the cured product is used as, for example, a semiconductor encapsulating material, it is necessary to prevent the occurrence of cracks in the semiconductor encapsulation and the peeling of the interface between the element mounting surface of the substrate and the cured product of the epoxy resin composition from the viewpoint of improving reliability, and therefore, it is necessary to reduce the elastic modulus of the cured product. From this viewpoint, the storage elastic modulus at 250 ℃ of the present cured product is preferably 1GPa or less, more preferably 500MPa or less, and still more preferably 300MPa or less. Further, when mechanical durability under high temperature conditions is required, it is effective that the cured product has a high elastic modulus, and therefore the storage elastic modulus at 250 ℃ of the present cured product is preferably 50MPa or more, more preferably 70MPa or more, and further preferably 100MPa or more.
In order to adjust the storage elastic modulus (E') at 250 ℃ of the present cured product and the shear adhesion strength to copper of the present cured product to the above range, the present epoxy resin composition prepared by using the present epoxy resin containing the oligomer component X at a predetermined ratio may be cured. As the curing conditions for curing, for example, a phenolic curing agent is used, and it is preferable that the curing temperature is 100 to 200 ℃ and the curing time is 1 to 20 hours.
< use >
The epoxy resin composition and the cured product can be suitably used as materials in various fields such as adhesives, paints, civil engineering and construction materials, and insulating materials in the electric and electronic fields. In particular, the resin composition is useful as an insulating potting material, a laminating material, a sealing material, or the like in the electric and electronic fields. Examples of the applications include multilayer printed wiring boards, build-up wiring boards, solder resists, adhesives, semiconductor packaging materials, underfill materials, 3D-LSI interlayer filling (interposer fill) materials, insulating sheets, prepregs, and heat dissipating boards.
< other embodiment example >
The description of the epoxy resin obtained by replacing the compound of the formula (1) with the compound represented by the following formula (5) (also referred to as "compound of the formula (5)") can be the same as the above description of the present epoxy resin.
The epoxy resin can be produced in the same manner by replacing the compound of formula (2) with the compound represented by formula (6) (also referred to as "the compound of formula (6)"), the compound of formula (3) with the compound represented by formula (7) (also referred to as "the compound of formula (7)"), and the compound of formula (4) with the compound represented by formula (8) (also referred to as "the compound of formula (8)") in the above-described production method.
[ formula (5) ]
Figure BDA0003268561770000221
X in the formula (5) is-SO2-、-O-、-CO-、-C(CF3)2-, -S-or a divalent linking group selected from a hydrocarbon group having 1 to 20 carbon atoms.
[ formula (6) ]
Figure BDA0003268561770000231
X in the formula (6) is-SO2-、-O-、-CO-、-C(CF3)2-, -S-or a divalent linking group selected from a hydrocarbon group having 1 to 20 carbon atoms.
[ formula (7) ]
Figure BDA0003268561770000232
X in the formula (7) is-SO2-、-O-、-CO-、-C(CF3)2-, -S-or a divalent linking group selected from a hydrocarbon group having 1 to 20 carbon atoms.
[ formula (8) ]
Figure BDA0003268561770000233
X in the formula (8) is-SO2-、-O-、-CO-、-C(CF3)2-, -S-or a divalent linking group selected from a hydrocarbon group having 1 to 20 carbon atoms.
In the formulae (5) to (8), examples of the divalent linking group selected from the hydrocarbon groups having 1 to 20 carbon atoms include methylene, ethylene, propylene, isopropylene, butylene, phenylmethylene, phenylethylene, diphenylethylene, cyclohexylene, 3, 5-trimethylcyclohexylene, and the like.
< statement >
In the present specification, the expression "Y to Z" (Y, Z is an arbitrary number) includes the meaning of "preferably more than Y" or "preferably less than Z" in addition to the meaning of "Y to Z" unless otherwise specified.
In addition, the expression "Y or more" (Y is an arbitrary number) or "Z or less" (Z is an arbitrary number) is intended to include the meaning of "preferably more than Y" or "preferably less than Z".
[ examples ]
The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to the following examples as long as the scope of the present invention is not beyond the gist thereof.
The values of the various production conditions and evaluation results in the following examples are preferred values as the upper limit or the lower limit in the embodiment of the present invention, and the preferred ranges may be ranges defined by a combination of the values of the upper limit or the lower limit and the values in the following examples or values between the examples.
As noted, the materials used in the examples, unless otherwise indicated, were generally available as commercially available reagents. Further, various analysis methods in examples and comparative examples are as follows.
(GPC analysis)
An analysis device: dongcao HLC-8120GPC
Analysis software: dongcao GPC-8020Model II
The column was sequentially connected with TSKgel Super HM-L (Toso Cao, 6.0X 150mm, 3 μm) → TSKgel Super H1000 (Toso Cao, 6.0X 150mm, 3 μm) for use.
Column temperature: 40 deg.C
Eluent: special grade tetrahydrofuran
Flow rate: 0.4 mL/min
A detector: RI (differential refractive index) detector, 40 deg.C was set
Sample amount: 30 μ L of a 0.3 w/w% eluent solution was used
Correcting a sample: monodisperse polystyrene
The correction method comprises the following steps: polystyrene conversion (third order polynomial)
(HPLC analysis)
An analysis device: HPLC1100 manufactured by Agilent technologies
Temperature of the column: 35 deg.C
A chromatographic column: ODS-3V 3 μm 4.5X 100mm
Detector UV254nm
Eluent:
a: 0.1% by volume aqueous trifluoroacetic acid solution
B: acetonitrile
Consists of the following components: b60 was retained from 0 to 6 minutes, a gradient increasing from B60% to 90% between 6 to 11 minutes, and B90 was retained from 11 to 18 minutes.
Flow rate 1.0 mL/min
(epoxy equivalent)
According to JIS K7236: 2001.
(melting Point measurement)
An analysis device: DSC 7020 manufactured by SII Nanotechnology Inc
Measurement temperature range: 20 ℃ to 250 DEG C
Temperature rise rate: 10 ℃/min
(storage modulus of elasticity E' (250 ℃ C.))
Using a test piece obtained by cutting a cured product into pieces having a length of 5cm, a width of 1cm and a thickness of 4mm, Dynamic viscoelasticity measurement (DMA) was performed under the following conditions, and the storage elastic modulus (E') at 250 ℃ was measured.
An analysis device: EXSTAR6100 made by Seiko Instruments Inc
Measurement mode: three point bending mode
Measurement temperature range: 30 ℃ to 280 DEG C
Temperature rise rate: 5 ℃/min, cooling rate: 5 ℃/min
(shear adhesion strength to copper)
The procedure was carried out in accordance with JIS-K6850. That is, the above-mentioned composition prepared in example/comparative example having a width of 25mm × a length of 12.5mm was coated on 2 SPCC (cold rolled steel sheet) having a width of 25mm × a length of 100mm × a thickness of 1.6 mm. After the coating, the resultant was put into a thermostatic bath and cured at 120 ℃ for 2 hours and 175 ℃ for 6 hours to prepare a peel test piece.
The peel test piece thus produced was subjected to a tensile shear test at a rate of 5 mm/min using a tensile tester "Instron 5582" (manufactured by Instron corporation) and a number of times N of 3, and the tensile shear strength was measured.
< example 1>
A10L autoclave was charged with 840mL of N, N-dimethylformamide, 575g (7.51mol) of allyl chloride, 1245g (9.01mol) of potassium carbonate and 280g (1.50mol) of biphenol, and after sealing and heating to 40 ℃ the temperature was raised to 65 ℃ over 1 hour. After aging at 65 ℃ for 5 hours, the autoclave was opened after cooling to room temperature. To this were added 1678g of water and 1600g of methyl isobutyl ketone, and the inorganic salt and the crystals were dissolved, and the aqueous layer was removed by a liquid separation operation. 1678g of water was added to the remaining methyl isobutyl ketone layer three times, and after washing with water at 60 ℃, methyl isobutyl ketone was distilled off to obtain a compound of the formula (2).
(Process A)
Then, the obtained compound of formula (2) was heated at 180 ℃ for 3 hours to obtain 317g (1.19mol, two-step yield 79.3%) of the compound of formula (3).
(Process B)
Subsequently, 105g (394mmol) of the compound of the formula (3) synthesized as described above, 1028g (11.1mol) of epichlorohydrin, 400g of isopropyl alcohol and 143g of water were charged into a 3L four-necked flask, and after the mixture was dissolved by heating to 40 ℃ uniformly, 76g (912mmol) of an aqueous solution of sodium hydroxide having a concentration of 48 mass% was added dropwise thereto over 90 minutes while heating to 65 ℃. After completion of the dropwise addition, the mixture was aged at 65 ℃ for 30 minutes, and then 66g of water was added thereto to wash the mixture with water, thereby removing inorganic salts. Subsequently, epichlorohydrin and isopropanol were distilled off under reduced pressure to obtain a brown oily substance. 191g of methyl isobutyl ketone was added thereto to homogenize the mixture, and then 5.8g (69.6mmol) of a 48 mass% aqueous solution of sodium hydroxide was added thereto to react the mixture at 75 ℃ for 2 hours. To the obtained reaction solution, 223g of methyl isobutyl ketone was added, followed by washing 4 times with 525g of water at 70 ℃. Then, methyl isobutyl ketone was distilled off to obtain 142g of the compound of the formula (4) as a yellow oil.
(crystallization purification of Compound of formula (4))
56.1g of the compound of the formula (4) was put in a 1L round bottom flask, and 224mL of methanol and 101mL of 2-methoxyethanol were added and the mixture was heated to 50 ℃. The solution was slowly cooled, and white crystals precipitated when stirred at 4 ℃ for 1 hour, and were collected by filtration. After washing the white crystals with methanol, the crystals were dried under reduced pressure at 50 ℃ to obtain 29.8g (yield: 57%) of a purified product of the compound of the formula (4).
(Process C)
Subsequently, a mixed solution of 40.0g (106mmol) of the purified product of the compound of the formula (4) synthesized in the same manner as above, 1.74g (5.30mmol) of sodium tungstate dihydrate, 3.63mL (7.42mmol) of a 20% (mass/volume) aqueous phosphoric acid solution, 1.69g (2.65mmol) of N-butyl-N, N-bis [2- (4-tert-butylbenzoyloxy) ethyl ] -N-monomethylammonium sulfate, 80mL of toluene and 1.10mL of water was prepared. After the mixed solution was heated to 60 ℃ under a nitrogen stream, 26.8mL (318mmol) of 35% by mass hydrogen peroxide water was added dropwise over 5 hours, followed by aging for 2 hours. After completion of the reaction, 34mL of toluene was added, and the separated aqueous layer was taken out. After washing the remaining organic layer with 40L each of water and a 5 mass% aqueous solution of sodium thiosulfate, 40mL of methanol and 7.30g (530mmol) of potassium carbonate were added to the organic layer, and the mixture was stirred at 40 ℃ for 1 hour. To this was added 40mL of water to dissolve inorganic salts, and after removing the aqueous phase, the organic layer was washed with 40mL of 1mol/L aqueous sodium hydroxide solution 1 time and 200mL of 55 ℃ warm water 3 times. The obtained organic layer was concentrated to obtain a compound of formula (1) containing 10 mass% of toluene.
(crystallization purification of formula (1))
Subsequently, 24mL of methyl isobutyl ketone and 12mL of methanol were added to the compound of formula (1) containing 10 mass% of toluene obtained as described above, and the mixture was heated at 50 ℃ to obtain a uniform solution, and then slowly cooled to 17 ℃ to start precipitation. To this solution, 24mL of methanol was added, and the mixture was cooled in an ice bath, and the precipitated pale yellow crystals were collected by filtration. The crystals were washed with 20mL of methanol and dried under reduced pressure at 50 ℃ to obtain 41.6g (yield 78%) of pale yellow crystals of an epoxy resin containing the compound of formula (1). The epoxy resin as a purified product of the compound of the formula (1) had an epoxy equivalent of 105 and a melting point of 79 ℃.
The identification of the compound of formula (1), the compound of formula (2), the compound of formula (3) and the compound of formula (4) is performed by NMR (the same applies to the examples and comparative examples described below).
< example 2>
(method of adding a basic Compound in Process A)
165g (620mmol) of the compound of the formula (2) obtained in the same manner as in example 1 and 825mL of N, N-diethylaniline were charged into a 2L four-necked flask, heated at 200 ℃ for 6 hours, and then cooled to room temperature. Next, 495mL of water and 149mL (1.86mol) of a 50 mass% aqueous sodium hydroxide solution were added to a 2L split flask, and the resulting mixture was cooled to 10 ℃ and the N, N-diethylaniline solution was added dropwise over 15 minutes, stirred for 30 minutes and then allowed to stand, and then the upper layer and the lower layer were taken out. Next, 495mL of water and 93.1g (1.86mol) of concentrated sulfuric acid were added to a 2L split flask, and after cooling to 10 ℃ the lower layer taken out in the previous operation was added dropwise and stirred for 1 hour. The precipitated solid was collected by filtration, washed with water, and dried under reduced pressure to obtain 148g (1.19mol, two-step yield 80.4%) of the compound of formula (3) as a gray solid.
(Process B, Process C, and crystallization purification of Compound of formula (1))
The procedure of example 1 was repeated except that the compound of formula (4) was not subjected to crystallization purification to obtain a pale yellow powder of an epoxy resin containing the compound of formula (1). The epoxy resin had an epoxy equivalent of 107 and a melting point of 69 ℃.
< example 3>
(method of adding basic Compound in Process A, Process B, and Process C)
The yellow oil (compound of formula (4)) containing 9 mass% of toluene obtained in the same manner as in example 2 was further concentrated, and toluene was completely distilled off to obtain a yellow solid of an epoxy resin containing the compound of formula (1). The epoxy resin had an epoxy equivalent of 113 and a melting point of 65 ℃.
< comparative example 1>
(method of adding basic Compound in Process A, Process B)
The conversion from the compound of formula (2) to the compound of formula (3) was carried out in the same manner as in example 2, and the conversion from the compound of formula (3) to the compound of formula (4) was carried out in the same manner as in example 1, to obtain the compound of formula (4) as a pale yellow solid.
(column purification of Compound of formula (4), Process C)
The compound of formula (4) was purified by silica gel column to obtain white crystals of a purified compound of formula (4) having an HPLC purity of 99.7 area%. Using the purified product of the compound of formula (4), step C was performed in the same manner as in example 1 to obtain a pale yellow powder of an epoxy resin containing the compound of formula (1). The epoxy resin had an epoxy equivalent of 109 and a melting point of 79 ℃.
< comparative example 2>
(Process A, Process B)
The compound of formula (4) was synthesized according to the method of Japanese patent No. 2539648.
(Process C)
50.0g (132mmol) of the compound of the formula (4) was dissolved in 250mL of chloroform and heated to 50 ℃. 97.6g (396mmol) of m-chloroperoxybenzoic acid (containing 30 mass% water) was added thereto over a half hour, and further stirred at 50 ℃ for 30 minutes. After cooling to room temperature, 100mL of a 5% by mass aqueous solution of sodium thiosulfate was added, and after stirring for 1 hour, the aqueous layer was removed, and the remaining organic layer was washed with 400mL of a 1mol/L aqueous solution of sodium hydroxide. Further, the mixture was washed 3 times with 250mL of 75 ℃ warm water, and then concentrated. As a result, 38.2g of a brown oil of the epoxy resin containing the compound of the formula (1) was obtained. The epoxy resin had an epoxy equivalent of 121.
GPC analysis of the epoxy resins containing the compound of formula (1) obtained in examples 1 to 3 and comparative examples 1 to 2 was conducted under the above conditions, and it was found that the components having a standard polystyrene equivalent molecular weight of 60.8 or more were contained in the following area% as shown in Table 1.
[ Table 1]
Test specimen Comparative example 1 Example 1 Example 2 Example 3 Comparative example 2
A component having a standard styrene equivalent molecular weight of 60.8 or more in GPC (A%) 7.5 10.4 16.5 20.0 29.2
< examples 4 to 6 and comparative examples 3 to 4>
(curing of epoxy resin)
The epoxy resins produced in examples 1 to 3 and comparative examples 1 to 2 were mixed with a curing agent PSM4261 (manufactured by Sanyo chemical Co., Ltd.) in the ratio shown in Table 2 and mixed at 100 ℃ until uniform. Next, triphenyl phosphate (manufactured by hokken chemical industries, ltd.) as a curing accelerator was added thereto, and the mixture was stirred until uniform, thereby obtaining a liquid epoxy resin composition.
Using 2 pieces of sheet inside the side of the release PET film glass plate, to prepare a casting plate, adjusted to 2mm thickness, to the injection molding plate casting the epoxy resin composition (liquid), 120 degrees C2 hours, 175 degrees C6 hours heating, obtain the cured product.
[ Table 2]
Figure BDA0003268561770000301
It is found that the cured products of examples 4 to 6 have a higher storage elastic modulus (E') at 250 ℃ than those of comparative examples 3 and 4. Furthermore, the cured products of examples 4 and 5 have higher shear adhesion strength to copper than those of comparative examples 3 and 4. Since an epoxy resin containing an epoxy compound represented by the formula (1) has both moldability and heat resistance of a cured product as compared with conventional epoxy resins, it is suitable for use as a material for devices used in a high-temperature environment, has a high modulus of elasticity at high temperature, and has high shear adhesion strength to copper, and therefore, it is suitable for use as a matrix resin for composite materials requiring particularly high mechanical strength, and for use as a semiconductor encapsulating material requiring bondability to copper wires.
< comparative example 5, examples 7 to 8>
(Water extraction test)
An epoxy resin composition was prepared by adding a curing agent PSM4261 (manufactured by NIGHT CHEMICAL CO., LTD., 105, containing the epoxy compound represented by the formula (1) prepared in the same manner as in example 2, and curing products were prepared in the same manner as in examples 4 to 6.
The cured product was pulverized by a Wonder Blender (manufactured by Osaka chemical Co., Ltd.), and 8g of the obtained powder passing through a 20-mesh sieve was weighed in a bottle made of polyethylene. 80mL of ultrapure water was added thereto, the lid was closed, and the mixture was held in a 95 ℃ desiccator for 20 hours. Then, it was cooled to room temperature, and the supernatant was filtered with No.5A filter paper to obtain extract water. The pH and conductivity of the obtained extract water are shown in the following table.
[ Table 3]
Figure BDA0003268561770000311
The cured products of examples 7 to 8 showed less ionic components in the cured products than comparative example 5, since the pH of the extract water was high and the conductivity was low. Accordingly, the cured product of the epoxy resin composition of the present invention is expected to have an effect of inhibiting corrosion of metals in contact with each other, and therefore, can be suitably used for applications such as semiconductor sealing materials.
In the above examples, the content ratio of the component having a standard polystyrene equivalent molecular weight of 60.8 or more was adjusted to be within a predetermined range by purifying the component by crystallization so that the content ratio of the component having a standard polystyrene equivalent molecular weight of 60.8 or more was within a predetermined range, or by performing the claisen rearrangement reaction in the presence of a basic compound. However, based on the above examples and the test results conducted by the present inventors, it was confirmed that a predetermined effect can be obtained if the content ratio of the component having the standard polystyrene equivalent molecular weight of 60.8 or more is within a predetermined range, and therefore, it is considered that the same effect can be obtained even if another method is employed such that the content ratio of the component having the standard polystyrene equivalent molecular weight of 60.8 or more is within a predetermined range.
The compound represented by formula (1) has a structure in which 2 phenyl groups are covalently bonded by a single bond (direct bond). It is believed that even the 2 phenyl groups are bonded in various ways, e.g. via-SO2-、-O-、-CO-、-C(CF3)2The linkage of-S-or a divalent linking group selected from a hydrocarbon group having 1 to 20 carbon atoms does not significantly affect the properties of the epoxy resin. The present invention can be produced in the same manner as in the case of a single bond (direct bond). Therefore, it is expected that the compound represented by the formula (5) can be produced in the same manner as the compound represented by the formula (1) and can exhibit the same action and effect.

Claims (20)

1. An epoxy resin which is characterized by containing 3,3 '-diglycidyl biphenyl-4, 4' -diglycidyl ether represented by the following formula (1), also referred to as a "compound of the formula (1)",
the epoxy resin contains a component having a standard polystyrene equivalent molecular weight of not less than 9% by area and not more than 25% by area as measured by using an RI detector in gel permeation chromatography, namely referred to as "GPC",
[ formula (1) ]
Figure FDA0003268561760000011
2. An epoxy resin characterized by containing a compound represented by the following formula (5),
the epoxy resin contains a component having a standard polystyrene equivalent molecular weight of not less than 9% by area and not more than 25% by area as measured by using an RI detector in gel permeation chromatography, namely referred to as "GPC",
[ formula (5) ]
Figure FDA0003268561760000012
X in the formula (5) is-SO2-、-O-、-CO-、-C(CF3)2-, -S-or a divalent linking group selected from a hydrocarbon group having 1 to 20 carbon atoms.
3. The epoxy resin according to claim 1 or 2, wherein the component having a standard polystyrene equivalent molecular weight of 60.8 or more in GPC is a compound having 2 or more biphenyl skeletons.
4. A method for producing an epoxy resin, comprising the steps of: a step of obtaining an epoxy resin by carrying out a reaction of converting a compound represented by the following formula (2), also referred to as a "compound of formula (2"), into a compound represented by the following formula (3), also referred to as a "compound of formula (3)", then carrying out a reaction of converting the compound of formula (3) into a compound represented by the following formula (4), also referred to as a "compound of formula (4)", then carrying out a reaction of converting the compound of formula (4) into a compound of formula (1) represented by the following formula (1),
in the method for producing an epoxy resin, the content ratio of a component having a standard polystyrene equivalent molecular weight of 60.8 or more in the epoxy resin is 9 to 25 area% when measured by using an RI detector in GPC,
[ formula (1) ]
Figure FDA0003268561760000021
[ formula (2) ]
Figure FDA0003268561760000022
[ formula (3) ]
Figure FDA0003268561760000023
[ formula (4) ]
Figure FDA0003268561760000024
5. The method for producing an epoxy resin according to claim 4, wherein the following reaction is carried out: subjecting the compound of formula (2) to claisen rearrangement in the presence of a basic compound to convert into the compound of formula (3).
6. The method for producing an epoxy resin according to claim 5, wherein the basic compound is added to the compound of formula (2) in a proportion of 1.0 mol or more and 100 mol or less relative to 1.0 mol of the compound, and the mixture is reacted.
7. The method for producing an epoxy resin according to claim 5 or 6, wherein the basic compound is an aniline compound.
8. The method for producing an epoxy resin according to claim 4, wherein, after the reaction for converting the compound of formula (2) into the compound of formula (3) is carried out and before the reaction for converting the compound of formula (3) into the compound of formula (4) is carried out,
the compound of the formula (3) is purified by separating and removing components other than the compound.
9. The method for producing an epoxy resin according to claim 4 or 8, wherein, after the reaction for converting the compound of formula (3) into the compound of formula (4) is carried out and before the reaction for converting the compound of formula (4) into the compound of formula (1) is carried out,
the compound of the formula (4) is purified by separating and removing components other than the compound.
10. The method for producing an epoxy resin according to claim 4, 8 or 9, wherein, after the reaction for converting the compound of formula (4) into the compound of formula (1) is carried out,
the compound of the formula (1) is purified by separating and removing components other than the compound.
11. A method for producing an epoxy resin, comprising the steps of: a step of obtaining an epoxy resin by carrying out a reaction of converting a compound represented by the following formula (6), also referred to as a "compound of formula (6)," into a compound represented by the following formula (7), also referred to as a "compound of formula (7)," then carrying out a reaction of converting the compound of formula (7) into a compound represented by the following formula (8), also referred to as a "compound of formula (8)," then carrying out a reaction of converting the compound of formula (8) into a compound of formula (5) represented by the following formula (5),
in the method for producing an epoxy resin, the content ratio of a component having a standard polystyrene equivalent molecular weight of 60.8 or more in the epoxy resin is 9 to 25 area% when measured by using an RI detector in GPC,
[ formula (5) ]
Figure FDA0003268561760000041
X in the formula (5) is-SO2-、-O-、-CO-、-C(CF3)2-, -S-or a divalent linking group selected from a hydrocarbon group having 1 to 20 carbon atoms,
[ formula (6) ]
Figure FDA0003268561760000042
X in the formula (6) is-SO2-、-O-、-CO-、-C(CF3)2-, -S-or a divalent linking group selected from a hydrocarbon group having 1 to 20 carbon atoms,
[ formula (7) ]
Figure FDA0003268561760000043
X in the formula (7) is-SO2-、-O-、-CO-、-C(CF3)2-, -S-or a divalent linking group selected from a hydrocarbon group having 1 to 20 carbon atoms,
[ formula (8) ]
Figure FDA0003268561760000051
X in the formula (8) is-SO2-、-O-、-CO-、-C(CF3)2-, -S-or a divalent linking group selected from a hydrocarbon group having 1 to 20 carbon atoms.
12. The method for producing an epoxy resin according to claim 11, wherein the following reaction is carried out: subjecting the compound of formula (6) to claisen rearrangement in the presence of a basic compound to convert into the compound of formula (7).
13. The method for producing an epoxy resin according to claim 12, wherein the basic compound is added to the compound of formula (6) in a proportion of 1.0 mol or more and 100 mol or less relative to 1.0 mol of the compound, and the mixture is reacted.
14. The method for producing an epoxy resin according to claim 12 or 13, wherein the basic compound is an aniline compound.
15. The method for producing an epoxy resin according to claim 11, wherein, after the reaction for converting the compound of formula (6) into the compound of formula (7) is carried out and before the reaction for converting the compound of formula (7) into the compound of formula (8) is carried out,
purification is carried out by separating and removing components other than the compound of the formula (7).
16. The method for producing an epoxy resin according to claim 11 or 15, wherein, after the reaction for converting the compound of formula (7) into the compound of formula (8) is carried out and before the reaction for converting the compound of formula (8) into the compound of formula (5) is carried out,
purification is carried out by separating and removing components other than the compound of the formula (8).
17. The method for producing an epoxy resin according to claim 11, 15 or 16, wherein, after the reaction for converting the compound of formula (8) into the compound of formula (5) is carried out,
the compound of the formula (5) is purified by separating and removing components other than the compound.
18. The method for producing an epoxy resin according to claim 8, 9, 10, 15, 16 or 17, wherein the purification is performed by crystallization.
19. An epoxy resin composition comprising the epoxy resin according to any one of claims 1 to 3 and an epoxy curing agent in a proportion of 0.80 equivalent or more and 1.03 equivalent or less of functional group equivalent to the epoxy resin.
20. A cured product obtained by curing the epoxy resin composition according to claim 19.
CN202080022416.7A 2019-03-25 2020-03-09 Epoxy resin and method for producing same Active CN113710719B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2019056074 2019-03-25
JP2019-056074 2019-03-25
PCT/JP2020/009918 WO2020195733A1 (en) 2019-03-25 2020-03-09 Epoxy resin and method for producing same

Publications (2)

Publication Number Publication Date
CN113710719A true CN113710719A (en) 2021-11-26
CN113710719B CN113710719B (en) 2024-03-01

Family

ID=72611449

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202080022416.7A Active CN113710719B (en) 2019-03-25 2020-03-09 Epoxy resin and method for producing same

Country Status (5)

Country Link
JP (1) JP7556347B2 (en)
KR (1) KR20210151777A (en)
CN (1) CN113710719B (en)
TW (1) TW202100603A (en)
WO (1) WO2020195733A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115340809A (en) * 2022-08-30 2022-11-15 深圳新红进科技有限公司 Antistatic epoxy floor coating and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20240149393A (en) * 2022-02-01 2024-10-14 아지노모토 가부시키가이샤 Underfill

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4789711A (en) * 1986-12-02 1988-12-06 Ciba-Geigy Corporation Multifunctional epoxide resins
CN102372835A (en) * 2010-07-08 2012-03-14 日东电工株式会社 Method for manufacturing cured product of thermosetting resin composition and cured product obtained thereby
JP2015127397A (en) * 2013-11-27 2015-07-09 昭和電工株式会社 Curable resin composition
JP2015166335A (en) * 2013-10-02 2015-09-24 三菱化学株式会社 Method for producing epoxy compound and catalyst composition for epoxidation reaction
JP2016094353A (en) * 2014-11-12 2016-05-26 昭和電工株式会社 Method for producing polyvalent glycidyl compound
JP2016204647A (en) * 2015-04-15 2016-12-08 三菱化学株式会社 Polyfunctional epoxy resin and intermediate, epoxy resin composition, and cured product
JP2017149878A (en) * 2016-02-25 2017-08-31 国立大学法人横浜国立大学 Curable resin composition and curable molding material
CN108026228A (en) * 2015-09-29 2018-05-11 日本化药株式会社 Allyl ether resin, methacrylic ether resin, epoxy resin, epoxy resin component and its hardening thing being substituted
JP2018141151A (en) * 2017-02-28 2018-09-13 三菱ケミカル株式会社 Polyfunctional epoxy resin composition, and cured product obtained by curing the polyfunctional epoxy resin composition

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4789711A (en) * 1986-12-02 1988-12-06 Ciba-Geigy Corporation Multifunctional epoxide resins
CN102372835A (en) * 2010-07-08 2012-03-14 日东电工株式会社 Method for manufacturing cured product of thermosetting resin composition and cured product obtained thereby
JP2015166335A (en) * 2013-10-02 2015-09-24 三菱化学株式会社 Method for producing epoxy compound and catalyst composition for epoxidation reaction
JP2015127397A (en) * 2013-11-27 2015-07-09 昭和電工株式会社 Curable resin composition
JP2016094353A (en) * 2014-11-12 2016-05-26 昭和電工株式会社 Method for producing polyvalent glycidyl compound
JP2016204647A (en) * 2015-04-15 2016-12-08 三菱化学株式会社 Polyfunctional epoxy resin and intermediate, epoxy resin composition, and cured product
CN108026228A (en) * 2015-09-29 2018-05-11 日本化药株式会社 Allyl ether resin, methacrylic ether resin, epoxy resin, epoxy resin component and its hardening thing being substituted
JP2017149878A (en) * 2016-02-25 2017-08-31 国立大学法人横浜国立大学 Curable resin composition and curable molding material
JP2018141151A (en) * 2017-02-28 2018-09-13 三菱ケミカル株式会社 Polyfunctional epoxy resin composition, and cured product obtained by curing the polyfunctional epoxy resin composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115340809A (en) * 2022-08-30 2022-11-15 深圳新红进科技有限公司 Antistatic epoxy floor coating and preparation method thereof
CN115340809B (en) * 2022-08-30 2023-08-15 宁波恒翔涂料有限公司 Antistatic epoxy floor coating and preparation method thereof

Also Published As

Publication number Publication date
JP7556347B2 (en) 2024-09-26
CN113710719B (en) 2024-03-01
KR20210151777A (en) 2021-12-14
WO2020195733A1 (en) 2020-10-01
JPWO2020195733A1 (en) 2020-10-01
TW202100603A (en) 2021-01-01

Similar Documents

Publication Publication Date Title
TWI396716B (en) Epoxy resin composition, cured article, novel epoxy resin, novel phenol resin and semiconductor encapsulating material
CN107400198B (en) Epoxy resin composition and cured product thereof
EP2343327A1 (en) Curable resin composition and cured product thereof, printed circuit board, and epoxy resin and method for producing same
CN112334513A (en) Maleimide resin, curable resin composition, and cured product thereof
WO2020054526A1 (en) Maleimide resin, curable resin composition, and cured product thereof
KR20100126490A (en) Polyphenolic compounds and epoxy resins comprising cycloaliphatic moieties and process for the production thereof
KR101143131B1 (en) Epoxy compound, preparation method thereof, and use thereof
CN113710719B (en) Epoxy resin and method for producing same
WO2017170844A1 (en) Thermosetting resin composition, prepreg and cured product thereof
KR101407434B1 (en) Liquid Epoxy Resin, Epoxy Resin Composition, and Cured Product
JP5002897B2 (en) Polyhydric hydroxy compound, epoxy resin, production method thereof, epoxy resin composition and cured product
JP6227505B2 (en) Epoxy resin composition and cured epoxy resin
TWI438216B (en) Modified liquid epoxy resin, epoxy resin composition by using modified liquid epoxy resin and cured product thereof
KR20020031316A (en) Epoxy Resin Composition and Process for Producing the Same
JP2004010877A (en) Crystalline epoxy resin and its manufacturing method
JP2017061665A (en) Calixarene compound, composition, method for producing the same, epoxy resin curing agent, epoxy resin composition, laminate, semiconductor sealing material and semiconductor device
KR101954484B1 (en) Method for producing cyanuric acid-modified phosphorus-containing epoxy resin, resin composition containing cyanuric acid-modified phosphorus-containing epoxy resin, and cured product of same
TW202006038A (en) Reactive diluent, composition, sealing material, cured product, substrate, electronic component, epoxy compound, and method of producing compound
TW201835134A (en) Substituted allyl ether resin, methallyl ether resin, epoxy resin, curable resin composition, and cured products of these
KR102708618B1 (en) Tetramethylbiphenol epoxy resin and method for preparing the same
JP3721319B2 (en) Method for producing phenolic resin and epoxy resin
JP4674884B2 (en) Production method of epoxy resin
JP4004787B2 (en) Phenol resin, epoxy resin, production method thereof, and resin composition for semiconductor encapsulant
JP3955199B2 (en) Phenol resin, epoxy resin, production method thereof, and resin composition for semiconductor encapsulant
JP6043602B2 (en) Resin composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant