CN110719926B - Epoxy resin, method for producing same, epoxy resin composition, and cured product thereof - Google Patents

Epoxy resin, method for producing same, epoxy resin composition, and cured product thereof Download PDF

Info

Publication number
CN110719926B
CN110719926B CN201880037755.5A CN201880037755A CN110719926B CN 110719926 B CN110719926 B CN 110719926B CN 201880037755 A CN201880037755 A CN 201880037755A CN 110719926 B CN110719926 B CN 110719926B
Authority
CN
China
Prior art keywords
epoxy resin
resin composition
mass
resin
cured product
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.)
Active
Application number
CN201880037755.5A
Other languages
Chinese (zh)
Other versions
CN110719926A (en
Inventor
广田阳祐
中村信哉
秋元源祐
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.)
DIC Corp
Original Assignee
DIC 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 DIC Corp filed Critical DIC Corp
Publication of CN110719926A publication Critical patent/CN110719926A/en
Application granted granted Critical
Publication of CN110719926B publication Critical patent/CN110719926B/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
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/02—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising combinations of reinforcements, e.g. non-specified reinforcements, fibrous reinforcing inserts and fillers, e.g. particulate fillers, incorporated in matrix material, forming one or more layers and with or without non-reinforced or non-filled layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
    • C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with 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
    • C07D303/12—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
    • 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
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Epoxy Compounds (AREA)

Abstract

An object of the present invention is to provide an epoxy resin, a composition and a cured product thereof, which are excellent in the balance between the molding shrinkage rate of the composition containing the epoxy resin during heat curing and the heat resistance of the cured product. Specifically disclosed is an epoxy resin which is a tetramethylbiphenol-type epoxy resin represented by the following structural formula (wherein n represents a repeating number and is an integer of 0-5), wherein the content of 1, 2-diol in the resin is 0.065-0.10 meq/g.

Description

Epoxy resin, method for producing same, epoxy resin composition, and cured product thereof
Technical Field
The present invention relates to an epoxy resin which has a low shrinkage ratio during heat curing and an excellent balance between heat resistance of a cured product and which is suitable for use in a semiconductor sealing material or the like, a method for producing the same, an epoxy resin composition containing the epoxy resin, and a cured product thereof.
Background
Curable resin compositions using epoxy resins and various curing agents are widely used in the electrical/electronic fields such as semiconductor sealing materials and insulating materials for printed wiring boards, from the viewpoint of excellent heat resistance and moisture resistance of the resulting cured products, in addition to adhesives, molding materials, paints, photoresist materials, color developing materials, and the like.
Among these various applications, there is a strong demand for reduction in thickness and weight in the electrical and electronic fields, and as one of mounting techniques to meet these demands, there is a chip-scale packaging technique. The wafer level packaging technology is a mounting technology for manufacturing a semiconductor package by performing resin sealing, rewiring, and electrode formation in a wafer state and dicing to obtain individual pieces. Since the collective sealing is performed with the sealing resin, warpage occurs due to shrinkage at the time of curing the resin and a difference in shrinkage amount caused by a linear expansion coefficient of the chip and a linear expansion coefficient of the sealing resin. Since this warpage significantly reduces the reliability of the package, the sealing resin is required to have a low viscosity, a low molding shrinkage, and a low elastic modulus for the purpose of suppressing warpage.
For example, biphenyl type epoxy resins having excellent moisture resistance and heat resistance are known as epoxy resins that can be suitably used for electronic material applications, particularly semiconductor sealing materials and laminate sheets (see, for example, patent document 1). Alternatively, it is also known that an epoxy resin having a naphthyl ether skeleton is suitable as a semiconductor sealing material (for example, see patent document 2).
By using the epoxy resin proposed in the above patent document and the like as a main component of a curable resin composition, although a certain effect can be obtained in terms of the fluidity of the composition, the strength of a cured product, and the like, as compared with the case of using a general bisphenol type epoxy resin, the balance levels of the molding shrinkage ratio at the time of heat curing of a resin composition and the heat resistance of a cured product, which have been required in recent years, cannot be sufficiently satisfied, and further improvement has been required.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016-108562
Patent document 2: japanese patent laid-open publication No. 2016-089096
Disclosure of Invention
Problems to be solved by the invention
Accordingly, an object of the present invention is to provide an epoxy resin having an excellent balance between a molding shrinkage ratio of a composition containing an epoxy resin during heat curing and heat resistance of a cured product, a method for producing the same, a composition, and a cured product thereof.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the present inventors have completed the present invention by finding that a biphenyl type epoxy resin containing a certain amount of a 1, 2-diol can reduce the molding shrinkage rate during heat curing without impairing the heat resistance of a cured product by using the resin as one component of a curable composition.
Specifically disclosed is an epoxy resin which is a tetramethylbiphenol-type epoxy resin represented by the following formula (1) and which is characterized in that the content of 1, 2-diol in the resin is 0.065-0.10 meq/g.
Figure BDA0002306079340000021
(wherein n represents a repetition number and is an integer of 0 to 5.)
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided an epoxy resin which is excellent in the balance between the molding shrinkage rate of the resin composition during heat curing and the heat resistance of the molded product and which can be suitably used for a semiconductor sealing material or the like, a method for producing the same, an epoxy resin composition, a cured product having the above-mentioned properties, a semiconductor sealing material, a semiconductor device, a prepreg, a circuit board, a build-up film, a build-up substrate, a fiber-reinforced composite material, and a fiber-reinforced molded product.
Drawings
FIG. 1 is a GPC chart of the epoxy resin synthesized in example 1.
FIG. 2 is a GPC chart of the epoxy resin synthesized in example 2.
Detailed Description
< epoxy resin >
The present invention will be described in detail below.
The epoxy resin is a tetramethylbiphenol-type epoxy resin represented by the following structural formula (1), and the content of 1, 2-diol in the resin is 0.065-0.10 meq/g.
Figure BDA0002306079340000031
(wherein n represents a repetition number of 0 to 5.)
In the above formula, n represents the number of repetitions, and is particularly suitable for use in a semiconductor sealing material or the like, and the average value thereof is preferably in the range of 0.01 to 0.30, and particularly preferably in the range of 0.01 to 0.15, from the viewpoint of low viscosity.
The 1, 2-diol in the epoxy resin of the present invention is a 1, 2-diol in which the terminal epoxy group in the above formula forms a 1, 2-diol, and may be an epoxy group at one terminal or a 1, 2-diol formed at both terminals, and in the present invention, the content obtained by the measurement method described below based on the total of these components is necessarily 0.065 to 0.10 meq/g.
Typical examples of the 1, 2-diol compound in the present invention include compounds represented by the following formulae.
Figure BDA0002306079340000041
(wherein n represents a repetition number and is an integer of 0 to 5.)
The 1, 2-diol has been conventionally considered as an impurity in the epoxidation reaction, and since it has no epoxy group or only a single terminal epoxy group and thus does not participate in the three-dimensional crosslinking structure, it is considered to be a substance that adversely affects the heat resistance of a cured product, and it has been conventionally considered that it is necessary to maintain the heat resistance of a cured product to make the content of the 1, 2-diol as zero as possible.
However, if all the raw materials undergo a crosslinking reaction during thermal curing, shrinkage occurs during heating, and as a result, problems such as warpage are likely to occur. In the present invention, a method for reducing such thermal shrinkage is studied, and as a result, it is found that: it is effective to include 1, 2-diol bodies in the composition.
Therefore, when the content of the 1, 2-diol is less than 0.065meq/g, the shrinkage rate during heat molding becomes high as in the case of the conventional biphenyl type epoxy resin, while when the content exceeds 0.10meq/g, the heat resistance of the resulting cured product is easily affected.
The epoxy equivalent of the epoxy resin of the present invention is preferably 178 to 250g/eq, and particularly preferably 178 to 220g/eq, from the viewpoint of the balance between the molding shrinkage rate during heat curing and the heat resistance of the cured product.
The n in the structural formula (1) of the epoxy resin in the present invention and the average value thereof are calculated by GPC measurement under the following conditions.
< GPC measurement conditions >
A measuring device: HLC-8320GPC, manufactured by Tosoh corporation,
Column: "HXL-L" protective column manufactured by Tosoh corporation "
+ TSK-GEL G2000HXL manufactured by Tosoh corporation "
+ TSK-GEL G2000HXL manufactured by Tosoh corporation "
+ TSK-GEL G3000HXL manufactured by Tosoh corporation "
+ manufactured by Tosoh corporation of "TSK-GEL G4000 HXL"
A detector: RI (differential refractometer)
Data processing: "GPC workstation Eco SEC-Work Station" manufactured by Tosoh corporation "
The measurement conditions were as follows: column temperature 40 deg.C
Tetrahydrofuran as developing solvent
Flow rate 1.0 ml/min
The standard is as follows: the following monodisperse polystyrenes of known molecular weights were used according to the manual of the aforementioned "GPC workstation Eco SEC-Work Station".
(use of polystyrene)
"A-500" made by Tosoh corporation "
"A-1000" made by Tosoh corporation "
"A-2500" made by Tosoh corporation "
"A-5000" manufactured by Tosoh corporation "
"F-1" made by Tosoh corporation "
"F-2" made by Tosoh corporation "
"F-4" made by Tosoh corporation "
"F-10" made by Tosoh corporation "
"F-20" made by Tosoh corporation "
"F-40" made by Tosoh corporation "
"F-80" made by Tosoh corporation "
"F-128" made by Tosoh corporation "
Sample preparation: a tetrahydrofuran solution (1.0 mass% in terms of solid content of the resin) was filtered through a microfilter to obtain a sample (50. mu.l).
The method of measuring the content of 1, 2-diol in the present invention is carried out according to the method described in "quantification of 1, 2-diol contained in epoxy resin by potentiometric titration and reliability thereof" report by analysis by saitoi et al, "BUNSEKI KAGAKU vol.57, No.6, pp.499-503(2008), which is improved to a method using a commercially available automatic titrator based on JIS K7146, and can be calculated by adding potassium iodide to the remaining periodic acid and titrating the generated iodine with a sodium thiosulfate solution, in view of the fact that 1, 2-diol reacts with periodic acid quantitatively and is cleaved to be oxidized into carbonyl compounds.
< method for producing epoxy resin >
As described above, the epoxy resin of the present invention is represented by the structural formula (1), and contains 1, 2-diol in a certain range. Therefore, the 1, 2-diol separately synthesized may be added to the resin composed of only the compound represented by the structural formula (1) to adjust the range specified in the present invention, but from the viewpoint of obtaining the epoxy resin of the present invention by a single reaction, a production method having a reaction step of performing epoxidation using 3,3 ', 5, 5' -tetramethylbiphenol, glycidol and epihalohydrin is preferably used.
Commercially available products of 3,3 ', 5, 5' -tetramethylbiphenol, glycidol and epihalohydrin, which are industrially available, can be used, respectively.
The ratio of the glycidol is preferably 1 to 10 parts by mass, particularly preferably 1 to 8 parts by mass, based on 100 parts by mass of 3,3 ', 5, 5' -tetramethylbiphenol, from the viewpoint of easily adjusting the content of the 1, 2-diol in the obtained epoxy resin to the range specified in the present invention.
The following methods can be exemplified: the epihalohydrin is added in an amount of 1 to 10 moles based on 1 mole of hydroxyl groups contained in the raw material 3,3 ', 5, 5' -tetramethylbiphenol ester, and the mixture is reacted at a temperature of 20 to 120 ℃ for 0.5 to 10 hours while adding 0.9 to 2.0 moles of a basic catalyst together or slowly to 1 mole of hydroxyl groups of the raw material. The basic catalyst may be in a solid state or an aqueous solution thereof, and when an aqueous solution is used, the following method may be used: while continuously adding, water and epihalohydrins are continuously distilled out of the reaction mixture under reduced pressure or atmospheric pressure, liquid separation is further performed to remove water, and the epihalohydrins are continuously returned to the reaction mixture.
From the viewpoint of easily adjusting the content of the 1, 2-diol in the epoxy resin of the present invention to the range specified in the present invention, the reaction temperature is preferably in the range of 20 to 90 ℃, and the reaction time is preferably in the range of 0.5 to 24 hours.
In the case of industrial production, all the epihalohydrins used in the charge are new in the first batch of the production of the epoxy resin, but it is preferable to use the epihalohydrins recovered from the crude reaction product and new epihalohydrins in an amount equivalent to the amount lost by the reaction after the next batch. In this case, the epihalohydrin to be used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, β -methylepichlorohydrin, and the like. Among these, epichlorohydrin is preferable from the viewpoint of easy industrial availability.
Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, from the viewpoint of excellent catalytic activity of the epoxy resin synthesis reaction, an alkali metal hydroxide is preferable, and examples thereof include sodium hydroxide and potassium hydroxide. When used, these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or may be used in the form of a solid. In addition, the use of an organic solvent in combination can increase the reaction rate in the synthesis of an epoxy resin. Such an organic solvent is not particularly limited, and examples thereof include ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, sec-butanol and tert-butanol; cellosolves such as methyl cellosolve and ethyl cellosolve; ethers such as tetrahydrofuran, 1, 4-dioxane, 1, 3-dioxane, diethoxyethane, etc.; aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone, or two or more of them may be used in combination as appropriate for adjusting the polarity.
Further, from the viewpoint of suitably obtaining the epoxy resin of the present invention, it is preferable to use the aforementioned organic solvent and water in combination. In this case, the ratio of water in the mixed solvent is preferably 5 to 60 parts by mass, and particularly preferably 10 to 50 parts by mass, per 100 parts by mass of the mixed solvent.
In addition, the epoxy resin of the present invention can be obtained by increasing the ratio of water used in the mixed solvent as a raw material without using glycidol, and in this case, the content of water in the mixed solvent is preferably about 10 to 50 mass%.
When the basic catalyst used in the epoxidation reaction is an aqueous solution, the content of water contained in the aqueous solution is not included in the water defined as the water in the mixed solvent.
Next, the epoxidation reaction product is washed with water, and then unreacted epihalohydrin and a solvent used in combination are distilled off by distillation under reduced pressure and heating. In order to further produce an epoxy resin having a small amount of hydrolyzable halogen, the obtained epoxy resin may be dissolved again in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, or the like, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, or the like may be added thereto to further perform the reaction. In this case, a transfer catalyst such as a quaternary ammonium salt or a crown ether may be present for the purpose of increasing the reaction rate. The amount of the phase transfer catalyst used is preferably in the range of 0.1 to 3.0% by mass based on the epoxy resin used. After the reaction is completed, the formed salt is removed by filtration, washing with water, or the like, and a solvent such as toluene or methyl isobutyl ketone is distilled off under heating and reduced pressure, whereby an epoxy resin having a low content of hydrolyzable chlorine can be obtained.
< epoxy resin composition >
The epoxy resin of the present invention may use the curing agent (B) in combination. By adding the curing agent (B) to the epoxy resin, a curable epoxy resin composition can be produced.
Examples of the curing agent (B) usable herein include various known curing agents for epoxy resins such as amine compounds, amide compounds, acid anhydride compounds, and phenol compounds.
Specific examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, and BF3Examples of the amide compound include polyamide resins synthesized from ethylenediamine and dimers of dicyandiamide and linolenic acid. Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Examples of the phenol compound include phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, and bicyclo resinPentadienylphenol addition type resin, phenol aralkyl resin (ZYLOC resin), naphthol aralkyl resin, trishydroxyphenylmethane resin, tetrahydroxyphenylethane resin, naphthol novolac resin, a naphthol-phenol co-condensed novolak resin, a naphthol-cresol co-condensed novolak resin, a biphenyl-modified phenolic resin (a polyhydric phenol-containing hydroxyl compound in which phenol nuclei are linked by a dimethylene group), a biphenyl-modified naphthol resin (a polyhydric naphthol compound in which phenol nuclei are linked by a dimethylene group), an aminotriazine-modified phenolic resin (a polyhydric phenol-containing hydroxyl compound in which phenol nuclei are linked by melamine, benzoguanamine, or the like), an alkoxy group-containing aromatic ring-modified phenolic novolak resin (a polyhydric phenol-containing hydroxyl compound in which phenol nuclei and an alkoxy group-containing aromatic ring are linked by formaldehyde), and other polyhydric phenol-containing hydroxyl compounds.
Further, the epoxy resin composition of the present invention may be used in combination with an epoxy resin (C) other than the epoxy resin of the present invention within a range not impairing the effects of the present invention.
Examples of the epoxy resin (C) include bisphenol a type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, polyhydroxynaphthalene type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane type epoxy resins, dicyclopentadiene-phenol addition reaction type epoxy resins, phenol aralkyl type epoxy resins, naphthol novolac type epoxy resins, naphthol aralkyl type epoxy resins, naphthol-phenol condensed novolac type epoxy resins, naphthol-cresol condensed novolac type epoxy resins, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resins, biphenyl modified novolac type epoxy resins, and the like. Among these epoxy resins, tetramethylbiphenol-type epoxy resins, biphenylaralkyl-type epoxy resins, polyhydroxy naphthalene-type epoxy resins, and novolac-type epoxy resins are preferably used from the viewpoint of obtaining cured products excellent in flame retardancy, and dicyclopentadiene-phenol addition reaction-type epoxy resins are preferably used from the viewpoint of obtaining cured products excellent in dielectric characteristics. In addition, when another epoxy resin (C) is used in combination, from the viewpoint of easily exhibiting the effect of the present invention, it is preferable that the epoxy resin of the present invention is contained in an amount of 50 to 98 parts by mass with respect to 100 parts by mass of the total of the epoxy resin of the present invention and the epoxy resin (C).
In the epoxy resin composition of the present invention, the amount of the epoxy resin of the present invention and the curing agent (B) to be mixed is preferably in a ratio of 0.8 to 1.2 equivalents to 1 equivalent of the total of the active groups in the curing agent (B) based on the total of the epoxy groups in the epoxy resin of the present invention and the epoxy resin (C) used in combination as needed, from the viewpoint of excellent curability.
In addition, the epoxy resin composition may be used in combination with another thermosetting resin.
Examples of the other thermosetting resin include cyanate ester resins, resins having a benzoxazine structure, maleimide compounds, active ester resins, vinylbenzyl compounds, acrylic compounds, and copolymers of styrene and maleic anhydride. When the other thermosetting resins are used in combination, the amount thereof is not particularly limited as long as the effect of the present invention is not impaired, and is preferably in the range of 1 to 50 parts by mass in 100 parts by mass of the resin composition.
Examples of the cyanate ester resin include bisphenol a type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol thioether type cyanate ester resin, phenylene ether type cyanate ester resin, naphthalene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolak type cyanate ester resin, cresol novolak type cyanate ester resin, triphenylmethane type cyanate ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol copolycondensation type cyanate ester resin, naphthol-cresol copolycondensation type cyanate ester resin, naphthol-phenol copolycondensation type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, phenol novolac type cyanate ester resin, and the like, Aromatic hydrocarbon formaldehyde resin-modified phenol resin type cyanate ester resin, biphenyl-modified novolac type cyanate ester resin, anthracene type cyanate ester resin, and the like. These may be used alone or in combination of 2 or more.
Among these cyanate ester resins, bisphenol a type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, naphthalene ether type cyanate ester resin, and novolac type cyanate ester resin are preferably used from the viewpoint of obtaining a cured product excellent in heat resistance, and dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferably used from the viewpoint of obtaining a cured product excellent in dielectric characteristics.
Examples of the resin having a benzoxazine structure include, but are not particularly limited to, a reaction product of bisphenol F and formalin and aniline (F-a type benzoxazine resin), a reaction product of diaminodiphenylmethane and formalin and phenol (P-d type benzoxazine resin), a reaction product of bisphenol a and formalin and aniline, a reaction product of dihydroxydiphenyl ether and formalin and aniline, a reaction product of diaminodiphenyl ether and formalin and phenol, a reaction product of dicyclopentadiene-phenol addition type resin and formalin and aniline, a reaction product of phenolphthalein and formalin and aniline, and a reaction product of diphenyl sulfide and formalin and aniline. These may be used alone or in combination of 2 or more.
Examples of the maleimide compound include various compounds represented by any of the following structural formulae (i) to (iii).
Figure BDA0002306079340000111
(wherein R is an m-valent organic group, α and β are each independently a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and s is an integer of 1 or more.)
Figure BDA0002306079340000112
(wherein R is any of a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxyl group and an alkoxy group, s is an integer of 1 to 3, and t is 0 to 10 in the average of the repeating units.)
Figure BDA0002306079340000113
(wherein R is any one of a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxyl group and an alkoxy group, s is an integer of 1 to 3, and t is 0 to 10 in terms of the average of the repeating units). These may be used alone or in combination of 2 or more.
The active ester resin is not particularly limited, and compounds having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds, are generally preferably used. The active ester resin is preferably a resin obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound or an acid halide thereof and a hydroxyl compound is preferable, and an active ester resin obtained from a carboxylic acid compound or an acid halide thereof and a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like, or acid halides thereof. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol a, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α -naphthol, β -naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, and dicyclopentadiene-phenol addition type resins.
Specifically, the active ester resin is preferably an active ester resin having a dicyclopentadiene-phenol addition structure, an active ester resin having a naphthalene structure, an active ester resin being an acetylate of a phenol novolac, an active ester resin being a benzoylate of a phenol novolac, or the like, and more preferably an active ester resin having a dicyclopentadiene-phenol addition structure or an active ester resin having a naphthalene structure, from the viewpoint of excellent improvement in peel strength. More specifically, the active ester resin having a dicyclopentadiene-phenol addition structure includes a compound represented by the following general formula (iv).
Figure BDA0002306079340000121
Wherein in the formula (iv), R is phenyl or naphthyl, u represents 0 or 1, and n is 0.05 to 2.5 in terms of the average of repeating units. In view of reducing the dielectric loss tangent of a cured product of the resin composition and improving heat resistance, R is preferably a naphthyl group, u is preferably 0, and n is preferably 0.25 to 1.5.
The epoxy resin composition of the present invention is cured only with the epoxy resin composition, but a curing accelerator may be used in combination. Examples of the curing accelerator include tertiary amine compounds such as imidazole and dimethylaminopyridine; phosphorus compounds such as triphenylphosphine; boron trifluoride amine complexes such as boron trifluoride and boron trifluoride monoethylamine complexes; organic acid compounds such as thiodipropionic acid; benzoxazine compounds such as thiodiphenol benzoxazine and sulfonyl benzoxazine; sulfonyl compounds and the like. These may be used alone or in combination of 2 or more. The amount of the catalyst added is preferably in the range of 0.001 to 15 parts by mass in 100 parts by mass of the epoxy resin composition.
When the epoxy resin composition of the present invention is used in applications requiring high flame retardancy, a non-halogen flame retardant containing substantially no halogen atom may be added.
The non-halogen flame retardant may include, for example, a phosphorus flame retardant, a nitrogen flame retardant, a silicon flame retardant, an inorganic flame retardant, an organic metal salt flame retardant, and the like, and when they are used, they are not limited at all, and may be used alone, or a plurality of flame retardants of the same system may be used, or further, flame retardants of different systems may be used in combination.
The phosphorus flame retardant may be either inorganic or organic. Examples of the inorganic compound include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amides.
The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis or the like, and examples of the surface treatment method include (i) a method of performing a covering treatment with an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, bismuth oxide, bismuth hydroxide, bismuth nitrate, or a mixture thereof; (ii) a method of performing a covering treatment with a mixture of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide and a thermosetting resin such as a phenol resin; (iii) and a method of performing a double coating treatment on a coating film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide with a thermosetting resin such as a phenol resin.
Examples of the organic phosphorus-based compound include general-purpose organic phosphorus-based compounds such as phosphate compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphine compounds, and organic nitrogen-containing phosphorus compounds, cyclic organic phosphorus compounds such as 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10- (2, 7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives obtained by reacting these compounds with compounds such as epoxy resins and phenolic resins.
The amount of the phosphorus-based flame retardant to be blended is appropriately selected depending on the kind of the phosphorus-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy, and for example, when red phosphorus is used as the non-halogen-based flame retardant, it is preferably blended in a range of 0.1 to 2.0 parts by mass, and when an organic phosphorus compound is used, it is also preferably blended in a range of 0.1 to 10.0 parts by mass, and more preferably in a range of 0.5 to 6.0 parts by mass, in 100 parts by mass of the resin composition in which the non-halogen-based flame retardant, other filler, additive, and the like are blended.
When the phosphorus flame retardant is used, hydrotalcite, magnesium hydroxide, a boron compound, zirconia, a black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, or the like may be used in combination with the phosphorus flame retardant.
Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.
Examples of the triazine compound include melamine, methylguanamine, benzoguanamine, cyanuramide (melon), melam, succinylguanamine, ethylenebis (melamine), melamine polyphosphate, and triguanamine; and aminotriazine sulfate compounds such as (1) guanylmelamine sulfate, melem sulfate, melam sulfate and the like; (2) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol, and nonylphenol, melamines such as melamine, benzoguanamine, methylguanamine, and formylguanamine, and formaldehyde; (3) a mixture of the co-condensate of the above (2) and a phenolic resin such as a phenol formaldehyde condensate; (4) and (3) a product obtained by further modifying the above (2) and (3) with tung oil, isomerized linseed oil, or the like.
Examples of the cyanuric acid compound include cyanuric acid and melamine cyanurate.
The amount of the nitrogen-based flame retardant to be blended is appropriately selected depending on the kind of the nitrogen-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy, and for example, the amount is preferably in the range of 0.05 to 10 parts by mass, and more preferably in the range of 0.1 to 5 parts by mass, per 100 parts by mass of the resin composition in which the non-halogen-based flame retardant, other fillers, additives, and the like are blended.
When the nitrogen-based flame retardant is used, a metal hydroxide, a molybdenum compound, or the like may be used in combination.
The silicon-based flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin. The amount of the silicon-based flame retardant to be blended is appropriately selected depending on the type of the silicon-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy, and is preferably in the range of 0.05 to 20 parts by mass, for example, based on 100 parts by mass of the resin composition in which the non-halogen-based flame retardant, other fillers, additives, and the like are all blended. When the silicon-based flame retardant is used, a molybdenum compound, alumina, or the like may be used in combination.
Examples of the inorganic flame retardant include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass.
Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.
Examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, nickel oxide, copper oxide, and tungsten oxide.
Examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, titanium carbonate, and the like.
Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.
Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.
Examples of the low melting point glass include CEEPRE (Bokusui Brown Co., Ltd.), hydrated glass SiO2-MgO-H2O、PbO-B2O3Is of ZnO-P series2O5-MgO system, P2O5-B2O3-PbO-MgO system, P-Sn-O-F system, PbO-V system2O5-TeO2System, Al2O3-H2And glassy compounds such as O-type and lead borosilicate-type compounds.
The amount of the inorganic flame retardant to be blended is appropriately selected depending on the kind of the inorganic flame retardant, other components of the resin composition, and the desired degree of flame retardancy, and for example, is preferably in the range of 0.05 to 20 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, based on 100 parts by mass of the resin composition in which the non-halogen flame retardant, other filler, additive, and the like are all blended.
Examples of the organic metal salt-based flame retardant include ferrocene, acetylacetone metal complexes, organic metal carbonyl compounds, organic cobalt salt compounds, organic sulfonic acid metal salts, and compounds obtained by ionic bonding or coordinate bonding of a metal atom to an aromatic compound or a heterocyclic compound.
The amount of the organic metal salt-based flame retardant to be blended is appropriately selected depending on the kind of the organic metal salt-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy, and is preferably in the range of 0.005 to 10 parts by mass, for example, per 100 parts by mass of the resin composition in which the non-halogen-based flame retardant, other fillers, additives, and the like are blended.
The epoxy resin composition of the present invention may be compounded with an inorganic filler as required. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. In the case where the amount of the inorganic filler to be mixed is extremely increased, fused silica is preferably used. The fused silica may be in a crushed form or a spherical form, and it is preferable to use mainly a spherical form in order to increase the amount of the fused silica to be blended and to suppress an increase in melt viscosity of the molding material. Further, in order to increase the amount of the spherical silica to be blended, it is preferable to appropriately adjust the particle size distribution of the spherical silica. In view of flame retardancy, the filling ratio is preferably high, and is particularly preferably 20% by mass or more based on the total mass of the epoxy resin composition. When the conductive paste is used for applications such as a conductive paste, a conductive filler such as silver powder or copper powder may be used.
In addition to the epoxy resin composition of the present invention, various blending agents such as a silane coupling agent, a release agent, a pigment, an emulsifier and the like may be added as necessary.
< uses of epoxy resin compositions >
The epoxy resin composition of the present invention is applicable to semiconductor sealing materials, semiconductor devices, prepregs, printed circuit boards, build-up films, fiber-reinforced composites, fiber-reinforced resin moldings, conductive pastes, and the like.
1. Semiconductor sealing material
Examples of the method for obtaining a semiconductor sealing material from the epoxy resin composition of the present invention include the following methods: the epoxy resin composition, the curing accelerator, and the compounding agent such as an inorganic filler are sufficiently melt-mixed to be uniform by using an extruder, a kneader, a roll, or the like as needed. In this case, fused silica is generally used as the inorganic filler, and when used as a high thermal conductive semiconductor sealing material for a power transistor or a power IC, highly filled crystalline silica, alumina, silicon nitride, or the like having a higher thermal conductivity than fused silica, crystalline silica, alumina, silicon nitride, or the like can be used. The filling rate is preferably 30 to 95% by mass of an inorganic filler per 100 parts by mass of the epoxy resin composition, and more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more, in order to improve flame retardancy, moisture resistance, solder cracking resistance, and reduce a linear expansion coefficient.
2. Semiconductor device with a plurality of semiconductor chips
Examples of the method for obtaining a semiconductor device from the epoxy resin composition of the present invention include the following methods: the semiconductor sealing material is molded by a casting molding machine, a transfer molding machine, an injection molding machine, or the like, and further heated at 50 to 200 ℃ for 2 to 10 hours.
3. Prepreg
Examples of the method for obtaining a prepreg from the epoxy resin composition of the present invention include the following methods: the curable resin composition is obtained by impregnating a reinforcing base material (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, or the like) with a curable resin composition prepared by compounding an organic solvent into a varnish, and heating the resultant mixture at a heating temperature according to the type of the solvent used, preferably at 50 to 170 ℃. The mass ratio of the resin composition to be used in this case to the reinforcing base material is not particularly limited, and it is usually preferably prepared so that the resin component in the prepreg is 20 to 60 mass%.
Examples of the organic solvent used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, and the like, and the selection and the appropriate amount thereof can be appropriately selected depending on the application, and for example, in the case of producing a printed circuit board from a prepreg as described below, it is preferable to use a polar solvent having a boiling point of 160 ℃ or less, such as methyl ethyl ketone, acetone, and dimethylformamide, and to use the solvent in a proportion such that the nonvolatile content is 40 to 80 mass%.
4. Printed circuit board
The method for obtaining a printed circuit board from the epoxy resin composition of the present invention includes the following methods: laminating the prepregs by a conventional method, properly overlapping copper foils, and heating and pressing at 170-300 ℃ under a pressure of 1-10 MPa for 10 minutes-3 hours.
5. Laminated substrate
The method for obtaining a laminated substrate from the epoxy resin composition of the present invention includes a method in which the steps 1 to 3 are performed. In step 1, the curable resin composition containing a rubber, a filler, and the like as appropriate is first applied to a circuit board on which a circuit is formed by a spray coating method, a curtain coating method, or the like, and then cured. In step 2, after a circuit board coated with the epoxy resin composition is perforated with a specific via portion or the like as required, the surface thereof is treated with a roughening agent and then washed with hot water to form irregularities on the board, thereby plating a metal such as copper. In step 3, the operations of steps 1 to 2 are repeated in sequence as desired, and the resin insulation layers and the conductor layers of the specific circuit pattern are alternately laminated to form a laminated substrate. In the foregoing step, the opening of the through hole portion may be performed after the outermost resin insulation layer is formed. In addition, the laminated substrate of the present invention can be produced by forming a roughened surface by heat-pressing a copper foil with a resin, which is obtained by semi-curing the resin composition on a copper foil, onto a wiring board having a circuit formed thereon at 170 to 300 ℃.
6. Laminated film
Examples of the method for obtaining a laminated film from the epoxy resin composition of the present invention include the following methods: for example, a curable resin composition is applied to a support film, and then dried to form a resin composition layer on the support film. When the epoxy resin composition of the present invention is used for a laminate film, it is important that: the film is softened under the lamination temperature condition (usually 70 to 140 ℃) in the vacuum lamination method, and exhibits fluidity (resin flow) capable of filling resin into a via hole or a through hole existing in a circuit board simultaneously with lamination of the circuit board, and it is preferable to blend the above-mentioned components so as to exhibit such characteristics.
Here, the diameter of the through hole of the circuit board is usually 0.1 to 0.5mm, and the depth is usually 0.1 to 1.2mm, and it is usually preferable that the through hole can be filled with resin within this range. When laminating both surfaces of the circuit board, it is desirable that about 1/2 of the through hole is filled.
Specific examples of the method for producing the laminated film include the following methods: after preparing an epoxy resin composition prepared by blending an organic solvent to prepare a varnish, the composition is applied to the surface of the support film (Y), and the organic solvent is dried by heating or blowing hot air or the like, thereby forming a layer (X) of the epoxy resin composition.
As the organic solvent used herein, ketones such as acetone, methyl ethyl ketone, cyclohexanone; acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc.; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like, and is preferably used in such a proportion that the nonvolatile content is 30 to 60 mass%.
The thickness of the layer (X) of the resin composition to be formed is generally required to be equal to or greater than the thickness of the conductor layer. The thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, and therefore, the thickness of the resin composition layer is preferably 10 to 100 μm. The layer (X) of the resin composition of the present invention may be protected by a protective film described later. By protecting the surface of the resin composition with the protective film, adhesion of dirt or the like to the surface of the resin composition layer and scratches can be prevented.
Examples of the support film and the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes simply referred to as "PET") and polyethylene naphthalate, polycarbonates, polyimides, and further metal foils such as release paper, copper foil, and aluminum foil. The support film and the protective film may be subjected to a mold release treatment in addition to the precipitate treatment and the corona treatment. The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and preferably 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.
The supporting film (Y) is laminated on a circuit board or cured by heating to form an insulating layer, and then peeled off. If the support film (Y) is peeled off after the epoxy resin composition layer constituting the multilayer film is cured by heating, adhesion of dirt and the like in the curing step can be prevented. When the support film is peeled after curing, the support film is usually subjected to a mold release treatment in advance.
A multilayer printed circuit board can be produced from the laminated film obtained in the above manner. For example, in the aforementioned resinsWhen the layer (X) of the composition is protected by a protective film, the layer (X) of the resin composition is peeled off and then laminated on one surface or both surfaces of a circuit board by, for example, a vacuum lamination method so as to be in direct contact with the circuit board. The laminating method may be a batch method or a continuous method using a roll. Further, the build-up film and the circuit board may be heated (preheated) as necessary before lamination, if necessary. The laminating conditions are preferably such that the pressure bonding temperature (laminating temperature) is 70 to 140 ℃ and the pressure bonding pressure is 1 to 11kgf/cm2(9.8×104～107.9×104N/m2) The lamination is preferably performed under reduced pressure with an air pressure of 20mmHg (26.7hPa) or less.
7. Fiber-reinforced composite material
Examples of a method for obtaining a fiber-reinforced composite material (a sheet-like intermediate material obtained by impregnating a reinforcing fiber with a resin) from the epoxy resin composition of the present invention include the following methods: the epoxy resin composition is produced by uniformly mixing the respective components constituting the epoxy resin composition to prepare a varnish, impregnating the varnish into a reinforcing base material containing reinforcing fibers, and then causing a polymerization reaction to occur.
Specifically, the curing temperature in the polymerization reaction is preferably in the range of 50 to 250 ℃, and particularly preferably 50 to 100 ℃ to cure the polymer to form a non-adhesive cured product, and then the cured product is further treated at a temperature of 120 to 200 ℃.
Here, the reinforcing fiber may be any of a Twisted yarn (Twisted yarn), Untwisted yarn (Untwisted yarn), Non-Twisted yarn (Non-Twisted yarns), and the like, and is preferably Untwisted yarn or Non-Twisted yarn in view of compatibility between moldability and mechanical strength of the fiber-reinforced plastic member. Further, as the form of the reinforcing fiber, a form or a fabric in which the fiber direction is aligned in one direction may be used. The woven fabric may be selected from plain weave, satin weave, and the like, depending on the use site and the application. Specifically, from the viewpoint of excellent mechanical strength and durability, carbon fibers, glass fibers, aramid fibers, boron fibers, alumina fibers, silicon carbide fibers, and the like can be mentioned, and 2 or more of them can be used in combination. Among these, carbon fibers are preferable from the viewpoint of particularly good strength of molded articles, and various carbon fibers such as polyacrylonitrile-based, pitch-based, rayon-based, and the like can be used for the carbon fibers. Among them, polyacrylonitrile-based carbon fibers, from which high-strength carbon fibers are easily obtained, are preferable. Here, the amount of the reinforcing fibers used when the fiber-reinforced composite material is produced by impregnating the reinforcing base material containing the reinforcing fibers with the varnish is preferably such an amount that the volume content of the reinforcing fibers in the fiber-reinforced composite material is in the range of 40% to 85%.
8. Fiber-reinforced resin molded article
Examples of a method for obtaining a fiber-reinforced molded article (a molded article obtained by curing a sheet-like member in which reinforcing fibers are impregnated with a resin) from the epoxy resin composition of the present invention include the following methods: a hand lay-up (hand lay-up) method in which a fibrous aggregate is laid in a mold and the varnish is gradually layered in multiple layers; spray-up (spray-up) method; a vacuum bag method in which a base material including reinforcing fibers is subjected to build-up molding while impregnating varnish into the base material, and a flexible mold capable of applying pressure to a molded product is covered with one of a male mold and a female mold, and vacuum (reduced pressure) molding is performed after hermetic sealing; an SMC pressing method in which varnish containing reinforcing fibers is formed into a sheet in advance and then compression-molded in a mold; a prepreg in which the reinforcing fibers are impregnated with the varnish is produced by an RTM method or the like in which the varnish is injected into a mold equipped with fibers, and the prepreg is baked to be strong in a large autoclave. The fiber-reinforced resin molded article obtained as described above is a molded article having a cured product of a reinforcing fiber and an epoxy resin composition, and specifically, the amount of the reinforcing fiber in the fiber-reinforced molded article is preferably in the range of 40 to 70 mass%, and particularly preferably in the range of 50 to 70 mass% from the viewpoint of strength.
9. Conductive paste
As a method for obtaining a conductive paste from the epoxy resin composition of the present invention, for example, a method of dispersing fine conductive particles in the curable resin composition can be mentioned. The conductive paste can be made into a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the kind of fine conductive particles used.
Examples
The present invention is described specifically by examples and comparative examples, and the following "parts" and "%" are based on mass unless otherwise specified. GPC was measured under the following conditions.
< GPC measurement conditions >
A measuring device: HLC-8320GPC, manufactured by Tosoh corporation,
Column: "HXL-L" protective column manufactured by Tosoh corporation "
+ TSK-GEL G2000HXL manufactured by Tosoh corporation "
+ TSK-GEL G2000HXL manufactured by Tosoh corporation "
+ TSK-GEL G3000HXL manufactured by Tosoh corporation "
+ manufactured by Tosoh corporation of "TSK-GEL G4000 HXL"
A detector: RI (differential refractometer)
Data processing: "GPC WorkStation Eco SEC-workbench" manufactured by Tosoh corporation "
The measurement conditions were as follows: column temperature 40 deg.C
Tetrahydrofuran as developing solvent
Flow rate 1.0 ml/min
The standard is as follows: the following monodisperse polystyrenes of known molecular weights were used according to the manual of the aforementioned "GPC WorkStation Eco SEC-WorkStation".
(use of polystyrene)
"A-500" made by Tosoh corporation "
"A-1000" made by Tosoh corporation "
"A-2500" made by Tosoh corporation "
"A-5000" manufactured by Tosoh corporation "
"F-1" manufactured by Tosoh corporation "
"F-2" made by Tosoh corporation "
"F-4" manufactured by Tosoh corporation "
"F-10" made by Tosoh corporation "
"F-20" made by Tosoh corporation "
"F-40" made by Tosoh corporation "
"F-80" made by Tosoh corporation "
"F-128" made by Tosoh corporation "
Sample preparation: a tetrahydrofuran solution (1.0 mass% in terms of solid content of the resin) was filtered through a microfilter to obtain a sample (50. mu.l).
Example 1 Synthesis of epoxy resin (A-1)
While a flask equipped with a thermometer, a cooling tube, and a stirrer was purged with nitrogen, 242 parts by mass (1 mol) of 3,3 ', 5, 5' -tetramethylbiphenol, 1110 parts by mass (12 mol) of epichlorohydrin, 8.6 parts by mass (0.12 mol) of glycidol, 389 parts by mass of 2-propanol, and 185 parts by mass of water were charged and dissolved. After the temperature was raised to 40 ℃, 90 parts by mass (0.77 mol) of a 48 mass% potassium hydroxide aqueous solution was added thereto over 1 hour, and the mixture was heated to 70 ℃ and reacted for 1 hour. Then, the mixture was allowed to stand for liquid separation, and the lower aqueous layer was discharged. Further, 180 parts by mass (1.5 moles) of a 48% by mass potassium hydroxide aqueous solution was added over 2 hours, and after 2 hours of reaction, 250 parts by mass of water was added to separate the solution, and the lower aqueous layer was discharged. After the completion of the reaction, unreacted epichlorohydrin was distilled off under reduced pressure at 150 ℃. Subsequently, 800 parts by mass of methyl isobutyl ketone was added to the obtained crude epoxy resin to dissolve the resin. To this solution, 15 parts by mass of a 10 mass% aqueous sodium hydroxide solution and 5 parts by mass of a 50 mass% aqueous benzyltrimethylammonium chloride solution were added, and after allowing to react at 80 ℃ for 2 hours, the solution was repeatedly washed with 200 parts by mass of water 3 times until the pH of the washing solution became neutral. Then, the inside of the system was dehydrated by azeotropic distillation, followed by microfiltration, and then the solvent was distilled off under reduced pressure to obtain an epoxy resin (A-1). The epoxy equivalent of the obtained epoxy resin (A-1) was 191g/eq, and the content of 1, 2-diol was 0.067 meq/g. The GPC spectrum is shown in FIG. 1.
Example 2 Synthesis of epoxy resin (A-2)
An epoxy resin (a-2) was obtained in the same manner as in example 1, except that the amount of water added at the start of dissolution was changed to 256 parts by mass. The epoxy equivalent of the obtained epoxy resin (A-2) was 195g/eq, and the content of 1, 2-diol was 0.095 meq./g. The GPC spectrum is shown in FIG. 2.
Example 3 Synthesis of epoxy resin (A-3)
While a flask equipped with a thermometer, a cooling tube, and a stirrer was purged with nitrogen, 191 parts by mass of epoxy resin (a-1) and 500 parts by mass of methyl isobutyl ketone were added and dissolved. After the temperature was raised to 110 ℃, 0.75 part by mass of a 48 mass% potassium hydroxide aqueous solution was added and reacted for 1 hour. Thereafter, the temperature was lowered to 80 ℃ and 10 parts by mass of a 10 mass% aqueous solution of potassium hydroxide was added to the mixture to react the mixture for 2 hours, and then the reaction mixture was repeatedly washed with 200g of water 3 times until the pH of the washing solution became neutral. Then, the inside of the system was dehydrated by azeotropic distillation, followed by microfiltration, and then the solvent was distilled off under reduced pressure to obtain an epoxy resin (A-3). The epoxy equivalent of the obtained epoxy resin (A-3) was 192g/eq, and the content of 1, 2-diol was 0.076 meq./g.
Comparative example 1 synthesis of epoxy resin (A' -1): reproduction (trace) of example of Japanese patent laid-open publication No. 2016-108562
Into a four-necked flask having an internal volume of 2L and equipped with a thermometer, a stirrer and a cooling tube, 137 parts by mass of 3,3 ', 5, 5' -tetramethylbiphenol, 627 parts by mass of epichlorohydrin, 244 parts by mass of isopropyl alcohol and 87 parts by mass of water were charged, and after heating to 65 ℃ and uniformly dissolving them, 108 parts by mass of a 48.5 mass% aqueous sodium hydroxide solution was added dropwise over 90 minutes. After completion of the dropwise addition, the reaction mixture was held at 65 ℃ for 30 minutes to complete the reaction, and the reaction mixture was transferred to a 3L separatory funnel, allowed to stand at 65 ℃ for 1 hour, and then the aqueous layer was taken out from the separated oil layer and aqueous layer, and by-produced salt and excess sodium hydroxide were taken out. Subsequently, excess epichlorohydrin and isopropanol were distilled off from the product under reduced pressure. To this was added 300 parts by mass of methyl isobutyl ketone to dissolve it, and 4g of a 48.5 mass% aqueous sodium hydroxide solution was added and the reaction was carried out again at a temperature of 65 ℃ for 1 hour. After 167g of methyl isobutyl ketone was added, 130g of water was added and transferred to a 3L separatory funnel, and after standing at 65 ℃ for 1 hour, the aqueous layer was taken out from the separated oil layer and aqueous layer. To this solution, 2g of sodium dihydrogenphosphate and 160g of water were added, and the mixture was allowed to stand at 65 ℃ for 1 hour, then the aqueous layer was separated from the oil layer and the aqueous layer, and the inside of the system was dehydrated by azeotropy, followed by microfiltration and evaporation of the solvent under reduced pressure to obtain epoxy resin (A' -1). The epoxy equivalent of the obtained epoxy resin (A' -1) was 185g/eq, and the content of 1, 2-diol was 0.061meq.
Comparative example 2 Synthesis of epoxy resin (A' -2)
An epoxy resin (a' -2) was obtained in the same manner as in example 1, except that the amount of water added at the time of initial dissolution was changed to 306 parts by mass. The epoxy equivalent of the obtained epoxy resin (A' -2) was 197g/eq, and the content of 1, 2-diol was 0.12 meq./g.
< preparation of composition and cured product >
The following compounds were compounded in the compositions shown in table 2, and then melt-kneaded at a temperature of 90 ℃ for 5 minutes using a two-roll mill to prepare the objective epoxy resin compositions. Note that the abbreviations in table 1 refer to the following compounds.
Epoxy resin A-1: epoxy resin obtained in example 1
Epoxy resin A-2: epoxy resin obtained in example 2
Epoxy resin A-3: epoxy resin obtained in example 3
Epoxy resin a' -1: epoxy resin obtained in comparative example 1
Epoxy resin a' -2: epoxy resin obtained in comparative example 2
Curing agent TD-2131: phenol novolac resin hydroxyl equivalent: 104g/eq (DIC corporation)
TPP: triphenylphosphine
Fused silica: spherical silica "FB-560", manufactured by DENKA K.K
Silane coupling agent: gamma-glycidoxy-triethoxysilane "KBM-403", manufactured by shin-Etsu chemical Co., Ltd
Carnauba wax: "PEARL WAX No. 1-P", manufactured by DENKA K.K.)
Then, the obtained resin composition is pulverized and the resultant is transferred to a molding machineUnder a pressure of 70kg/cm2Molding at 175 ℃ for 180 seconds
Figure BDA0002306079340000241
Further cured at 180 ℃ for 5 hours.
< measurement of glass transition temperature >
1) Preparation of evaluation sample
The following compounds were compounded in the compositions shown in table 2 to obtain curable compositions. The molded article was poured into a mold of 11cm × 9cm × 2.4mm, molded at a temperature of 150 ℃ for 10 minutes by pressing, and then the molded article was taken out of the mold, followed by curing at a temperature of 175 ℃ for 5 hours, thereby obtaining an evaluation sample.
2) Determination of glass transition temperature
The temperature at which the change in elastic modulus was maximized (tan. delta. rate of change was maximized) was measured for the above-described evaluation sample using a viscoelasticity measuring apparatus (DMA: solid viscoelasticity measuring apparatus RSAII manufactured by Rheometric Co., Ltd., Rectangular tensile method; frequency: 1Hz, temperature rise rate: 3 ℃/min) and evaluated as the glass transition temperature. The results are shown in Table 1.
< measurement of shrinkage at Molding >
A test piece having a height of 110mm, a width of 12.7mm and a thickness of 1.6mm was prepared by injection molding the resin composition using a transfer molding machine (KTS-15-1.5C manufactured by KOHTAKI corporation) under conditions of a mold temperature of 150 ℃, a molding pressure of 9.8MPa and a curing time of 600 seconds. Thereafter, the test piece was post-cured at 175 ℃ for 5 hours, and the inner diameter of the mold cavity and the outer diameter of the test piece at room temperature (25 ℃) were measured to calculate the shrinkage ratio by the following formula.
Shrinkage (%) { (inner diameter dimension of mold) - (longitudinal dimension of cured product at 25 ℃) }/(inner diameter dimension of mold cavity at 175 ℃) x 100 (%)
The results are shown in tables 1 and 2.
[ Table 1]
Figure BDA0002306079340000261
[ Table 2]
Figure BDA0002306079340000262

Claims (14)

1. An epoxy resin characterized by being a tetramethylbiphenol-type epoxy resin represented by the following structural formula (1),
Figure FDA0003556757560000011
wherein n represents a repetition number of 0 to 5,
the content of 1, 2-diol in the resin is 0.065 to 0.095 meq/g.
2. The epoxy resin according to claim 1, wherein the epoxy equivalent is 178 to 250 g/eq.
3. An epoxy resin composition comprising the epoxy resin according to claim 1 or 2 and a curing agent (B) as essential components.
4. A cured product of the epoxy resin composition according to claim 3.
5. A semiconductor sealing material comprising the epoxy resin composition according to claim 3 and an inorganic filler.
6. A semiconductor device which is a cured product of the semiconductor sealing material according to claim 3.
7. A prepreg which is a semi-cured product of an impregnated substrate comprising the epoxy resin composition according to claim 3 and a reinforcing substrate.
8. A circuit board comprising the sheet-like form of the epoxy resin composition according to claim 3 and a copper foil.
9. A multilayer film comprising a cured product of the epoxy resin composition according to claim 3 and a base film.
10. A fiber-reinforced composite material comprising the epoxy resin composition according to claim 3 and a reinforcing fiber.
11. A fiber-reinforced molded article which is a cured product of the fiber-reinforced composite material according to claim 10.
12. A method for producing the epoxy resin according to claim 1 or 2, comprising the following reaction steps: epoxidation was carried out using 3,3 ', 5, 5' -tetramethylbiphenol, glycidol and epihalohydrin.
13. The method for producing an epoxy resin according to claim 12, wherein a mixed solvent of water and an organic solvent is used as the medium, and the content of water is in the range of 5 to 60 parts by mass per 100 parts by mass of the mixed solvent.
14. The method for producing an epoxy resin according to claim 12 or 13, wherein the ratio of glycidol used is in the range of 1 to 10 parts by mass with respect to 100 parts by mass of 3,3 ', 5, 5' -tetramethylbiphenol.
CN201880037755.5A 2017-06-07 2018-04-24 Epoxy resin, method for producing same, epoxy resin composition, and cured product thereof Active CN110719926B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2017-112542 2017-06-07
JP2017112542 2017-06-07
PCT/JP2018/016549 WO2018225411A1 (en) 2017-06-07 2018-04-24 Epoxy resin, production method, epoxy resin composition, and cured product thereof

Publications (2)

Publication Number Publication Date
CN110719926A CN110719926A (en) 2020-01-21
CN110719926B true CN110719926B (en) 2022-05-13

Family

ID=64567317

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201880037755.5A Active CN110719926B (en) 2017-06-07 2018-04-24 Epoxy resin, method for producing same, epoxy resin composition, and cured product thereof

Country Status (5)

Country Link
JP (1) JP7140115B2 (en)
KR (1) KR102409661B1 (en)
CN (1) CN110719926B (en)
TW (1) TWI794235B (en)
WO (1) WO2018225411A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7249162B2 (en) * 2019-02-01 2023-03-30 積水化学工業株式会社 Resin composition, cured product, and build-up film
US10961208B1 (en) 2019-12-24 2021-03-30 Chang Chun Plastics Co., Ltd. Product of glycidyl ether of a mono or polyhydric phenol

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62290717A (en) * 1986-06-09 1987-12-17 Asahi Chem Ind Co Ltd Epoxy resin liquid composition for electronic component
KR0168057B1 (en) * 1990-04-12 1999-03-20 베르너 발데크 Process ror the preparation of epoxy resins
JP3760612B2 (en) * 1997-12-18 2006-03-29 大日本インキ化学工業株式会社 Production method of epoxy resin
JP4684538B2 (en) 2003-04-08 2011-05-18 三菱化学株式会社 Epoxy resin, its production method, epoxy resin composition and semiconductor device
JP2006291094A (en) 2005-04-13 2006-10-26 Yokohama Rubber Co Ltd:The Epoxy resin composition for reinforced composite material
JP5551389B2 (en) * 2009-08-06 2014-07-16 新日鉄住金化学株式会社 Epoxy resin powder coating composition
JP5544184B2 (en) * 2010-02-08 2014-07-09 新日鉄住金化学株式会社 Method for producing phosphorus-containing epoxy resin, epoxy resin composition and cured product thereof
US20130052381A1 (en) * 2011-08-22 2013-02-28 Robert R. Gallucci Polyepoxides and epoxy resins and methods for the manufacture and use thereof
JP5967401B2 (en) 2011-11-21 2016-08-10 Dic株式会社 High molecular weight urethane resin, epoxy resin composition containing the urethane resin, and cured product thereof
TWI641628B (en) * 2014-10-24 2018-11-21 新日鐵住金化學股份有限公司 Epoxy resin composition and cured article thereof
JP6558671B2 (en) 2014-11-07 2019-08-14 パナソニックＩｐマネジメント株式会社 Epoxy resin composition for sealing and semiconductor device
MY181374A (en) * 2014-12-04 2020-12-21 Mitsubishi Chem Corp Tetramethylbiphenol type epoxy resin, epoxy resin composition, cured product, and semiconductor sealing material
KR101854503B1 (en) * 2015-07-20 2018-05-04 삼성에스디아이 주식회사 Phosphonium compound, epoxy resin composition comprising the same and semiconductor device prepared from using the same

Also Published As

Publication number Publication date
TW201902714A (en) 2019-01-16
JP7140115B2 (en) 2022-09-21
JPWO2018225411A1 (en) 2020-04-09
TWI794235B (en) 2023-03-01
KR20200016216A (en) 2020-02-14
WO2018225411A1 (en) 2018-12-13
CN110719926A (en) 2020-01-21
KR102409661B1 (en) 2022-06-17

Similar Documents

Publication Publication Date Title
WO2018180451A1 (en) Epoxy resin, production method, and epoxy resin composition and cured object obtained therefrom
JP5904387B1 (en) Epoxy resin, curable resin composition, cured product, semiconductor sealing material, semiconductor device, prepreg, circuit board, buildup film, buildup board, fiber reinforced composite material, and fiber reinforced molded product
US9056990B2 (en) Phosphorus-atom-containing oligomer composition, curable resin composition, cured product thereof, and printed circuit board
CN108368237B (en) Epoxy resin, method for producing epoxy resin, curable resin composition, and cured product thereof
CN110719926B (en) Epoxy resin, method for producing same, epoxy resin composition, and cured product thereof
JP6809200B2 (en) Epoxy resin, curable resin composition and its cured product
JP6874359B2 (en) Epoxy resin, epoxy resin composition and cured product thereof
JP6809206B2 (en) Epoxy resin, curable resin composition and its cured product
CN109153768B (en) Epoxy resin, method for producing same, epoxy resin composition, and cured product thereof
JP2017105898A (en) Epoxy resin, manufacturing method of epoxy resin, curable resin composition and cured article thereof
JP7024227B2 (en) Epoxy resin manufacturing method, epoxy resin, epoxy resin composition and cured product thereof
JP6992932B2 (en) Polyfunctional phenol resin, polyfunctional epoxy resin, curable resin composition containing them and cured product thereof
JP6750427B2 (en) Polyfunctional epoxy resin, production method thereof, curable resin composition and cured product thereof
JP7192485B2 (en) Xanthene type resin, curable resin composition and cured product thereof
CN114341227A (en) Phenolic resin, curable resin composition, and cured product thereof

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