Classifications

• • 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
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
  • H01L2924/0001—Technical content checked by a classifier
  • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

• the present invention relates to an epoxy resin and a resin composition.
• Epoxy resins are used as binders for various purposes because they are solvent-soluble and have excellent mechanical properties. Epoxy resins are usually obtained by reacting phenolic compounds with epichlorohydrin, and therefore contain a large amount of chlorine such as hydrolyzable chlorine and organic bondable chlorine. When an epoxy resin containing a chlorine content is used for an electronic material, it causes corrosion of wiring and the like, and thus an epoxy resin with a reduced chlorine content is required.
• a resin composition in which naphthalene epoxy is added to a phenoxy resin solution is disclosed as a low chlorinated epoxy resin composition (see, for example, Patent Document 2).
• Epoxy resins generally tend to crystallize when the chlorine content is reduced. This tendency is particularly strong in resins such as aromatic epoxy resins that have a strong intermolecular force and are easy to work. The crystallized epoxy resin is unsuitable for so-called sealing applications from the viewpoint of handleability.
• Patent Document 2 Although the method described in Patent Document 2 can uniformly disperse or dissolve naphthalene epoxy in a solvent, the resulting epoxy resin composition may not be suitable for sealing applications because the solvent needs to be removed. .
• Patent Document 3 does not require solvent removal, the heat resistance of the resulting cured product tends to be significantly reduced.
• the present invention has been made in view of such points, and has an epoxy resin and a resin composition that have low viscosity, good storage stability, and can exhibit excellent heat resistance when used as a cured product.
• the purpose is to provide.
• the present invention is as follows.
• the resin (B) is at least one selected from the group consisting of epoxy resins, phenoxy resins, phenol novolacs, polyamic acids, polyimides, polybenzoxazoles and (meth) acrylate resins, [1] to [8]
• the resin composition in any one.
• the proportion of the epoxy resin (A) is 20% by mass or more and 90% by mass or less, and the proportion of the resin (B) is 10% by mass or more and 80% by mass or less.
• the total concentration of the compounds represented by the following general formulas (9) to (11) contained in the total resin composition and the chlorine concentration derived from the alkali metal chloride is 0.01 ppm or more and 1000 ppm or less.
• Resin composition In the formulas (1) to (3), R 1 to R 6 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x, y, and z represent 0 to 10 Represents an integer.)
• R 8, R 9 , R 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and R 7 and R 10 Each independently represents a divalent organic group having 1 to 10 carbon atoms.
• R 1 to R 6 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x, y, and z are 0 to 10 Rx and Ry each independently represents any structure
• the resin (B) is at least one selected from the group consisting of the general formulas (4) and (5),
• the sum total of the concentration of the compound represented by the general formulas (9) and (10) contained in the total resin composition and the chlorine concentration derived from the alkali metal chloride is 0.01 ppm or more and 1000 ppm or less.
• the epoxy resin (A) is a resin represented by the general formula (1)
• the resin (B) is a resin represented by the general formula (4)
• the total of the concentration of the compound represented by the general formula (9) and the chlorine concentration derived from sodium chloride and potassium chloride contained in the entire resin composition is 0.01 ppm or more and 1000 ppm or less
• the epoxy resin (A) is represented by the following general formula (1):
• the compound (C) having the dioxane structure is the following general formula (12), Hardened
• R 1 represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x represents an integer of 0 to 5)
• each R 1 independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x represents an integer of 0 to 10.
• the epoxy resin (A) is represented by the following general formula (2):
• the compound (C) having the dioxane structure is the following general formula (13), Hardened
• R 2 represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and y represents an integer of 0 to 5)
• each R 2 independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and y represents an integer of 0 to 10.
• each R 1 independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms
• x represents an integer of 0 or more and 5 or less
• An epoxy resin represented by the general formula (2) The epoxy resin whose total chlorine amount contained in the said epoxy resin is 0.01 ppm or more and 1000 ppm or less.
• R 2 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms
• y represents an integer of 0 or more and 5 or less
• An underfill material comprising the resin composition according to any one of [1] to [15] or the curable resin composition according to any one of [21] to [26].
• a die attach material comprising the resin composition according to any one of [1] to [15] or the curable resin composition according to any one of [21] to [26].
• a liquid sealing material comprising the resin composition according to any one of [1] to [15] or the curable resin composition according to any one of [21] to [26].
• An electronic component comprising at least one selected from the group consisting of an underfill material according to [27], a die attach material according to [28], and a liquid sealing material according to [29].
• the viscosity is low, the storage stability is good, and when the resin composition is used, excellent heat resistance can be realized.
• the present embodiment a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
• the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
• the present invention can be implemented with appropriate modifications within the scope of the gist thereof.
• the resin composition according to the present embodiment contains an epoxy resin (A) having a total chlorine content of 0.01 ppm to 1000 ppm and a resin (B) having a melting point or a softening point of 50 ° C. or higher, Inside, content of resin (A) is 20 mass% or more and 90 mass% or less.
• the low chlorine epoxy resin (A) having a total chlorine content of 0.01 ppm to 1000 ppm is generally solid, and the resin (B) having a melting point or softening point of 50 ° C. or higher is also solid. And it is very difficult to mix resin of solids,
• the resin composition concerning this embodiment is a liquid state of low viscosity by adjusting content of resin (A) to said range. While maintaining the above, the cured product can exhibit high heat resistance. Generally, when mixing resins between solids, it is known to melt by heating or the like to form a liquid, but when this is returned to room temperature, the obtained liquid resin composition It is common for things to return to a solid state again.
• the resin composition according to the present embodiment can maintain a low-viscosity liquid state even when the temperature is returned to room temperature.
• the reason for this is not clear, but since the amount of chlorine in the epoxy resin (A) is low, impurities in the resin composition are reduced and the interaction with the resin (B) is strengthened.
• B) It is presumed that each intermolecular force has decreased and it has become easier to maintain a liquid state.
• a plurality of resins are melt-mixed, it is necessary to heat them to the melting point or more of each resin. And in the case of the heating, the hydroxyl group contained in a hydrolyzable chlorine content etc.
• the epoxy resin (A) used in the present embodiment is a low chlorine epoxy resin having a total chlorine content of 0.01 ppm to 1000 ppm.
• the epoxy resin (A) is not particularly limited as long as the total chlorine amount is in the above range.
• total chlorine amount means the total amount of chlorine contained in the epoxy resin, and indicates the total amount of organic bondable chlorine, hydrolyzable chlorine, and inorganic chlorine. Unless otherwise specified, ppm, which is the unit of total chlorine, is based on mass.
• the total chlorine amount was determined by adding a potassium hydroxide solution to an epoxy resin, heating and refluxing, and then adding acetic acid, and using a potentiometric titrator (manufactured by Kyoto Electronics Co., Ltd., automatic potentiometric titrator “AT-510”). It can be measured by precipitation titration.
• the total chlorine content in the epoxy resin (A) is 0.01 ppm or more, crystallization of the epoxy resin can be suppressed, so that a low viscosity can be maintained. High heat resistance (glass transition temperature) can be achieved.
• the total chlorine content in the epoxy resin (A) is preferably 0.1 ppm or more and 1000 ppm from the viewpoint of further suppressing crystallization and maintaining low viscosity, and has a glass transition temperature (hereinafter also referred to as “Tg”) of the cured product. From the viewpoint, 1 ppm to 650 ppm is more preferable, and from the viewpoint of a balance between the viscosity of the resin composition and the heat resistance of the cured product, 1 ppm to 200 ppm is particularly preferable.
• the content of the epoxy resin (A) is 20% by mass or more and 90% by mass or less. If the content of the epoxy resin (A) is 20% by mass or more, the viscosity of the resin composition tends to be sufficiently low, and if it is 90% by mass or less, the heat resistance of the cured product is good.
• the content of the epoxy resin (A) is preferably 30% by mass or more and 90% by mass or less from the viewpoint of low viscosity of the resin composition, and 30% by mass or more and 85% by mass or less from the viewpoint of heat resistance when a cured product is obtained. From the viewpoint of storage stability, 50% by mass or more and 85% by mass or less is particularly preferable.
• the epoxy resin (A) preferably has a melting point or softening point of 30 ° C or higher. If the melting point or softening point of the epoxy resin (A) is 30 ° C. or higher, the heat resistance when cured is likely to be good.
• the melting point or softening point of the epoxy resin (A) is more preferably 30 to 80 ° C., further preferably 30 to 50 ° C. In the present embodiment, the melting point and the softening point can be measured with a differential scanning calorimeter or the like.
• the structure of the epoxy resin (A) is not particularly limited, and examples of such an epoxy resin (A) include an aromatic epoxy resin, an aliphatic epoxy resin, and an alicyclic epoxy resin.
• an aromatic epoxy resin is preferable from a compatible viewpoint with resin (B).
• the aromatic epoxy resin contains an aromatic in the epoxy resin skeleton, it becomes easy to interact with the resin (B), the compatibility is improved, and the resin composition tends to have a low viscosity.
• the aromatic epoxy resin is not limited as long as it has an aromatic structure and an epoxy group.
• aromatic epoxy resins include resins having an aromatic glycidyl ether structure, an aromatic glycidyl ester structure, and an aromatic glycidyl amine structure.
• a resin having an aromatic glycidyl ether structure and an aromatic glycidyl ester structure is preferable from the viewpoint of low viscosity of the resin composition, and a resin having an aromatic glycidyl ether structure from the viewpoint of heat resistance of the cured product. More preferred is a resin having an aromatic diglycidyl ether structure.
• the resin having an aromatic glycidyl ether structure (aromatic glycidyl ether compound) used in the present embodiment is preferably at least one selected from the group consisting of the following general formulas (1) to (3).
• R 1 to R 6 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and x, y, and z are integers of 0 to 10 Represents.
• R 1 in the general formula (1) are each independently a monovalent organic group hydrogen atom or a C 1-10.
• the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as a methyl group and an ethyl group.
• the hydrocarbon group may be substituted with a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, or may be unsubstituted.
• R 1 in the general formula (1) is independently preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom, from the viewpoint of heat resistance when a cured product is obtained.
• X in the general formula (1) represents an integer of 0 to 10.
• x is preferably 0 to 5 from the viewpoint of low viscosity of the epoxy resin.
• the bonding position of the glycidyl ether group in the general formula (1) is not particularly limited, but the meta position and the para position are preferable from the viewpoint of heat resistance when the cured product is formed, and the meta position is more preferable from the viewpoint of the viscosity of the epoxy resin. .
• x in the general formula (1) represents an integer of 0 to 10, but may be in a state where compounds having different numerical values of x are mixed.
• R 2 in the general formula (2) is each independently a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.
• the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as a methyl group and an ethyl group.
• the hydrocarbon group may be substituted with a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, or may be unsubstituted.
• R 2 in the general formula (2) is preferably independently a hydrogen atom or a methyl group, more preferably a hydrogen atom, from the viewpoint of heat resistance when a cured product is used.
• Y in the general formula (2) represents an integer of 0 to 10.
• y is preferably 0 to 5 from the viewpoint of low viscosity of the epoxy resin.
• the bonding position of the glycidyl ether group in the general formula (2) is not particularly limited, but from the viewpoint of heat resistance when a cured product is obtained, the 1,5-position, 1,6-position, 1,7-position, 1,8-position 2,6 and 2,7 are preferable, and the 1,6th and 1,7th positions are more preferable from the viewpoint of the low viscosity of the epoxy resin.
• y in the general formula (2) represents an integer of 0 to 10, but may be a state in which compounds having different y values are mixed.
• R 3 and R 4 in the general formula (3) are each independently a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.
• the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as a methyl group and an ethyl group.
• the hydrocarbon group may be substituted with a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, or may be unsubstituted.
• R 5 and R 6 in the general formula (3) are each independently a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.
• the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as a methyl group and an ethyl group.
• the hydrocarbon group may be substituted with a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, or may be unsubstituted.
• R 5 and R 6 in the general formula (3) are preferably each independently a hydrogen atom or a methyl group from the viewpoint of heat resistance of the obtained cured product, and further R 5 and R 6.
• R 5 and R 6 in the general formula (3) are preferably each independently a hydrogen atom or a methyl group from the viewpoint of heat resistance of the obtained cured product, and further R 5 and R 6.
• Z in the general formula (3) represents an integer of 0 to 10.
• z is preferably 0 to 5 from the viewpoint of the low viscosity of the epoxy resin.
• the bonding position of the glycidyl ether group in the general formula (3) is not particularly limited, but a meta position and a para position are preferable from the viewpoint of heat resistance when a cured product is used.
• z in the general formula (3) represents an integer of 0 to 10, but may be in a state where compounds having different numerical values of z are mixed.
• the numerical values of x, y and z in the general formulas (1) to (3) and the content of the compound in which x, y and z in the epoxy resin are 0 are as described in Examples described later. It can be measured by a method by liquid chromatography. Moreover, when a high molecular weight body is included in an epoxy resin, it can measure by the method by a gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• the epoxy resin (A) is represented by the general formula (1) or the general formula (2) from the viewpoint of the balance between the viscosity of the resin composition and the heat resistance of the cured product. It is preferable that it is, and more preferably, it is general formula (1).
• An epoxy resin (A) may be used individually by 1 type, and may be used together 2 or more types.
• the resin (B) used in the present embodiment has a melting point or softening point of 50 ° C. or higher.
• the melting point or softening point of the resin (B) is more preferably 50 to 150 ° C, and further preferably 60 to 130 ° C. If the melting point or softening point of the resin (B) is within the above numerical range, the resin (B) is not particularly limited, but preferably has an aromatic structure or a heterocyclic structure.
• Such a resin (B) is preferably at least one selected from the group consisting of epoxy resins, phenoxy resins, phenol novolacs, polyamic acids, polyimides, polybenzoxazoles and (meth) acrylate resins.
• resin (B) epoxy resin, polyamic acid, polyimide, and polybenzoxazole are preferable from the viewpoint of heat resistance of the obtained cured product, and epoxy resin is preferable from the viewpoint of low viscosity of the resin composition. More preferred.
• Resin (B) may be used individually by 1 type, and may be used together 2 or more types.
• the resin (B) is a resin different from the epoxy resin (A).
• the resin (B) is preferably at least one selected from the group consisting of the following general formulas (4) to (8).
• R 8, R 9 , R 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms
• R 7 and R 10 Each independently represents a divalent organic group having 1 to 10 carbon atoms.
• R 7 in the general formula (4) independently represents a divalent organic group having 1 to 10 carbon atoms.
• R 7 in the general formula (4) is independently preferably a divalent organic group having 1 to 5 carbon atoms, from the viewpoint of heat resistance of the cured product to be obtained.
• a valent organic group is more preferable.
• An example of the compound when R 7 is a divalent organic group having 1 carbon atom is triglycidyl isocyanurate.
• R 8 in the general formula (5) independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.
• the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as a methyl group and an ethyl group.
• the hydrocarbon group may be substituted with a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, or may be unsubstituted.
• R 8 is independently preferably a hydrogen atom or a monovalent organic group having 1 to 5 carbon atoms, and preferably a hydrogen atom or 1 to 3 carbon atoms.
• a monovalent organic group is more preferable.
• the bonding position of the glycidyl ether group in the general formula (5) is not particularly limited, but a meta position and a para position are preferable from the viewpoint of heat resistance when a cured product is used.
• These compounds include biphenyl type epoxy resins.
• R 9 in the general formula (6) each independently represents a monovalent organic group hydrogen atom or a C 1-10.
• the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as a methyl group and an ethyl group.
• the hydrocarbon group may be substituted with a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, or may be unsubstituted.
• each R 9 is independently preferably a hydrogen atom or a monovalent organic group having 1 to 5 carbon atoms, and is preferably a hydrogen atom or 1 to 3 carbon atoms.
• a monovalent organic group is more preferable.
• R 10 in the general formula (6) is not limited as long as a divalent organic group having 1 to 10 carbon atoms.
• a divalent organic group having 1 to 5 carbon atoms is preferable, and a divalent organic group having 1 to 3 carbon atoms is more preferable.
• the bonding position of the glycidyl ether group in the general formula (6) is not particularly limited, but from the viewpoint of heat resistance when a cured product is used, the 1,5-position, 1,6-position, 1,7-position, 1,8-position 2,6 and 2,7 are preferable, and the 1,6th and 1,7th positions are more preferable from the viewpoint of the low viscosity of the epoxy resin.
• R 11 in the general formula (7) each independently represents a monovalent organic group hydrogen atom or a C 1-10.
• the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as a methyl group and an ethyl group.
• the hydrocarbon group may be substituted with a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, or may be unsubstituted.
• each R 11 is preferably a hydrogen atom or a monovalent organic group having 1 to 5 carbon atoms, preferably a hydrogen atom or 1 to 3 carbon atoms.
• a monovalent organic group is more preferable.
• the bonding position of the glycidyl ether group in the general formula (7) is not particularly limited, but a meta position and a para position are preferable from the viewpoint of heat resistance when a cured product is obtained.
• R 12 in the general formula (8) each independently represents a monovalent organic group hydrogen atom or a C 1-10.
• the monovalent organic group having 1 to 10 carbon atoms include hydrocarbon groups such as a methyl group and an ethyl group.
• the hydrocarbon group may be substituted with a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom, or may be unsubstituted.
• R 12 is each independently preferably a hydrogen atom or a monovalent organic group having 1 to 5 carbon atoms, and preferably a hydrogen atom or 1 to 3 carbon atoms.
• a monovalent organic group is more preferable.
• the bonding position of the glycidyl ether group in the general formula (8) is not particularly limited, but a meta position and a para position are preferable from the viewpoint of heat resistance when a cured product is obtained.
• the resin (B) is selected from the group consisting of the general formulas (4) and (5). It is preferable that it is one.
• the content of the resin (B) is not limited, but is preferably 10% by mass or less and 80% by mass or less in the total resin.
• the content of the resin (B) is preferably 15% by mass or more and 70% by mass or less, and particularly preferably 15% by mass or more and 50% by mass or less from the viewpoint of storage stability of the resin composition.
• the resin composition of the present embodiment includes at least one epoxy resin (A) selected from the group consisting of general formulas (1) to (3) and at least selected from the group consisting of general formulas (4) to (8).
• the following general formulas (9) to (11) included in the total resin composition The total of the concentration of the compound represented and the chlorine concentration derived from the alkali metal chloride is preferably 0.01 ppm or more and 1000 ppm or less. Such a resin composition can achieve high heat resistance when it is made into a cured product while maintaining low viscosity.
• R 1 to R 6 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms
• x, y, and z are integers of 0 to 10
• Rx and Ry each independently represents any structure selected from the following formulas (a) to (e), provided that Rx and Ry are not simultaneously represented by the following formula (a).
• R 1 to R 6 , x, y, and z in formulas (9) to (11) have the same meanings as those in formulas (1) to (3) described above.
• the epoxy resin (A) used in the present embodiment is preferably at least one selected from the group consisting of the general formulas (1) and (2) from the viewpoint of the viscosity of the resin composition. 1) is more preferable.
• the resin (B) used in the present embodiment is preferably at least one selected from the group consisting of general formulas (4) and (5) from the viewpoint of heat resistance of the cured product. It is more preferable that
• the epoxy resin (A) is at least one selected from the group consisting of the general formulas (1) and (2), and the resin (B) is represented by the general formulas (4) and (4).
• the concentration of the compound represented by the general formulas (9) and (10), which is at least one selected from the group consisting of 5) and contained in the total resin composition, and the chlorine concentration derived from the alkali metal chloride Is more preferably 0.01 ppm or more and 1000 ppm or less.
• the epoxy resin (A) is a resin represented by the general formula (1)
• the resin (B) is a resin represented by the general formula (4). More preferably, the sum of the concentration of the compound represented by the general formula (9) contained in the total resin composition and the chlorine concentration derived from sodium chloride and potassium chloride is 0.01 ppm or more and 1000 ppm or less. .
• the sum of the concentration of the compounds represented by the general formulas (9) to (11) contained in the total resin composition and the chlorine concentration derived from the alkali metal chloride is 0.01 ppm. It is preferable that it is 1000 ppm or less.
• the total concentration is 0.01 ppm or more, there is a tendency to suppress crystallization of the resin composition and maintain a low viscosity, and when it is 1000 ppm or less, the heat resistance (glass transition temperature) of the cured product is high. Tend to be.
• the total concentration is preferably from 0.1 ppm to 1000 ppm from the viewpoint of suppressing crystallization, and more preferably from 1 ppm to 650 ppm from the viewpoint of the glass transition temperature (hereinafter also referred to as “Tg”) of the cured product. From the viewpoint of the balance between the viscosity of the cured product and the heat resistance of the cured product, 1 ppm to 200 ppm is particularly preferable.
• the concentrations of the compounds represented by the general formulas (9) to (11) and the chlorine concentration derived from the alkali metal chloride can be measured by the methods described in the examples below. .
• the ratio of the epoxy resin (A) in the total resin is 20% by mass or more and 90% by mass or less. If the proportion of the epoxy resin (A) is 20% by mass or more, the viscosity of the resin composition tends to be sufficiently low, and if it is 90% by mass or less, the heat resistance of the cured product is good.
• the proportion of the epoxy resin (A) is preferably 30% by mass or more and 90% by mass or less from the viewpoint of the viscosity of the resin composition, and more preferably 30% by mass or more and 85% by mass or less from the viewpoint of heat resistance when a cured product is obtained.
• 50% by mass or more and 85% by mass or less is particularly preferable.
• the ratio of the resin (B) in the total resin is preferably 10% by mass or less and 80% by mass or less. If the ratio of the resin (B) is 10% by mass or more, the heat resistance of the obtained cured product tends to be high, and if it is 80% by mass or less, the handleability tends to be good and the viscosity tends to be low.
• the proportion of the resin (B) is more preferably 15% by mass or more and 70% by mass or less, and particularly preferably 15% by mass or more and 50% by mass or less from the viewpoint of the storage stability of the resin composition.
• the cured product for sealing includes an epoxy resin (A) having a melting point or softening point of 30 ° C. or higher, a resin (B) having a melting point or softening point of 50 ° C. or higher, and a compound having a dioxane structure.
• the ratio of the compound (C) containing (C) and having the dioxane structure is 0.01 ppm or more and 5000 ppm or less.
• the compound (C) having a dioxane structure used in the present embodiment is not limited as long as it has a dioxane structure in the molecular structure.
• the dioxane structure include 1,2-dioxane, 1,3-dioxane, and 1,4-dioxane structure.
• 1,3-dioxane and 1,4-dioxane are preferable and 1,4-dioxane is more preferable from the viewpoint of heat resistance of the encapsulated cured product.
• the structure of the compound (C) having a dioxane structure used in this embodiment is preferably the following general formula (12) or (13).
• the following general formula (12) or (13) corresponds to a compound in which Rx and / or Ry in the general formula (9) or (10) are reacted with each other between the compounds represented by the formula (c).
• the resin composition it exists in the state represented by the general formula (9) or (10), but when this is heated to obtain a cured product, an intermolecular reaction proceeds, and the formula (12 Or a compound having a dioxane structure represented by (13).
• the ratio of the compound (C) having a dioxane structure is 0.01 ppm or more in the encapsulated cured product, the compound represented by the formula (c) at the end has a dioxane structure. If it is 5000 ppm or less, the crosslink density is high, so that the heat resistance is improved.
• the ratio of the compound (C) having a dioxane structure is not limited as long as it is 0.01 ppm or more and 5000 ppm or less, but the epoxy resin (A) is represented by the general formula (1).
• the compound (C) having a dioxane structure is a compound represented by the general formula (12)
• it is preferably 0.035 ppm or more and 3450 ppm or less.
• the proportion of the compound (C) having a dioxane structure is such that the epoxy resin (A) is the general formula (2) and the compound (C) having the dioxane structure is the general formula.
• the structure represented by (13) it is preferably 0.04 ppm or more and 4000 ppm or less.
• the ratio of the compound (C) which has a dioxane structure can be measured by the method as described in the below-mentioned Example.
• a method for producing an epoxy resin (A) having a total chlorine content of 0.01 ppm or more and 1000 ppm or less will be described below, taking the case where the epoxy resin (A) is a compound represented by the general formula (1) as an example. To do.
• the method for reducing the chlorine content is not particularly limited, and examples thereof include a method of heating in the presence of a basic substance (alkali heating method) and a method of molecular distillation. By these methods, the amount of chlorine can be sufficiently reduced. Among them, molecular distillation alone and a method of performing molecular distillation after alkali treatment are preferable.
• the basic substance used in this embodiment is not limited as long as the chlorination of the epoxy resin can be performed without increasing the molecular weight or gelling.
• These basic substances include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrides such as sodium hydride and lithium hydride, potassium t-butoxide, sodium t-butoxide, potassium iso Examples include alkali metal alkoxides such as propoxide. Among these, alkali metal alkoxides are preferable from the viewpoint of the hue of the epoxy resin described later.
• a purification step purification method including a process is mentioned.
• the total chlorine content in the resulting epoxy resin (A) is 0.01 ppm or more and 1000 ppm or less, preferably 0.1 ppm or more and 1000 ppm, from the viewpoint of the glass transition temperature of the cured product (hereinafter also referred to as “Tg”).
• Tg glass transition temperature of the cured product
• 1 ppm or more and 650 ppm or less are more preferable, and 1 ppm or more and 200 ppm or less are particularly preferable from the viewpoint of the balance between the viscosity of the resin composition and the heat resistance of the cured product.
• the crude epoxy resin used for this embodiment can be obtained by a well-known method, for example, can be obtained by the manufacturing method including the process of making a phenol compound and an epichlorohydrin compound react.
• the crude epoxy resin obtained by such a production method contains chlorine as an impurity in addition to the compound represented by the general formula (1).
• the chlorine content include hydrolyzable chlorine and organic bond chlorine.
• the content of chlorine in the crude epoxy resin (hereinafter also referred to as “total chlorine content”) is, for example, 1000 to 8000 ppm.
• An epoxy resin (A) in which the amount of chlorine is reduced (hereinafter also referred to as “low chlorination”) can be obtained by the production method including the purification step.
• the crude epoxy resin contains, for example, both hydrolyzable chlorine and organic bond chlorine as the chlorine component.
• hydrolyzable chlorine refers to, for example, chlorine existing in a state as shown in the following formula (1-2)
• organic bond chlorine refers to, for example, the following formula (1) -3) Chlorine that exists in the state shown in the figure.
• a hydrogen atom that is supposed to be extracted by the mechanism shown in the following formula (3-2) has a low acidity and is conventionally considered to be difficult to be extracted. Nevertheless, according to the above-described method for producing the epoxy resin (A), hydrogen atoms are extracted as shown in the following formula (3-2), and organic bond chlorine can be removed.
• the gelation of the epoxy resin proceeds.
• the alkoxide acts as a base in preference to a nucleophilic reaction. It is thought that the removal of the chlorine content proceeds without the gelation of.
• the epoxy resin (A) production method described above is an epoxy having an excellent hue by performing the above-mentioned step (a), which is a treatment using an alkali metal alkoxide among alkali treatments, and further combining a distillation step (b). A resin can be obtained. This will be described in detail below.
• a crude epoxy resin is obtained by reacting a phenol compound with an epichlorohydrin compound, it contains various impurities in addition to the target epoxy compound.
• many impurities in the crude epoxy resin tend to be removed, but impurities having a boiling point similar to that of the target epoxy compound cannot be removed.
• an epoxy compound having a large equivalent among the epoxy compounds represented by the general formula (1) can be separated from impurities by carrying out distillation.
• the impurity which is the cause of coloring has a boiling point comparable as the objective epoxy compound, even if it distills, it cannot isolate
• an epoxy resin excellent in hue can be obtained by combining (a) the step of treating the crude epoxy resin with an alkali metal alkoxide in an organic solvent and (b) the step of distillation.
• the manufacturing method of the above-mentioned epoxy resin (A) is an epoxy resin having an excellent hue by performing both (a) a step of treating with an alkali metal alkoxide in an organic solvent and (b) a step of distillation. A) can be obtained.
• a crude epoxy resin contains the compound represented by the said General formula (1), for example.
• the content of the compound represented by the general formula (1) is, for example, 90 to 95% by mass.
• the compound represented by the general formula (1) exists as a mixture containing two or more compounds having different values of x in the formula (1).
• the above-mentioned method for producing an epoxy resin includes (a) a step of treating a crude epoxy resin containing a compound represented by the general formula (1) and a chlorine content with an alkali metal alkoxide in an organic solvent, and (b) distillation. A purification process including the process is performed.
• step (a) and (b) are not limited, but it is more preferable to carry out the step (b) after the step (a) from the viewpoint of the hue of the epoxy resin. Each step will be described below.
• organic solvent used in the present embodiment is not particularly limited as long as the organic solvent can uniformly dissolve or disperse the crude epoxy resin.
• organic solvents include ethers such as tetrahydrofuran, dioxane, and dibutyl ether; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane and cyclohexane; acetone, methyl ethyl ketone, and isobutyl ketone.
• Ketones such as methyl acetate and ethyl acetate; Amides such as dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone; Sulfur compounds such as dimethyl sulfoxide Is mentioned. These may be used alone or in combination of two or more.
• alkali metal alkoxide Since the epoxy group in the compound represented by the general formula (1) has high reactivity with the nucleophile, the alkali metal alkoxide used in this embodiment does not act as a nucleophile on the epoxy group. In addition, it is preferable to use a bulky alkali metal alkoxide having strong basicity and low nucleophilicity. Specific examples of the alkali metal alkoxide include potassium t-butoxide, sodium t-butoxide, potassium isopropoxide, sodium isopropoxide, potassium ethoxide, sodium ethoxide and the like. These may be used alone or in combination of two or more.
• potassium t-butoxide, sodium t-butoxide, potassium isopropoxide, and sodium isopropoxide are preferable from the viewpoint of suppression of gelation of the epoxy resin and basicity, and chlorine contained in the epoxy resin. From the viewpoint of reducing the amount, potassium t-butoxide and sodium t-butoxide are more preferable, and potassium t-butoxide is particularly preferable.
• the treatment time in step (a) is not limited as long as the epoxy resin does not gel and the chlorine content in the crude epoxy resin is reduced, but is preferably 1 minute to 24 hours, more preferably 5 minutes to 10 hours. 15 minutes to 5 hours is more preferable. It is particularly preferable that the treatment time in the step (a) is within the above range from the viewpoint of achieving both suppression of the progress of gelation of the epoxy resin and reduction of the chlorine content in the crude epoxy resin.
• the treatment temperature in the step (a) is not limited as long as the epoxy resin does not gel and the chlorine content in the crude epoxy resin is reduced, but it is preferably ⁇ 20 ° C. or higher and 90 ° C. or lower, and ⁇ 10 ° C. or higher and 80 ° C. or lower. The following is more preferable, and 0 ° C. or higher and 60 ° C. or lower is further preferable. It is particularly preferable that the treatment temperature in the step (a) is in the above range from the viewpoint of achieving both suppression of the progress of gelation of the epoxy resin and reduction of the chlorine content in the crude epoxy resin.
• the addition amount of the alkali metal alkoxide used in the present embodiment is not limited as long as the total chlorine amount in the crude epoxy resin is sufficiently reduced and gelation of the epoxy resin does not occur, but the total amount contained in the crude epoxy resin is not limited.
• the amount is preferably 1 to 20 molar equivalents relative to the amount of chlorine, more preferably 2 to 15 molar equivalents from the viewpoint of reducing the amount of chlorine in the crude epoxy resin, and 3 to 15 molar equivalents. More preferably, it is 5 to 12 molar equivalents, particularly preferably 5 to 10 molar equivalents.
• the concentration of the crude epoxy resin used in the step (a) is 10 to 90 when the total amount of the crude epoxy resin and the organic solvent used in the step (a) is 100% by mass.
• the content is preferably in the range of mass%, more preferably in the range of 15 mass% to 70 mass% from the viewpoint of suppressing side reactions.
• the weight of the crude epoxy resin and the organic solvent in the step (a) preferably satisfies 0.1 ⁇ (weight of the crude epoxy resin) / (weight of the crude epoxy resin + weight of the organic solvent) ⁇ 0.9. It is more preferable that 15 ⁇ (weight of crude epoxy resin) / (weight of crude epoxy resin + weight of organic solvent) ⁇ 0.7. If the weight of the crude epoxy resin and the organic solvent in the step (a) satisfies the above conditions, the epoxy resin tends to be reduced in the chlorine content efficiently without the gelation of the epoxy resin proceeding.
• the method for producing the epoxy resin is not limited as long as the epoxy resin does not gel and the chlorine content in the crude epoxy resin is reduced, but from the viewpoint of separation from the inorganic salt after the step (a). Further, it is preferable to further include a post-processing step.
• a treatment step with an acid or water and a treatment step with a liquid separation operation are preferable.
• the acid used in the post-treatment step is not particularly limited. For example, phosphoric acid, sodium phosphate, potassium phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, acetic acid, oxalic acid, hydrochloric acid, sulfuric acid, nitric acid Etc.
• the crude epoxy resin is not limited as long as distillation method can be purified. Examples of such distillation methods include simple distillation and thin film distillation.
• the step (b) of distillation is preferably performed at a degree of vacuum of 0.05 kPa to 0.3 kPa and a distillation internal temperature of 150 ° C. to 180 ° C.
• the degree of vacuum is 0.05 kPa or more, it is preferable that a compound having a ring-opening as an impurity can be suppressed in addition to the target epoxy compound (for example, resorcinol diglycidyl ether).
• the degree of vacuum is 0.3 kPa or less, it is preferable that the heating temperature exceeds 180 ° C., so that the gelation of the epoxy resin proceeds during distillation and the yield can be significantly reduced.
• the degree of vacuum is preferably from 0.1 kPa to 0.2 kPa, and the distillation internal temperature is preferably from 155 ° C. to 175 ° C.
• the epoxy resin which concerns on this embodiment is an epoxy resin represented by following General formula (1), Comprising: The total chlorine amount contained in the said epoxy resin is 0.01 ppm or more and 1000 ppm or less.
• each R 1 independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms
• x represents an integer of 0 or more and 5 or less
• the epoxy resin which concerns on this embodiment is an epoxy resin represented by following General formula (2), Comprising:
• the total chlorine amount contained in the said epoxy resin is 0.01 ppm or more and 1000 ppm or less.
• R 2 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms
• y represents an integer of 0 or more and 5 or less
• the curable resin composition according to this embodiment preferably contains the above-described resin composition or the above-described epoxy resin (A) and the curing accelerator (A).
• the content of the above-described resin composition or the above-described epoxy resin (A) is preferably 20 to 99% by mass from the viewpoint of heat resistance of the cured product.
• the content is more preferably -98% by mass, and further preferably 40-96% by mass.
• the curable resin composition according to the present embodiment can further contain other epoxy resins within a range that does not adversely affect the performance.
• epoxy resins include alicyclic epoxy resins having a total chlorine content of 0 ppm, such as 3,4-epoxy-6-methylcyclohexylmethyl carboxylate and 3,4-epoxycyclohexylmethylcarboxylate.
• the amount of other epoxy resin added is not limited as long as it does not adversely affect the performance, but it is preferably 30% by mass or less in the total resin.
• ⁇ Curing accelerator (I)> As a hardening accelerator (I), what is necessary is just a compound which can accelerate
• a hardening accelerator (I) a nitrogen compound, a phosphorus compound, and a latent hardening accelerator are preferable from a compatible viewpoint with the resin composition mentioned above or the epoxy resin (A) mentioned above.
• a hardening accelerator (I) may be used individually by 1 type, and may be used together 2 or more types.
• nitrogen compound examples include 1,8-diaza-bicyclo (5,4,0) undecene-7, 1,5-diaza-bicyclo (4,3,0) nonene, 5,6-dibutylamino-1, Cycloamidine compounds such as 8-diaza-bicyclo (5,4,0) undecene-7; tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and their derivatives Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and derivatives thereof.
• Examples of the phosphorus compound include organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, and phenylphosphine. These may be used alone or in combination of two or more.
• organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, and phenylphosphine. These may be used alone or in combination of two or more.
• latent curing accelerators dispersion type curing accelerators, thermal decomposition type curing accelerators, photodegradation type curing accelerators, moisture curing type curing accelerators, molecular sieve encapsulated type curing accelerators, and microencapsulated potentials A hardening accelerator etc. are mentioned.
• the latent curing accelerator is a curing accelerator that can extremely slow the curing reaction rate at room temperature while maintaining the curing reaction rate at the curing temperature of the epoxy resin.
• dispersion type curing accelerator examples include dicyandiamide, adipic acid hydrazide, diamino maleonitrile, diallyl melamine, poly (piperidine-sebatic acid) amide, and imidazole / triazine derivatives.
• a thermal decomposition type curing agent is a compound that decomposes into an amine compound such as a tertiary amine and a compound such as isocyanate when heated.
• amine compound such as a tertiary amine
• compound such as isocyanate when heated.
• examples thereof include amine imide synthesized from carboxylic acid ester, methyl hydrazine and epoxy compound.
• a photodegradable curing accelerator is a compound that is decomposed by irradiation with ultraviolet rays or visible light and activated as a curing accelerator.
• aromatic diazonium salt, diallyl iodonium salt, triallyl sulfonium salt, triallyl selenium salt and the like can be mentioned.
• moisture curable curing accelerator examples include ketimine compounds synthesized from aliphatic polyamines and ketone compounds.
• Examples of the molecular sieve encapsulated curing accelerator include those obtained by absorbing an aliphatic polyamine in a molecular sieve.
• the microencapsulated curing accelerator refers to a curing accelerator having a curing accelerator as a core and a shell structure around it.
• a curing accelerator having a curing accelerator as a core and a shell structure around it.
• an amine-epoxy adduct type in which an imidazole compound is arranged in the core structure and an epoxy resin is arranged in the shell structure, and “Novacure (registered trademark)” and the like correspond to this.
• the content of the curing accelerator (A) is more preferably 1 to 50% by mass from the viewpoint of heat resistance of the cured product, and 2 to 40% by mass. More preferably.
• the curable resin composition according to this embodiment preferably further contains a curing agent.
• the curing agent (c) is not particularly limited as long as it is a compound that can cure the above-described resin composition or the above-described epoxy resin (a).
• an acid anhydride compound, an acid dianhydride compound, an amine compound, a phenol compound, and the like are preferable from the viewpoint of reactivity with the above-described epoxy resin.
• curing agent (c) may be used individually by 1 type, and may be used together 2 or more types.
• Examples of the acid anhydride compound include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic acid anhydride, methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride, phthalic anhydride, and trimellitic anhydride. Acid, dodecenyl succinic anhydride and the like.
• acid dianhydride compound examples include pyromellitic anhydride, oxydiphthalic dianhydride, biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, and benzophenone-3,3 ′, 4,4.
• amine compounds include aromatic amines, aliphatic amines, and alicyclic amines.
• aromatic amine examples include metaxylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, metaphenylenediamine, and the like.
• aromatic amines for example, “Epicure W”, “Epicure Z” (all trade names made by Japan Epoxy Resin Co., Ltd.), “Kayahard AA”, “Kayahard A— B ”,“ Kayahard AS ”(all trade names, manufactured by Nippon Kayaku Co., Ltd.),“ Totoamine HM-205 ”(trade names, manufactured by Tohto Kasei Co., Ltd.),“ Adeka Hardener EH-101 ”(Asahi Denka Kogyo) And “Epomic Q-640”, “Epomic Q-643” (both trade names, Mitsui Chemicals), “DETDA80” (trade names, manufactured by Lonza), and the like.
• aliphatic amine examples include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and diethylaminopropylamine.
• alicyclic amines examples include mensendiamine, isophoronediamine, N-aminoethylpiperazine, bis (4-aminocyclohexyl) methane, and the like.
• phenol compound examples include phenol compounds such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol; phenols (phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, and phenylphenol). , Aminophenol, etc.) and / or naphthols ( ⁇ -naphthol, ⁇ -naphthol, dihydroxynaphthalene, etc.) and compounds having an aldehyde group (formaldehyde, benzaldehyde, salicylaldehyde, etc.) in the presence of an acidic catalyst.
• phenol compounds such as phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol
• phenols phenol, cresol, resorcin, catechol, bisphenol A, bisphenol F, and phenylphenol
• Novolac-type phenolic resin obtained by mixing with phenols and / or naphthols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl
• Phenol-aralkyl resins synthesized from aralkyl
• aralkyl-type phenol resins such as naphthol-aralkyl resins
• dichloropentadiene-type phenol novolac resins synthesized by copolymerization from phenols and / or naphthols and cyclopentadiene
• naphthol novolaks Examples thereof include dichloropentadiene-type phenol resins such as resins; terpene-modified phenol resins.
• an acid anhydride compound is preferable from the viewpoint of the viscosity of the curable resin composition.
• the acid anhydride compounds tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic acid anhydride, and methyl nadic acid anhydride are more preferable from the viewpoint of heat resistance of the resulting cured product, and particularly nadic acid.
• An acid anhydride and methyl nadic acid anhydride are more preferable.
• the content of the curing agent (c) is P, the epoxy equivalent of the resin composition described above or the epoxy resin (a) described above, and the functional group equivalent of the curing agent (c).
• Q is Q
• 0.7 ⁇ Q / P ⁇ 1.3 is preferable from the viewpoint of heat resistance of the cured product
• 0.8 ⁇ Q / P ⁇ 1.2 is more preferable
• 0.9 ⁇ Q / P ⁇ 1.1 is particularly preferred.
• the curable resin composition of the present embodiment may contain an inorganic filler (d) if necessary.
• the inorganic filler (d) include fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, zirconia, zircon, fosterite, Examples thereof include powders such as steatite, spinel, mullite, and titania, beads formed by spheroidizing these, and glass fibers.
• examples of the inorganic filler (d) having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate.
• fused silica, crystalline silica, and alumina are preferable from the viewpoint of chemical resistance of the obtained cured product, and alumina is more preferable from the viewpoint of thermal conductivity.
• these inorganic fillers (d) are preferably surface-treated with a silane coupling agent or the like from the viewpoint of the viscosity of the curable resin composition.
• the amount of the inorganic filler (d) added is the above-mentioned epoxy resin (A) having a total chlorine content of 0.01 ppm to 1000 ppm, and a melting point or softening point of 50.
• the total content of the resin (B) at a temperature equal to or higher than 100 ° C. is 100 parts by mass, it is preferably 0 to 500 parts by mass, more preferably 0 to 300 parts by mass, and 0 to 200 parts by mass. More preferably.
• adhesion assistant examples include silane coupling agents, titanate coupling agents, aluminum coupling agents, etc. Among them, silane coupling agents are preferable.
• silane coupling agent examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -ureidopropyltriethoxysilane, and N- ⁇ -aminoethyl. - ⁇ -aminopropyltrimethoxysilane and the like.
• the blending amount of the coupling agent is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin composition or the epoxy resin (a), from the effect of addition and heat resistance.
• Examples of the flame retardant include phosphorus compounds such as phosphate ester compounds and phosphazene compounds, and nitrogen compounds such as melamine flame retardants.
• Examples of the phosphoric acid ester compound include phosphoric acid esters substituted with an aliphatic hydrocarbon group such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, triisobutyl phosphate, tris (2-ethylhexyl) phosphate; tris (butoxyethyl) Phosphate ester substituted with an aliphatic organic group containing an oxygen atom such as phosphate; aromatic organic group such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, resorcinol bis (diphenyl phosphate) as a substituent And phosphoric acid ester compounds.
• an aliphatic hydrocarbon group such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, triisobutyl phosphate, tris (2-ethylhexyl) phosphate; tris (butoxyeth
• Examples of the phosphazene compound include “Ravitor (registered trademark) FP-100” and “Ravitor (registered trademark) FP-300” manufactured by Fushimi Pharmaceutical.
• melamine flame retardant examples include melamine cyanurate and melamine polyphosphate.
• the ion scavenger examples include a copper damage preventing agent for preventing copper from being ionized and dissolved, and an inorganic ion adsorbent.
• the copper component used as a material may be ionized by contact with moisture or the like.
• the curable resin composition containing the copper damage inhibitor and the inorganic ion adsorbent described above it is possible to supplement and adsorb copper ions and the like that are eluted in contact with moisture and the like.
• Examples of copper damage inhibitors include triazine thiol compounds and bisphenol reducing agents. These can also use a commercial item, for example, "disnet DB” (trade name, manufactured by Sankyo Pharmaceutical Co., Ltd.) as a copper damage inhibitor containing a triazine thiol compound as a component, and copper damage containing a bisphenol-based reducing agent as a component. Examples of the inhibitor include “Yoshinox BB” (trade name, manufactured by Yoshitomi Pharmaceutical Co., Ltd.).
• Examples of the inorganic ion adsorbent include zirconium compounds, antimony bismuth compounds, magnesium aluminum compounds, and the like. Commercially available products can also be used as the inorganic ion adsorbent, and examples thereof include “IXE-100” (trade name, manufactured by Toa Gosei Chemical Co., Ltd.) as a cation exchange type.
• the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon.
• non-conductive glass, ceramic, plastic or the like may be used as a core, and the core may be coated with the metal particles or carbon.
• the conductive particles are made of plastic as a core and the core is coated with the metal particles or carbon, or are hot-melt metal particles, they have deformability due to heat and pressure. This is preferable because the contact area is increased and the connection reliability is improved.
• the fine particles obtained by further coating the surface of these conductive particles with a polymer resin or the like can suppress short-circuiting due to contact between the particles when the amount of the conductive particles is increased, and can improve the insulation between the electrode circuits. .
• the average particle diameter of the conductive particles is preferably 1 to 18 ⁇ m from the viewpoint of dispersibility and conductivity.
• the average particle diameter here is the primary particle diameter and can be measured by a particle size distribution meter or the like.
• the amount of the conductive particles used is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition or epoxy resin (a). .
• the amount of the conductive particles used is 0.1 parts by mass or more, the conductivity tends to be improved, and when it is 30 parts by mass or less, a short circuit tends to be prevented.
• Examples of the colorant include carbon black.
• mold release agent a conventionally known mold release agent can be used.
• examples of commercially available products include “SH 7020” (trade name, manufactured by Toray Dow Corning).
• the resin composition of the present embodiment and the curable resin composition using the resin composition are preferably used as an underfill material, a die attach material, a liquid sealing material, and a material for an electronic component including them. it can.
• Underfill material and liquid encapsulant of the present embodiment includes the above-mentioned resin composition or the curable resin composition.
• the underfill material and liquid sealing material of this embodiment can be manufactured by a known manufacturing method.
• it can be manufactured by sufficiently mixing the above-described curable resin composition and enclosing it in a container that can be dispensed.
• the resin composition and the curable resin composition described above has good workability, underfill material and liquid encapsulant comprising the resin composition and the curable resin composition, a semiconductor component or the like and the substrate with the It is possible to easily fill the gaps and the like.
• the underfill material and the liquid sealing material containing the resin composition and the curable resin composition are: Low performance degradation due to thermal history during soldering. It does not specifically limit as a kind of said base material, For example, a silicon wafer etc. are mentioned.
• the die attach material of this embodiment contains the above-mentioned resin composition or curable resin composition.
• the die attach material of this embodiment can be manufactured by a known manufacturing method. For example, it can be produced by applying the above-mentioned resin composition or curable resin composition to a base material and heating it until it loses fluidity at room temperature. It does not specifically limit as a kind of said base material, For example, a silicon wafer etc. are mentioned.
• the electronic component of the present embodiment includes at least one selected from the group consisting of the above-described underfill material, die attach material, and liquid sealing material.
• Examples of electronic components including the above-described underfill material, die attach material, and liquid sealing material include semiconductor packages, interposers, Si through electrodes, and the like.
• At least one selected from the group consisting of an underfill material, a die attach material, and a liquid sealing material containing the above-described resin composition or curable resin composition It can be formed by including at least one selected from the group consisting of a material, a die attach material and a liquid sealing material.
• the resin composition or the curable resin composition according to the present embodiment specifically, a protective layer formed of a printed wiring board and the circuit board used in the operation panel of various electronic devices and the like in the electronics field, the insulating laminated board Used for film formation for use in layer formation, silicon wafers used in semiconductor devices, semiconductor chips, semiconductor device peripherals, semiconductor mounting substrates, heat sinks, lead pins, semiconductors themselves, insulation and adhesion Is done.
• RDGE-H Resorcinol diglycidyl ether, trade name “ERISYS RDGE-H” manufactured by CVC Specialty Chemicals, hereinafter abbreviated as “RDGE-H”.
• R 1 are hydrogen atoms
• the bonding position of the glycidyl ether and epoxy group ring-opening sites to the benzene ring is the meta position
• the total amount of chlorine in RDGE-H was 3254 ppm.
• the total chlorine content in HP-4032 was 1400 ppm.
• the total chlorine content in AER260 was 1350 ppm.
• the total chlorine content in LX-01 was 10 ppm.
• TEPIC-S corresponds to a resin in which R 7 is a methylene group in the general formula (4). Melting point: 90-125 ° C.
• YX4000H is a resin in the formula (5) in which two R 8 out of four R 8 are methyl groups, the remaining two R 8 are hydrogen atoms, and the bonding positions of the glycidyl ether groups are each in the para position. Equivalent. Specifically, it corresponds to the following general formula (14). Melting point: 105-110 ° C.
• HP-4710 1-Chloro-2,3-epoxypropane, formaldehyde, 2,7-naphthalenediol polycondensate DIC Corporation, trade name “EPICRON HP-4710”, hereinafter also abbreviated as “HP-4710”.
• HP-4710 corresponds to a resin in formula (6) in which R 9 is all hydrogen atoms, R 10 is a methylene group, and the bonding positions of glycidyl ether groups are 1 and 4 positions, respectively. Specifically, it corresponds to the following general formula (15). Melting point: 95 ° C.
• 1031S Tetrakis (hydroxyphenyl) ethane type epoxy resin, trade name “jER 1031S” manufactured by Mitsubishi Chemical Corporation, hereinafter also abbreviated as “1031S”.
• 1031S corresponds to a resin in which R 11 is all hydrogen atoms and the bonding position of the glycidyl ether group is para-position in formula (7). Specifically, it corresponds to the following general formula (16). Melting point: 90-100 ° C.
• 1032H60 Tris (hydroxyphenyl) methane type epoxy resin, trade name “jER 1032H60” manufactured by Mitsubishi Chemical Corporation, hereinafter also abbreviated as “1032H60”.
• 1032H60 corresponds to a resin in which R 12 is all hydrogen atoms and the bonding position of the glycidyl ether group is para-position in formula (8). Specifically, it corresponds to the following general formula (17). Melting point: 56-62 ° C.
• HNA-100 is an acid anhydride compound.
• the said chlorine amount was made into the "total chlorine amount" contained in an epoxy resin or a resin composition.
• a composite silver electrode (for Ag precipitation titration, “C-373” manufactured by Kyoto Electronics Co., Ltd.) was used as an electrode, and titration was performed using a 0.01 mol / L silver nitrate aqueous solution.
• a composite silver electrode (for Ag precipitation titration, “C-373” manufactured by Kyoto Electronics Co., Ltd.) was used as an electrode, and titration was performed using a 0.01 mol / L silver nitrate aqueous solution.
• HCL-8320GPC manufactured by Tosoh Corporation
• Viscosity measurement> The viscosity was measured using a viscometer (manufactured by Toki Sangyo Co., Ltd., “VISCOMETER TV-20”). The measurement temperature was 23 ° C. or 40 ° C., and CORD-1 (1 ° 34 ′ ⁇ R24) was used as the rotor.
• ⁇ Storage stability evaluation> The initial viscosity (measured within 6 hours after adjusting the composition) and the viscosity after standing for 30 days at 23 ° C. were measured for the resin composition by the above viscosity measurement method, and the “viscosity after 30 days / initial viscosity” The storage stability was evaluated based on the calculated viscosity increase rate. The smaller the viscosity increase rate, the better the storage stability.
• the glass transition temperature (Tg) was measured using a differential scanning calorimeter (manufactured by Shimadzu Corporation, “DSC-60”).
• a sample epoxy resin composition (about 20 mg) was placed in an aluminum pan, heated to 250 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, held for 30 minutes, and cured. Then, after cooling the cured product of the epoxy resin composition to room temperature, the Tg of the cured product was measured by further raising the temperature to 280 ° C. at 10 ° C./min.
• ⁇ Measurement of ratio of compound (C) having dioxane structure in cured product The ratio of the compound (C) having a dioxane structure in the cured product was measured using pyrolysis gas chromatography. After the epoxy resin composition was cured (in air atmosphere, the temperature was raised from room temperature to 120 ° C. at 10 ° C./min, held for 30 minutes, then heated to 180 ° C. at 10 ° C./min and held for 30 minutes). The cured product was measured by pyrolysis gas chromatography. The ratio of the compound (C) having a dioxane structure was calculated from the ratio between the total peak area and the peak area derived from the compound (C).
• ⁇ Melting point or measurement of resin> The melting point of the resin was measured using a differential scanning calorimeter (“DSC-60” manufactured by Shimadzu Corporation). A sample resin (about 20 mg) was placed in an aluminum pan, heated to 250 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, and the temperature at which an endothermic peak was observed was defined as the melting point or softening point.
• DSC-60 differential scanning calorimeter
• Example 1 Resorcinol diglycidyl ether: RDGE-H (386.75 g) was placed in an eggplant-shaped flask, a T-tube, a thermometer and a condenser were attached, and molecular distillation was performed at a reduced pressure of 0.1 kPa. Distillation was started at a system temperature of 137 ° C, and the first distillation was performed until the system temperature increased to 157 ° C. Distillation was started when the system temperature reached 165 ° C. A molecular distillate of resorcinol diglycidyl ether was obtained with a yield of 57.7%. The total amount of chlorine in the obtained molecular distillate was 610 ppm.
• the total chlorine content of resorcinol diglycidyl ether not subjected to molecular distillation was 3254 ppm, and the viscosity at 40 ° C. was 150 mPa ⁇ s.
• the detected peak was only the monomer, and no dimer or higher peak was detected, and both were below the detection limit (0.01% by mass or less).
• the resulting molecular distillate had a melting point of 39-40 ° C.
• Example 2 Resorcinol diglycidyl ether (168.59 g) obtained in Example 1 and subjected to molecular distillation once was subjected to molecular distillation again in the same manner as in Example 1.
• distillation was started at a reduced pressure of 0.2 kPa and an internal temperature of 145 ° C, and the first distillation was performed until the internal temperature increased to 160 ° C. Distillation was started when the system temperature reached 170 ° C. A molecular distillate was obtained with a yield of 58.0%. The total amount of chlorine in the obtained molecular distillate was 420 ppm.
• the detected peak was only the monomer, and the dimer The above peaks were not detected, and all were below the detection limit (0.01% by mass or less).
• the resulting molecular distillate had a melting point of 39-40 ° C.
• Example 3 Resorcinol diglycidyl ether (41.04 g) obtained by carrying out the molecular distillation twice obtained in Example 2 was again subjected to molecular distillation in the same manner as in Example 1.
• distillation was started at a reduced pressure of 0.11 kPa and an internal temperature of 135 ° C., and the initial distillation was performed until the internal temperature increased to 155 ° C. Distillation was started when the system temperature reached 160 ° C. A molecular distillate was obtained with a yield of 59.8%. The total amount of chlorine in the obtained molecular distillate was 130 ppm.
• the detected peak was only the monomer, and the dimer The above peaks were not detected, and all were below the detection limit (0.01% by mass or less).
• the resulting molecular distillate had a melting point of 39-40 ° C.
• the organic phase was washed with distilled water (50.0) three times and separated to obtain an organic phase.
• the obtained organic phase was distilled off under reduced pressure to obtain an epoxy resin with a yield of 75.5%.
• the obtained epoxy resin was distilled at a reduced pressure of 0.12 kPa and an internal temperature of 135 ° C., and the initial distillation was performed until the internal temperature increased to 155 ° C. Distillation was started when the system temperature reached 160 ° C.
• a molecular distillate was obtained with a two-stage yield of 43.8%.
• the total amount of chlorine in the obtained molecular distillate was 8 ppm.
• the detected peak was only the monomer, and the dimer The above peaks were not detected, and all were below the detection limit (0.01% by mass or less).
• the resulting molecular distillate had a melting point of 39-40 ° C.
• Example 5 In an eggplant-shaped flask, 1,6-bis (glycidyloxy) naphthalene: HP-4032 (15.0 g) was added, toluene (30.0 g) and N-methyl-2-pyrrolidone (30.0 g) were added, and magnetic. The mixture was stirred with a stirrer until uniform. Further, 0.67 g of potassium t-butoxide (10 molar equivalents relative to the total amount of chlorine in HP4032) was added and stirred at 35 ° C. for 30 minutes. Distilled water (15.0 g) was added to the stirred solution and stirred for 10 minutes.
• the obtained solution was transferred to a separating funnel, and distilled water (15.0 g), 2-propanol (15.0 g) and methyl isobutyl ketone (15.0 g) were added and washed. After washing, the organic phase was obtained by further washing with distilled water (15.0 g) three times. The obtained organic phase was distilled off under reduced pressure to obtain an epoxy resin (1,6-bis (glycidyloxy) naphthalene).
• the obtained epoxy resin was distilled at a reduced pressure of 0.08 kPa and an internal temperature of 155 ° C., and the initial distillation was performed until the internal temperature increased to 175 ° C. Distillation was started when the system temperature reached 180 ° C. A molecular distillate was obtained with a two-stage yield of 47.4%. The total amount of chlorine in the obtained molecular distillate was 4 ppm. Further, the epoxy resin, which is the molecular distillate obtained, was subjected to gel permeation chromatography (GPC) measurement to analyze the detected peak. As a result, the monomer ratio was 96.5% by mass. . The obtained molecular distillate had a melting point of 45 to 48 ° C.
• Example 6 Resorcinol diglycidyl ether (85 parts by mass) obtained in Example 1 and TEPIC-S (15 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1.
• Example 7 Resorcinol diglycidyl ether (70 parts by mass) obtained in Example 1 and TEPIC-S (30 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1. Moreover, it was 1200 ppm when this resin composition was measured by the measuring method of the ratio of the compound (C) which has a dioxane structure in the above-mentioned hardened
• Example 8 Resorcinol diglycidyl ether (40 parts by mass) obtained in Example 1 and TEPIC-S (60 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1.
• Example 9 Resorcinol diglycidyl ether (88 parts by mass) obtained in Example 1 and TEPIC-S (12 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1.
• Example 10 Resorcinol diglycidyl ether (70 parts by mass) obtained in Example 2 and TEPIC-S (30 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1.
• Example 11 Resorcinol diglycidyl ether (70 parts by mass) obtained in Example 3 and TEPIC-S (30 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1.
• Example 12 Resorcinol diglycidyl ether (70 parts by mass) obtained in Example 4 and TEPIC-S (30 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1.
• Example 13 By mixing 85 parts by weight of resorcinol diglycidyl ether obtained in Example 1 with TEPIC-S (15 parts by weight) and HNA-100 (161.1 parts by weight), heating at 130 ° C. TEPIC-S was dissolved to obtain a solution. After this solution was cooled to 25 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg and storage stability at 23 ° C. of this epoxy resin composition were measured. The results are shown in Table 1.
• Example 14 After mixing TEPIC-S (20 parts by mass) and HNA-100 (162 parts by mass) with 80 parts by mass of resorcinol diglycidyl ether obtained in Example 1, the TGIC was heated at 130 ° C. Dissolved to obtain a solution. After this solution was cooled to 25 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.
• Example 15 After mixing TEPIC-S (30 parts by mass) and HNA-100 (164 parts by mass) with 70 parts by mass of resorcinol diglycidyl ether obtained in Example 1, TGIC was heated at 130 ° C. Dissolved to obtain a solution. After this solution was cooled to 25 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.
• Example 16 After mixing TEPIC-S (30 parts by mass) and HNA-100 (164 parts by mass) with 70 parts by mass of resorcinol diglycidyl ether obtained in Example 1, TGIC was heated at 130 ° C. Dissolved to obtain a solution. After cooling this solution to 25 ° C., NovaCure HX-3941HP (4 parts by mass) and alumina filler (177.4 parts by mass) were mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.
• Example 17 After mixing YH4000H (15 parts by mass) with 85 parts by mass of resorcinol diglycidyl ether obtained in Example 1, YH4000H was dissolved by heating at 130 ° C. to obtain a solution. After cooling to 0 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability at 23 ° C. of this epoxy resin composition were measured by the method described above. The results are shown in Table 1.
• Example 18 YX4000H (15 parts by mass) and HNA-100 (149.1 parts by mass) were mixed with 85 parts by mass of resorcinol diglycidyl ether obtained in Example 1, and then heated at 130 ° C. to obtain YX4000H. Dissolved to obtain a solution. After this solution was cooled to 25 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability at 23 ° C. of this epoxy resin composition were measured by the method described above. The results are shown in Table 1.
• Example 19 After mixing HP4710 (15 parts by mass) with 85 parts by mass of resorcinol diglycidyl ether obtained in Example 1, HP4710 was dissolved by heating at 130 ° C. to obtain a solution. After this solution was cooled to 25 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.
• Example 20 HP4710 (15 parts by mass) and HNA-100 (150.4 parts by mass) were mixed with 85 parts by mass of resorcinol diglycidyl ether obtained in Example 1, and then heated at 130 ° C. to obtain HP4710. Dissolved to obtain a solution. After this solution was cooled to 25 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.
• Example 21 After mixing 1031S (15 parts by mass) with 85 parts by mass of resorcinol diglycidyl ether obtained in Example 1, HP 4710 was dissolved by heating at 130 ° C. to obtain a solution. After this solution was cooled to 25 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.
• Example 22 After mixing 1032S (15 parts by mass) with 85 parts by mass of resorcinol diglycidyl ether obtained in Example 1, HP 4710 was dissolved by heating at 130 ° C. to obtain a solution. After this solution was cooled to 25 ° C., NovaCure HX-3941HP (4 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity and Tg at 23 ° C. of this epoxy resin composition were measured. The results are shown in Table 1.
• Example 23 1,6-bis (glycidyloxy) naphthalene (85 parts by mass) obtained in Example 5 and TEPIC-S (15 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1.
• Example 24 1,6-Bis (glycidyloxy) naphthalene (70 parts by mass) obtained in Example 5 and TEPIC-S (30 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1. Moreover, it was 1000 ppm when this resin composition was measured by the measuring method of the ratio of the compound (C) which has a dioxane structure in the above-mentioned hardened
• Example 25 1,6-Bis (glycidyloxy) naphthalene (50 parts by mass) obtained in Example 5 and TEPIC-S (50 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX3941-HP (4.0 parts by mass) was added and stirred to prepare a resin composition. The viscosity, Tg and storage stability at 23 ° C. of the composition were measured. The results are shown in Table 1.
• Example 26 1,6-bis (glycidyloxy) naphthalene obtained in Example 5 (80 parts by mass), TEPIC-S (20 parts by mass) and HNA-100 (138.7 parts by mass) were mixed at 130 ° C. A solution was obtained by heating. After the solution was cooled to room temperature, NovaCure HX-3941HP (4.0 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.
• Example 27 1,6-bis (glycidyloxy) naphthalene obtained in Example 5 (70 parts by mass), TEPIC-S (30 parts by mass) and HNA-100 (143.4 parts by mass) were mixed, and at 130 ° C. A solution was obtained by heating. After the solution was cooled to room temperature, NovaCure HX-3941HP (4.0 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.
• Example 28 LX-01 (85 parts by mass) and TEPIC-S (15 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX-3941HP (4.0 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.
• Example 29 LX-01 (70 parts by mass), TEPIC-S (30 parts by mass) and HNA-100 (124.2 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. After the solution was cooled to room temperature, NovaCure HX-3941HP (4.0 parts by mass) was mixed to prepare an epoxy resin composition. The viscosity, Tg, and storage stability of this epoxy resin composition at 23 ° C. were measured. The results are shown in Table 1.
• Example 1 Resorcinol diglycidyl ether (92 parts by mass) obtained in Example 1 and TEPIC-S (8 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. When the solution was cooled to room temperature and allowed to stand at room temperature for a while, it crystallized and a liquid composition could not be obtained.
• Example 2 Resorcinol diglycidyl ether (15 parts by mass) obtained in Example 1 and TEPIC-S (85 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. When the solution was cooled to room temperature and allowed to stand at room temperature for a while, it crystallized and a liquid composition could not be obtained.
• Example 5 1,6-Bis (glycidyloxy) naphthalene (92 parts by mass) obtained in Example 5 and TEPIC-S (8 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. When the solution was cooled to room temperature and allowed to stand at room temperature for a while, it crystallized and a liquid composition could not be obtained.
• Example 6 1,6-Bis (glycidyloxy) naphthalene (15 parts by mass) obtained in Example 5 and TEPIC-S (85 parts by mass) were mixed and heated at 130 ° C. to obtain a solution. When the solution was cooled to room temperature and allowed to stand at room temperature for a while, it crystallized and a liquid composition could not be obtained.
• Example 23 and Comparative Example 7 According to the comparison between Example 23 and Comparative Example 7, and the comparison between Example 27 and Comparative Example 8, by using 1,6-bis (glycidyloxy) naphthalene having low chlorination, As compared with the case of using 6-bis (glycidyloxy) naphthalene, it was found that the composition had a low viscosity and the cured product had a high Tg.
• Example 28 and Comparative Example 9 By comparing the comparison between Example 28 and Comparative Example 9 and the comparison between Example 29 and Comparative Example 10 with the use of a low chlorinated bisphenol A type epoxy resin, a chlorinated bisphenol A type epoxy resin was used. It was found that the composition had a low viscosity and the Tg of the cured product was high as compared with the case where it was.
• the epoxy resin and the resin composition according to the present invention have low viscosity, they are suitably used for adhesives for electronic parts.
• the epoxy resin and resin composition according to the present invention have low viscosity and high heat resistance of the cured product after being cured. Therefore, in the underfill material, die attach material, liquid sealing material, and electronics field.

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