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
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/56—Amines together with other curing agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/5033—Amines aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
  • H10W74/473—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins containing a filler

Definitions

• Patent Document 1 describes an epoxy resin represented by a specific general formula.
• Patent Document 2 describes an epoxy resin composition that contains (A) an epoxy resin, (B) an aromatic amine-based curing agent, (C) a curing accelerator, and (D) a stabilizer, in which the ratio of the equivalents of all amino groups in the aromatic amine-based curing agent (B) to 1 equivalent of all epoxy groups in the epoxy resin (A) is 0.7 to 1.5, the curing accelerator (C) is an organic boron compound selected from aryl borate salts or aryl borane complexes, and the stabilizer (D) is an aryl phosphine.
• the curing accelerator (C) is an organic boron compound selected from aryl borate salts or aryl borane complexes
• the stabilizer (D) is an aryl phosphine.
• the most commonly used epoxy resin compositions are so-called two-part epoxy resin compositions, in which the epoxy resin and the curing agent are mixed at the time of use.
• the demands include, for example, miniaturization, high functionality, weight reduction, high functionality, and multi-functionality. More specifically, for example, in semiconductor chip mounting technology, there is a demand for finer electrode pads and finer pad pitches to achieve finer miniaturization, miniaturization, and higher density.
• underfill is used as an adhesive placed in the gap between the chip and the substrate for the purpose of protecting the bump connections and the circuit surface of the chip, etc. From the viewpoint of meeting the demand for advanced fine pitch, there is a demand for underfill that can penetrate into narrower gaps. Furthermore, in recent years, there has been an increasing demand for not only finer pitches but also larger areas of semiconductor chips, which may increase the time required for underfill to penetrate. Therefore, underfills are also required to have small changes in viscosity during penetration in high-temperature environments and during storage.
• the latent curing agent that constitutes the one-part epoxy resin composition is required to have both good curing properties after mixing with the epoxy resin and good storage stability. In addition, it is also required to have good permeability into minute areas such as between densely packed fibers such as carbon fibers and glass fibers, and narrow gaps in electronic components.
• Patent Document 1 The hardener used in Patent Document 1 is solid, and there is room for improvement in terms of its ability to penetrate narrow gaps.
• Patent Document 2 requires a process of adding an additive to improve the storage stability and adhesiveness of the curing agent, and there is room for improvement in terms of storage and handling.
• the problem that the present invention aims to solve is to provide an epoxy resin curing agent that has excellent permeability after being mixed with an epoxy resin and that is capable of achieving both curing properties and storage stability, and an epoxy resin composition, cured product, sealant, and adhesive that contain the above-mentioned epoxy resin curing agent.
• An epoxy resin curing agent comprising: an aromatic amine compound (A-1); and an aromatic amine adduct (A-2) which is a reaction product between the aromatic amine compound and a reactive compound having a functional group capable of reacting with the aromatic amine compound, wherein the aromatic amine adduct (A-2) comprises an aromatic amine adduct (A-2-1) in which one molecule of the reactive compound is added to one molecule of the aromatic amine compound (A-1), and the ratio (A-1/A-2-1) of the aromatic amine compound to the aromatic amine adduct (A-2-1) obtained by liquid chromatography analysis (UV detector) is 0.50 to 2.00.
• the epoxy resin curing agent according to ⁇ 1> which has a glass transition temperature (Tg) of 20° C. or lower as detected by differential scanning calorimetry (DSC analysis) at a heating rate of 5° C./min.
• Tg glass transition temperature
• DSC analysis differential scanning calorimetry
• Tm melting point
• ⁇ 4> The epoxy resin curing agent according to any one of ⁇ 1> to ⁇ 3>, wherein in the aromatic amine adduct (A-2), a reaction ratio between the aromatic amine compound and the reactive compound (aromatic amine compound/reactive compound) is 1/0.95 to 1/0.40 on a substance amount basis.
• ⁇ 5> The epoxy resin curing agent according to any one of ⁇ 1> to ⁇ 4>, wherein the aromatic amine compound (A-1) is an aromatic amine compound represented by the following formula (1) or the following formula (2):
• R1 and R2 each independently represent a monovalent organic group having 1 to 20 carbon atoms or a halogen, a and b each independently represent an integer of 0 to 4, and X represents a divalent organic group or a single bond.
• R 3 represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and c is an integer of 1 to 4.
• R 3 represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and c is an integer of 1 to 4.
• ⁇ 6> The epoxy resin curing agent according to any one of ⁇ 1> to ⁇ 5>, wherein the reactive compound has a molecular weight of more than 150.
• ⁇ 7> The epoxy resin curing agent according to any one of ⁇ 1> to ⁇ 6>, wherein a molecular weight ratio of the reactive compound to the aromatic amine compound is 0.5 or more and 1.1 or less.
• ⁇ 8> The epoxy resin curing agent according to any one of ⁇ 1> to ⁇ 7>, wherein the reactive compound is an epoxy compound having one glycidyl group in the molecule.
• An epoxy resin composition comprising the epoxy resin curing agent according to any one of ⁇ 1> to ⁇ 8>, an epoxy resin (B), and an inorganic filler (C).
• the curing accelerator is at least one selected from the group consisting of a compound (D-1) represented by the following formula (4), the following formula (5), or the following formula (6), and an imidazole-based compound (D-2):
• R 1 's each independently represent a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms which may have a hydroxyl group, a carbonyl group, an ester bond or an ether bond
• R 2 and R 3 each independently represent an unsubstituted or substituted alkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms, or are linked to form a heterocycle having 7 or less carbon atoms
• R 4 's each independently represent a hydrogen atom or an n-valent organic group having 1 to 50 carbon atoms which may contain an oxygen atom
• n represents an integer of 1 to 3
• R 5 represents a negatively charged nitrogen atom
• R 6 represents a positively charged nitrogen atom.
• ⁇ 13> The epoxy resin composition according to any one of ⁇ 9> to ⁇ 12>, which has a viscosity of 0.01 Pa ⁇ s to 1.50 Pa ⁇ s after being left at 110° C. for 60 minutes.
• ⁇ 14> A cured product of the epoxy resin composition according to any one of ⁇ 9> to ⁇ 13>.
• ⁇ 15> An encapsulant comprising the cured product according to ⁇ 14>.
• ⁇ 16> The encapsulant according to ⁇ 15>, which is an encapsulant for semiconductors.
• An adhesive comprising the epoxy resin composition according to any one of ⁇ 9> to ⁇ 13>.
• ⁇ 18> A semiconductor package comprising the cured product according to ⁇ 14>.
• ⁇ 19> A method for producing a semiconductor package, comprising the step of producing a semiconductor package using the epoxy resin composition according to ⁇ 9>.
• the present invention provides an epoxy resin curing agent that has excellent permeability after mixing with an epoxy resin and is capable of achieving both curing properties and storage stability, as well as an epoxy resin composition, cured product, sealing material, and adhesive that contain the epoxy resin curing agent.
• the present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content.
• the present invention can be carried out with appropriate modifications within the scope of the gist of the present invention.
• ⁇ when " ⁇ " is used with a numerical value or physical property value between the two, the values before and after the " ⁇ " are included.
• the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range.
• the upper or lower limit of the numerical range may be replaced with a value shown in the examples.
• alkyl group encompasses not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (substituted alkyl groups).
• the epoxy resin curing agent of the present embodiment comprises an aromatic amine compound (A-1), and an aromatic amine adduct (A-2) which is a reaction product between the aromatic amine compound and a reactive compound having a functional group capable of reacting with the aromatic amine compound, the aromatic amine adduct (A-2) comprises an aromatic amine adduct (A-2-1) in which one molecule of the reactive compound is added to one molecule of the aromatic amine compound (A-1), and the ratio (A-1/A-2-1) of the aromatic amine compound to the aromatic amine adduct (A-2-1) obtained by liquid chromatography analysis (UV detector) is 0.50 to 2.00.
• the epoxy resin curing agent of this embodiment contains the above-mentioned components, and therefore has excellent permeability after mixing with epoxy resin, and is able to achieve both curability and storage stability.
• the epoxy resin curing agent of this embodiment may include an aromatic amine adduct (A-2) in which one molecule of a reactive compound is added to one molecule of an aromatic amine compound (A-1) (A-2-1), and an aromatic amine adduct (A-2-2X) in which two or more molecules of a reactive compound are added to one molecule of an aromatic amine compound (A-1).
• A-2 aromatic amine adduct
• A-2-2X aromatic amine adduct
• the aromatic amine adduct (A-2) contains an aromatic amine adduct (A-2-1) in which one molecule of a reactive compound is added to one molecule of an aromatic amine compound (A-1).
• the ratio (A-1/A-2-1) of the aromatic amine compound (A-1) to the aromatic amine adduct (A-2-1) obtained by liquid chromatography analysis (UV detector) is 0.50 to 2.00.
• the ratio (A-1/A-2-1) is 0.50 or more, the composition has excellent curability and therefore both curability and storage stability can be achieved.
• the composition also has improved heat resistance.
• (A-1/A-2-1) is preferably 0.60 or more, more preferably 0.70 or more, and even more preferably 0.80 or more.
• (A-1/A-2-1) is 2.00 or less, the composition has better penetration and storage stability, and therefore, both curability and storage stability can be achieved.
• (A-1/A-2-1) is preferably 1.80 or less, more preferably 1.60 or less, and even more preferably 1.40 or less.
• the aromatic amine compound an amine compound having electron-withdrawing properties and an amine compound having a plurality of functional groups in a side chain are inferior in reactivity as an amine but excellent in stability when made into an amine adduct, so the ratio (A-1/A-2-1) of the aromatic amine (A-1) to the aromatic amine adduct (A-2-1) may be large.
• the aromatic amine adduct (A-2) contains an aromatic amine adduct (A-2-1) in which one molecule of a reactive compound is added to one molecule of the aromatic amine compound (A-1).
• aromatic amine compound examples include 4,4'-diaminodiphenylsulfone, diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene), and dimethylthiotoluenediamine.
• aromatic amine compounds that do not have electron-withdrawing properties and amine compounds that do not have functional groups in the side chains are highly reactive as amines and have excellent curing properties when formed into amine adducts, so the ratio of aromatic amine (A-1) to aromatic amine adduct (A-2-1) may be small.
• aromatic amine adduct (A-2) contains aromatic amine adduct (A-2-1) in which one molecule of reactive compound is added to one molecule of aromatic amine compound (A-1).
• the ratio (A-1/A-2-1) of aromatic amine compound (A-1) to aromatic amine adduct (A-2-1) obtained from liquid chromatography analysis (UV detector) is preferably 0.50 to 2.00, more preferably 0.50 to 1.30, and even more preferably 0.50 to 1.10.
• aromatic amine compounds examples include 4-aminophenyl-4-aminobenzoate (APAB), 3,4'-diaminodiphenyl ether (34ODA), 1,3-bis(3-aminophenoxy)benzene (TPE-M), and the like, and among them, 4-aminophenyl-4-aminobenzoate (APAB) is particularly preferred.
• APAB 4-aminophenyl-4-aminobenzoate
• 34ODA 3,4'-diaminodiphenyl ether
• TPE-M 1,3-bis(3-aminophenoxy)benzene
• APAB 4-aminophenyl-4-aminobenzoate
• the solvent used here is not particularly limited, but examples thereof include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, naphtha, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.; esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, etc.; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, butyl carbitol, etc.; water, etc., and these solvents may be used in combination.
• hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, naphtha, etc.
• ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone
• aromatic amine compound examples include 4,4'-diaminodiphenylsulfone, diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene), dimethylthiotoluenediamine, and the like.
• aromatic amine compounds that do not have electron-withdrawing properties and amine compounds that do not have functional groups in the side chains are highly reactive as amines and have excellent curing properties when formed into amine adducts, so the ratio of aromatic amine (A-1) to aromatic amine adduct (A-2-1) may be small.
• the reaction ratio of the aromatic amine compound to the reactive compound is preferably 1/0.95 to 1/0.40, more preferably 1/0.95 to 1/0.6, and even more preferably 1/0.95 to 1/0.7, based on the amount of substance.
• the epoxy resin curing agent of the present embodiment preferably has a glass transition temperature (Tg) of 20° C. or lower as detected by differential scanning calorimetry (DSC analysis) at a heating rate of 5° C./min.
• Tg glass transition temperature
• DSC analysis differential scanning calorimetry
• the Tg is more preferably 20° C. or less, further preferably 15° C. or less, particularly preferably 10° C. or less, and even more preferably 0° C. or less.
• the Tg is ⁇ 50° C. or higher, the heat resistance is superior.
• the Tg is preferably ⁇ 50° C. or higher, more preferably ⁇ 40° C. or higher, and even more preferably ⁇ 30° C. or higher.
• the glass transition temperature (Tg) of the epoxy resin curing agent is measured by the following method. Using a differential scanning calorimeter (e.g., TA Instruments-Waters, Differential Scanning Calorimetry System, "DSC Q2000"), a 10 mg sample is heated from -50°C to 200°C at a heating rate of 5°C/min, and measured under a nitrogen stream (40 mL/min). The Tg of the epoxy resin curing agent is the peak top temperature of the DSC differential curve (JIS K6240:2011).
• DSC Q2000 Differential Scanning Calorimetry System
• the epoxy resin curing agent of the present embodiment preferably has at least one melting point (Tm) of less than 60° C. as detected by differential scanning calorimetry (DSC analysis) at a heating rate of 5° C./min.
• Tm melting point
• DSC analysis differential scanning calorimetry
• Tm is more preferably less than 60° C., further preferably 50° C. or less, and particularly preferably 40° C. or less.
• Tm is preferably ⁇ 40° C. or higher, more preferably ⁇ 30° C. or higher, and even more preferably ⁇ 20° C. or higher.
• Tm melting point
• DSC analysis differential scanning calorimetry
• the compounds having the structure represented by formula (1) or (2) have substituents on their side chains, which inhibits intermolecular interactions, making them amorphous.
• the compounds have no detectable melting point (Tm) in the range of -20°C to 60°C, and therefore have excellent viscosity at the temperature during penetration and excellent penetration properties.
• the melting point (Tm) of the epoxy resin curing agent is measured by the following method. Using a differential scanning calorimeter (e.g., TA Instruments-Waters, Differential Scanning Calorimetry System, "DSC Q2000"), a 10 mg sample is heated from -50°C to 200°C at a heating rate of 5°C/min, and measured under a nitrogen stream (40 mL/min).
• the Tm of an epoxy resin curing agent is defined as the apex temperature of the endothermic peak in the DSC curve (JIS K7121:1987).
• the epoxy resin composition of the present embodiment contains the epoxy resin curing agent of the present embodiment, an epoxy resin (B), and an inorganic filler (C).
• Epoxy resin (B)> any commonly used epoxy resin can be used without any particular limitation.
• an epoxy resin having two or more epoxy groups in one molecule is preferable.
• the epoxy resin may be solid or liquid at room temperature, but is preferably liquid at room temperature from the viewpoint of filling properties.
• the epoxy resin may be particularly an epoxy resin that is liquid at room temperature (hereinafter also referred to as "liquid epoxy resin"), and a commonly used liquid epoxy resin may be used.
• the liquid epoxy resin preferably has a viscosity of, for example, 0.0001 to 10 Pa ⁇ s as measured by an E-type viscometer at room temperature.
• epoxy resins examples include diglycidyl ether type epoxy resins such as bisphenol type epoxy resins such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and hydrogenated bisphenol A; epoxy resins obtained by epoxidizing novolac resins obtained from phenols and aldehydes, such as orthocresol novolac type epoxy resins; glycidyl ester type epoxy resins obtained by reacting polybasic acids such as phthalic acid and dimer acid with epichlorohydrin; glycidyl amine type epoxy resins obtained by reacting amine compounds such as p-aminophenol, diaminodiphenylmethane, and isocyanuric acid with epichlorohydrin; linear aliphatic epoxy resins and alicyclic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; and the like. Epoxy resins may be used alone or in combination of two or more.
• bisphenol type epoxy resins are preferred from the viewpoint of fluidity, and for example, glycidylamine type epoxy resins are preferred from the viewpoints of heat resistance, adhesiveness, and fluidity.
• the epoxy resin is preferably at least one selected from the group consisting of bisphenol type epoxy resins and glycidyl amine type epoxy resins.
• the bisphenol type epoxy resin from the viewpoint of fluidity, one or more types selected from the group consisting of diglycidyl ether type epoxy resins of bisphenol A (bisphenol A type epoxy resins) and diglycidyl ether type epoxy resins of bisphenol F (bisphenol F type epoxy resins) are preferred.
• the mass ratio thereof (bisphenol A type epoxy resin:bisphenol F type epoxy resin) is not particularly limited, but from the viewpoints of heat resistance, adhesiveness, and flowability, it is, for example, preferably 5:95 to 50:50, more preferably 10:90 to 40:60, and even more preferably 20:80 to 40:60. From the viewpoint of fluidity, it is preferable that both the bisphenol type epoxy resin and the glycidyl amine type epoxy resin are liquid at room temperature.
• the bisphenol type epoxy resin and the glycidylamine type epoxy resin may be used alone or in combination of two or more.
• the total content of the bisphenol type epoxy resin and the glycidylamine type epoxy resin is not particularly limited, but from the viewpoints of heat resistance, adhesion and fluidity, it is preferably, for example, 20% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and particularly preferably 80% by mass or more, based on the total amount of the epoxy resin.
• the total content is no particular upper limit to the total content, and it can be determined within a range in which desired properties and characteristics can be obtained from the viewpoints of viscosity, glass transition temperature, heat resistance, etc., and may be 100% by mass.
• a bisphenol type epoxy resin and a glycidyl amine type epoxy are used in combination, their mass ratio (bisphenol type epoxy resin:glycidyl amine type epoxy) is not particularly limited, but from the viewpoints of heat resistance, adhesion and flowability, it is preferably, for example, 20:80 to 95:5, more preferably 40:60 to 90:10, and even more preferably 60:40 to 80:20.
• an epoxy resin that is solid at room temperature can also be used. From the viewpoint of fluidity, the content of the epoxy resin that is solid at room temperature is, for example, preferably 0 to 20 mass %, more preferably 0 to 10 mass %, and even more preferably 0 to 5 mass %, relative to the total amount of the epoxy resin.
• the epoxy equivalent of the epoxy resin is not particularly limited, but from the viewpoint of heat resistance, it is preferably 60 to 400 g/mol, more preferably 70 to 300 g/mol, and even more preferably 80 to 250 g/mol.
• the epoxy equivalent is the mass (g/eq) of the resin per epoxy group, and can be measured according to the method specified in JIS K 7236.
• the epoxy resin is weighed into a 200 ml beaker, 90 ml of methyl ethyl ketone is dropped thereinto, and the resin is dissolved in an ultrasonic cleaner, after which 10 ml of glacial acetic acid and 1.5 g of cetyltrimethylammonium bromide are added, and the epoxy equivalent is determined by titration with a 0.1 mol/L perchloric acid/acetic acid solution. It is preferable that the epoxy resin has a high purity.
• the amount of hydrolyzable chlorine is preferably small because it is involved in corrosion of aluminum wiring on elements such as ICs (Integrated Circuits), and from the viewpoint of excellent moisture resistance, it is preferable that the amount of hydrolyzable chlorine is, for example, 500 ppm or less.
• the amount of hydrolyzable chlorine herein is measured by dissolving 1 g of a sample epoxy resin in 30 ml of dioxane, adding 5 ml of a 1N KOH (potassium hydroxide) methanol solution, refluxing for 30 minutes, and then measuring the amount of hydrolyzable chlorine by potentiometric titration.
• the content of the epoxy resin is not particularly limited, but from the viewpoints of heat resistance, adhesion, and flowability, it is, for example, preferably 40 to 90 mass %, more preferably 50 to 80 mass %, and even more preferably 55 to 70 mass %, of the total amount of the epoxy resin composition excluding the (C) inorganic filler.
• the inorganic filler is not particularly limited, but examples thereof include powders such as silica, such as fused silica and crystalline silica, calcium carbonate, clay, alumina, such as alumina oxide, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, and titania, as well as beads obtained by spheronizing these powders, and glass fibers.
• powders such as silica, such as fused silica and crystalline silica, calcium carbonate, clay, alumina, such as alumina oxide, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite
• an inorganic filler having a flame retardant effect may be used as the inorganic filler.
• inorganic fillers having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate.
• the inorganic filler may be used alone or in combination of two or more kinds. Among these, from the viewpoints of availability, chemical stability, and material cost, for example, silica is preferred, and fused silica is more preferred.
• the particle shape of the inorganic filler is not particularly limited and may be amorphous or spherical, but from the viewpoints of flowability and permeability into fine gaps in the epoxy resin composition, spherical silica, particularly spherical fused silica, is preferably used.
• the inorganic filler may be surface-treated. Specifically, the inorganic filler may be surface-treated with a silane coupling agent.
• the silane coupling agent include aminosilane coupling agents, epoxysilane coupling agents, phenylsilane coupling agents, alkylsilane coupling agents, alkenylsilane coupling agents, alkynylsilane coupling agents, haloalkylsilane coupling agents, siloxane coupling agents, hydrosilane coupling agents, silazane coupling agents, alkoxysilane coupling agents, chlorosilane coupling agents, (meth)acrylsilane coupling agents, aminosilane coupling agents, isocyanurate silane coupling agents, ureidosilane coupling agents, mercaptosilane coupling agents, sulfide silane coupling agents, and isocyanate silane coupling agents.
• the volume average particle diameter of the inorganic filler is not particularly limited, but is preferably 0.1 to 10 ⁇ m, more preferably 0.3 to 5 ⁇ m, and even more preferably 0.5 to 3 ⁇ m.
• the volume average particle size refers to the particle size at a point corresponding to 50% volume when a cumulative frequency distribution curve of particle size is calculated assuming the total volume of the particles to be 100%, and can be measured using a particle size distribution measuring device using a laser diffraction scattering method, etc.
• the content of the inorganic filler is not particularly limited, but is preferably 50% by mass to 70% by mass based on the total amount of the epoxy resin composition.
• the content of the inorganic filler 50% by mass or more, it is easy to obtain the effect of reducing the thermal expansion coefficient and the effect of improving the temperature cycle resistance.
• the lower limit value of the content of the inorganic filler is as high as possible. In this embodiment, even if the content of the inorganic filler is increased as described above, it is possible to maintain the viscosity of the epoxy resin composition at a low level.
• the epoxy resin composition of the present embodiment preferably further contains a curing accelerator (D).
• the curing accelerator is preferably at least one selected from the group consisting of the compounds (D-1) represented by formula (4), (5), or (6), and the imidazole-based compounds (D-2).
• R 1 's each independently represent a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms which may have a hydroxyl group, a carbonyl group, an ester bond or an ether bond
• R 2 and R 3 each independently represent an unsubstituted or substituted alkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms, or are linked to form a heterocycle having 7 or less carbon atoms
• R 4 's each independently represent a hydrogen atom or an n-valent organic group having 1 to 50 carbon atoms which may contain an oxygen atom
• n represents an integer of 1 to 3
• R 5 represents a negatively charged nitrogen atom
• R 6 represents a positively charged nitrogen atom.
• R1 is presumed to contribute to lowering the energy of the cleavage of the N-N bond.
• R2 and R3 are presumed to contribute to lowering the energy of the cleavage reaction by destabilization due to steric hindrance.
• R4 is presumed to contribute to liquefying the compound and suppressing a decrease in the glass transition temperature of the resulting cured product.
• each R 1 independently represents a hydrogen atom or an n-valent organic group having 1 to 15 carbon atoms which may have a hydroxyl group, a carbonyl group, an ester bond, or an ether bond.
• the organic group is not particularly limited, and examples thereof include a hydrocarbon group, a group in which a hydrogen atom bonded to a carbon atom in a hydrocarbon group is substituted with a hydroxyl group or a carbonyl group, and a group in which a part of the carbon atoms in a hydrocarbon group is substituted with an ester bond or an ether bond.
• examples of the hydrocarbon group include linear, branched, or cyclic alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and an ethylhexyl group; alkenyl groups such as a vinyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, an octynyl group, a decynyl group, a dodecynyl group, a hexadecynyl group, and an octadecynyl group; aryl groups such as a phenyl group; and aralkyl groups including a combination of an alkyl group and a phenyl group
• the organic group may have other substituents.
• the substituents are not particularly limited, but examples thereof include halogen atoms, alkoxy groups, carbonyl groups, cyano groups, azo groups, azido groups, thiol groups, sulfo groups, nitro groups, hydroxy groups, acyl groups, and aldehyde groups.
• the carbon number of the organic group is 1 to 15, preferably 1 to 12, and more preferably 1 to 7. When the carbon number of the organic group is within the above range, a liquid compound having an appropriate viscosity is easily obtained, and the curing performance of the compound tends to be further improved. In addition, when the carbon number of the organic group is within the above range, the availability of raw materials is further improved.
• R2 and R3 each independently represent an unsubstituted or substituted alkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms, or combine to form a heterocycle having 7 or less carbon atoms.
• the alkyl group having 1 to 12 carbon atoms is not particularly limited, and examples thereof include linear alkyl groups such as methyl group, ethyl group, propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group, and n-dodecyl group; branched alkyl groups such as isopropyl group, isobutyl group, t-butyl group, neopentyl group, 2-hexyl group, 2-octyl group, 2-decyl group, and 2-dodecyl group; and cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclodecyl group, and cyclododecyl group
• the alkyl group each independently has 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 5 to 10 carbon atoms.
• Asymmetric dialkylhydrazine compounds with a small number of carbon atoms in the alkyl group may be toxic to the human body as well as explosive, etc.
• By making the number of carbon atoms in the alkyl groups in R2 and R3 2 or more it is possible to avoid the use of raw materials that have the above-mentioned risks of toxicity, etc.
• a liquid compound having an appropriate viscosity is easily obtained, and the curing performance of the compound tends to be further improved.
• the aryl group is not particularly limited, but examples thereof include a phenyl group and a naphthyl group.
• the aralkyl group is not particularly limited, but examples thereof include a methylphenyl group, an ethylphenyl group, a methylnaphthyl group, and a dimethylnaphthyl group.
• R2 and R3 are preferably aralkyl groups, more preferably methylphenyl groups (benzyl groups). This tends to further improve the curing performance of the compound.
• the number of carbon atoms in the aryl group and aralkyl group represented by R2 or R3 is not particularly limited, but is 6 to 20.
• the substituent of the alkyl group, aryl group, or aralkyl group is not particularly limited, and examples thereof include a halogen atom, an alkoxy group, a carbonyl group, a cyano group, an azo group, an azido group, a thiol group, a sulfo group, a nitro group, a hydroxy group, an acyl group, and an aldehyde group.
• R2 and R3 may be linked to form a heterocycle having up to 7 carbon atoms.
• the heterocycle is not particularly limited, but examples thereof include four-membered rings such as an azetidine ring; five-membered rings such as a pyrrolidine ring, a pyrrole ring, a morpholine ring, and a thiazine ring; six-membered rings such as a piperidine ring; and seven-membered rings such as a hexamethyleneimine ring and an azepine ring.
• the heterocycle is preferably a pyrrole ring, a morpholine ring, a thiazine ring, a piperidine ring, a hexamethyleneimine ring, or an azepine ring, more preferably a 6-membered ring or a 7-membered ring.
• the substituent is not particularly limited, but examples thereof include an alkyl group, an aryl group, or the above-mentioned substituents in R2 and R3 . Furthermore, when the heterocycle has an alkyl group as a substituent, an example thereof is a methyl group bonded to the carbon atom adjacent to R6 .
• each R 4 independently represents a hydrogen atom or an n-valent organic group having 1 to 50 carbon atoms which may contain an oxygen atom.
• the organic group is not particularly limited, and examples thereof include a hydrocarbon group, a group in which a hydrogen atom bonded to a carbon atom in a hydrocarbon group is substituted with a hydroxyl group, a carbonyl group, or a group containing a silicon atom, and a group in which a part of the carbon atoms in a hydrocarbon group is substituted with an ester bond, an ether bond, or a silicon atom.
• examples of the hydrocarbon group include linear, branched, or cyclic alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and an ethylhexyl group; alkenyl groups such as a vinyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, an octynyl group, a decynyl group, a dodecynyl group, a hexadecynyl group, and an octadecynyl group; aryl groups such as a phenyl group; and aralkyl groups including a combination of an alkyl group and a phenyl group
• the hydrocarbon group may include a bisphenol skeleton such as a bisphenol A skeleton, a bisphenol AP skeleton, a bisphenol B skeleton, a bisphenol C skeleton, a bisphenol E skeleton, or a bisphenol F skeleton.
• the organic group containing a bisphenol skeleton is not particularly limited, but examples thereof include groups in which a polyoxyalkylene group is added to the hydroxyl group of each bisphenol skeleton.
• the organic group represented by R 4 in formula (4) or formula (5) is preferably an alkyl group, an alkenyl group, and an aralkyl group, more preferably an alkyl group and an alkenyl group, and even more preferably a branched alkyl group and a branched alkenyl group.
• These preferred groups may have a substituent.
• the carbon number of the organic group is 1 to 50, preferably 1 to 30, more preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8.
• the carbon number of the organic group in R 4 is within the above range, a liquid compound having a suitable viscosity is easily obtained, and the curing performance of the compound tends to be further improved.
• the Tg of the cured product obtained by using this compound is further improved, and further, when the carbon number of the organic group in R 4 is within the above range, the availability of raw materials is further improved.
• R 4 in formula (4) or formula (5) is preferably a linear or branched alkyl group having 3 to 12 carbon atoms, and a linear or branched alkenyl group having 3 to 6 carbon atoms.
• a liquid compound having an appropriate viscosity is easily obtained, and the curing performance of the compound tends to be further improved.
• the compound (D-1) contains a plurality of compounds represented by formula (4), formula (5) or formula (6). Note that the compound (D-1) may contain a plurality of compounds having different structures but represented by the same formula.
• the compound (D-1) preferably includes compounds represented by formulas (4) and (6).
• the content of the compound represented by formula (4) is preferably 0.1% by mass to 99.5% by mass relative to the total amount of the compounds represented by formula (4), (5), or (6), which allows easy control of the viscosity.
• a composition containing a plurality of compounds represented by formula (4), (5), or (6) can be obtained by mixing a plurality of compounds, or by simultaneously producing a plurality of compounds in a compound production method described later.
• the compound represented by formula (4), formula (5) or formula (6) can be produced, for example but not limited to, by reacting an ester compound, a hydrazine compound, and a glycidyl ether compound.
• the ester compound is not particularly limited, but examples include monocarboxylic acid ester compounds, dicarboxylic acid ester compounds, etc.
• the monocarboxylate ester compound examples include methyl lactate, ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, methyl isovalerate, methyl pivalate, methyl heptanoate, methyl octanoate, methyl acrylate, methyl methacrylate, methyl crotonate, methyl isocrotonate, methyl benzoylformate, 2-methoxybenzoylmethyl, 3-methoxybenzoylmethyl, 4-methoxybenzoylmethyl, 2-ethoxybenzoylmethyl, 4-t-butoxybenzoylmethyl, and the like.
• ethyl esters, propyl esters, etc. may be used.
• dicarboxylate compounds include dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl sebacate, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, and diethyl 1,3-acetonedicarboxylate, etc.
• cyclic esters, etc. may be used.
• cyclic esters include ⁇ -acetolactone, ⁇ -propionolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, etc.
• diethyl esters, dipropyl esters, etc. may be used.
• ester compounds are preferred: ethyl lactate, methyl mandelate, methyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl valerate, methyl isovalerate, methyl pivalate, methyl acrylate, methyl methacrylate, methyl crotonate, methyl isocrotonate, methyl benzoylformate, dimethyl oxalate, dimethyl malonate, dimethyl succinate, dimethyl tartrate, dimethyl glutarate, dimethyl adipate, dimethyl pimelate, dimethyl suberate, dimethyl azelate, dimethyl maleate, dimethyl fumarate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,3-acetonedicarboxylate, diethyl 1,3-acetonedicarboxylate, gamma buty
• the hydrazine compound is not particularly limited, but examples thereof include dimethylhydrazine, diethylhydrazine, methylethylhydrazine, methylpropylhydrazine, methylbutylhydrazine, methylpentylhydrazine, methylhexylhydrazine, ethylpropylhydrazine, ethylbutylhydrazine, ethylpentylhydrazine, ethylhexylhydrazine, dipropylhydrazine, dibutylhydrazine, dipentylhydrazine, dihexylhydrazine, methylphenylhydrazine, ethylphenylhydrazine, methyltolylhydrazine, ethyltolylhydrazine, diphenylhydrazine, benzylphenylhydrazine, dibenzylhydrazine, dini
• dimethylhydrazine, dibenzylhydrazine, 1-aminopiperidine, 1-aminopyrrolidine, and 1-aminomorpholine are preferred as the hydrazine compound.
• dibenzylhydrazine and 1-aminopiperidine are more preferred.
• the hydrazine compounds may be used alone or in combination of two or more kinds.
• the glycidyl ether compound is not particularly limited, but may be, for example, a monofunctional monoglycidyl ether compound or a bifunctional or higher polyglycidyl ether compound.
• monoglycidyl ether compounds include methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, higher alcohol glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, orthophenylphenol glycidyl ether, benzyl glycidyl ether, biphenylyl glycidyl ether, 4-t-butylphenyl glycidyl ether, t-butyldimethylsilyl glycidyl ether, 3-[diethoxy(methyl)silyl]propyl glycidyl ether, etc.
• polyglycidyl ether compounds include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, and glycerin polyglycidyl ether.
• polyglycidyl ether examples include aliphatic polyglycidyl ethers such as diglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, and sorbitol polyglycidyl ether; alicyclic polyglycidyl ether compounds such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, ethylene oxide-added bisphenol A diglycidyl ether, propylene oxide-added bisphenol A diglycidyl ether, and hydrogenated condensates of these compounds; and aromatic polyglycidyl ether compounds such as resorcinol diglycidyl ether.
• aliphatic polyglycidyl ethers such as diglycidyl ether, diglycerin polyglycidyl ether, polyglycerin polyglycidyl ether, and sorbitol
• glycidyl ether compounds are preferred: methyl glycidyl ether, ethyl glycidyl ether, n-butyl glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, t-butyldimethylsilyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, butanediol glycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, bisphenol A diglycidyl ether, bisphenol F dig
• epoxy resins having an ether structure are preferred, and specific examples thereof include polyethylene glycol diglycidyl ether and 1-phenoxy-1,4-(oxiranylmethoxy)-3,6,9,12-tetraoxatetradecane.
• the glycidyl ether compounds may be used alone or in combination of two or more kinds.
• the amounts of the ester compound, hydrazine compound, and glycidyl ether compound added to the reaction system can be set based on the molar ratio of the functional groups.
• the amount of the ester group of the ester compound is preferably 0.8 mol to 3.0 mol, more preferably 0.9 mol to 2.8 mol, and even more preferably 0.95 mol to 2.5 mol, per 1 mol of the primary amine of the hydrazine compound.
• the amount of the glycidyl group of the glycidyl ether compound is preferably 0.8 mol to 2.0 mol, more preferably 0.9 mol to 1.5 mol, and even more preferably 0.95 mol to 1.4 mol, per mol of the primary amine of the hydrazine compound.
• the amount of the glycidyl group of the glycidyl ether compound added relative to 1 mole of the primary amine of the hydrazine compound By controlling the amount of the glycidyl group of the glycidyl ether compound added relative to 1 mole of the primary amine of the hydrazine compound, a composition containing the compounds represented by formula (5) and formula (4) can be simultaneously produced.
• the amount of the glycidyl group of the glycidyl ether compound is preferably 0.1 mol to 3.0 mol, more preferably 0.3 mol to 2.0 mol, and even more preferably 0.5 mol to 1.0 mol, per 1 mol of the primary amine of the hydrazine compound.
• a solvent may be used in order to ensure that the reaction proceeds uniformly.
• the solvent is not particularly limited, but examples include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, butanol, and t-butyl alcohol; and ethers such as tetrahydrofuran and diethyl ether.
• the reaction temperature is preferably 10 to 100°C, more preferably 40 to 90°C.
• a reaction temperature of 10°C or higher tends to speed up the reaction and improve the purity of the resulting compound.
• a reaction temperature of 90°C or lower tends to efficiently suppress the polymerization reaction between glycidyl ether compounds, and therefore tends to improve the purity of the compound.
• the reaction time is preferably from 1 hour to 168 hours, more preferably from 1 hour to 96 hours, and further preferably from 1 hour to 48 hours.
• the obtained reaction product can be purified by known purification methods such as washing, extraction, recrystallization, column chromatography, etc.
• the reaction solution dissolved in an organic solvent is washed with water, and then the organic layer is heated under normal or reduced pressure to remove unreacted raw materials and organic solvent from the reaction solution, and the target compound can be recovered.
• the target compound can also be recovered by purification using column chromatography.
• the solvent used for the above-mentioned washing is not particularly limited as long as it can dissolve the residual raw materials, but 1-hexane, 1-pentane, and cyclohexane are preferred from the viewpoints of yield, purity, and ease of removal.
• the organic solvent used in the above extraction is not particularly limited as long as it can dissolve the target compound, but from the standpoint of yield, purity, and ease of removal, ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, toluene, diethyl ether, and methyl isobutyl ketone are preferred, and ethyl acetate, chloroform, toluene, and methyl isobutyl ketone are more preferred.
• the packing material used in column chromatography may be alumina, silica gel, or other known materials.
• the developing solvent may be ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, diethyl ether, acetone, methyl isobutyl ketone, acetonitrile, methanol, ethanol, isopropanol, or other known materials, either alone or in combination.
• n in formula (5) and formula (6) of compound (D-1) is 2 or 3. This improves the crosslink density during curing, making it possible to produce a tough cured product with improved adhesion and reliability.
• the imidazole compound (D-2) can be used without any particular limitation.
• Examples of the imidazole compound (D-2) include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecyl-imidazole trimellitate, imidazolyl succinic acid, 2-methylimidazole succinic acid, 2-ethylimidazole succinic acid, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-phenylimidazole.
• the epoxy resin composition of the present embodiment has a viscosity at 25° C. of preferably 50 Pa ⁇ s or less, more preferably 40 Pa ⁇ s or less, and even more preferably 20 Pa ⁇ s or less. From the viewpoint of curability, the epoxy resin composition of the present embodiment has a viscosity at 25° C. of preferably 0.1 Pa ⁇ s or more, more preferably 1 Pa ⁇ s or more, and even more preferably 2 Pa ⁇ s or more.
• an E-type viscometer for example, "TV-20” manufactured by Toki Sangyo Co., Ltd.
• the epoxy resin composition of the present embodiment has a viscosity after being left at 110°C for 60 minutes of preferably 0.01 Pa ⁇ s to 1.50 Pa ⁇ s, more preferably 0.01 Pa ⁇ s to 1.0 Pa ⁇ s, and even more preferably 0.01 Pa ⁇ s to 0.5 Pa ⁇ s.
• the viscosity after standing at 110° C. for 60 minutes is measured using a rheometer (for example, HAAKE MARS, manufactured by Thermo Scientific).
• the epoxy resin composition of the present embodiment preferably has a viscosity increase rate after being left at 110° C. for 60 minutes of 1.0 to 40.0 times, more preferably 1.0 to 30 times, and even more preferably 1.0 to 20 times.
• the viscosity after 5 minutes is designated as " ⁇ 1”
• the viscosity after 60 minutes is designated as " ⁇ 2”
• the value calculated by ⁇ 2/ ⁇ 1 is the viscosity increase rate.
• the epoxy resin composition of this embodiment preferably has a reaction rate of 70% or more and 100% or less when cured at 165°C, more preferably 80% or more and 100% or less, and even more preferably 90% or more and 100% or less.
• the reaction rate when the epoxy resin composition was cured at 165°C was calculated by increasing the temperature from 25°C to 300°C at a rate of 5°C/min using an EXSTER6000 (Hitachi High-Tech Science Corporation) and calculating the total amount of heat generated in the temperature range from 100°C to 250°C. Furthermore, the same measurement may be performed after placing the sample in a small high-temperature chamber (manufactured by Espec Corp.) at 180° C. for 2 hours, and the change in the calorific value within the same temperature range may be calculated as a percentage. The same measurement may also be performed after placing the sample in a small high-temperature chamber (manufactured by Espec Corp.) at 165° C.
• the epoxy resin composition and cured product of this embodiment are useful as adhesives, sealants, filling materials, insulating materials, conductive materials, anisotropic conductive materials, sealing materials, prepregs, etc.
• adhesives they are useful as liquid adhesives, film adhesives, die bonding materials, etc.
• sealants they are useful as solid sealants, liquid sealants, film sealants, etc., and as liquid sealants, they are useful as underfill materials, potting materials, dam materials, etc.
• insulating materials they are useful as insulating adhesive films, insulating adhesive pastes, solder resists, etc., as conductive materials, they are useful as conductive films, conductive pastes, etc., and as anisotropic conductive materials, they are useful as anisotropic conductive films, anisotropic conductive pastes, etc.
• the epoxy resin composition of the present embodiment can be suitably used as an adhesive.
• the adhesive of the present embodiment contains the epoxy resin composition of the present embodiment.
• the cured product of the present embodiment is a cured product of the epoxy resin composition of the present embodiment.
• the cured product of the present embodiment can be suitably used as a sealant, and the sealant is preferably a semiconductor sealant.
• the sealing material of the present embodiment includes the cured product of the present embodiment.
• the cured product of this embodiment can also be suitably used as a semiconductor package.
• the semiconductor package of the present embodiment includes the cured product of the present embodiment.
• the method for producing a semiconductor package of the present embodiment includes a step of producing a semiconductor package using the epoxy resin composition of the present embodiment.
• the process of manufacturing a semiconductor package using the epoxy resin composition of the present embodiment may include a process of preparing the epoxy resin composition of the present embodiment.
• the epoxy resin composition of the present embodiment may be obtained, for example, by stirring and mixing the components contained in the epoxy resin composition of the present embodiment using a planetary centrifugal mixer (e.g., ARE-310 manufactured by Thinky Corporation) and then kneading using a three-roll mill.
• a planetary centrifugal mixer e.g., ARE-310 manufactured by Thinky Corporation
• the process for manufacturing a semiconductor package using the epoxy resin composition of this embodiment may be a process for manufacturing a semiconductor package by appropriately molding a prepared epoxy resin composition and heating it at a predetermined temperature and time to harden it.
• Tg glass transition temperature
• Tm melting point
• the glass transition temperature (Tg) and melting point (Tm) of the epoxy resin curing agent were measured using a differential scanning calorimeter (TA Instruments-Waters, Differential Scanning Calorimetry System, "DSC Q2000") by heating a 10 mg sample from -50°C to 200°C at a heating rate of 5°C/min under a nitrogen gas flow (40 mL/min).
• DSC Q2000 Differential Scanning Calorimetry System
• Tm of the amine adduct was taken as the apex temperature of the endothermic peak in the DSC curve (JIS K7121-1987), and the Tg was taken as the peak top temperature in the DSC differential curve (Reference: JIS K6240).
• the obtained Tg and Tm were evaluated according to the following evaluation criteria. [Evaluation Criteria for Tg] A: Tg was less than -20°C. B: Tg was -20°C or higher and lower than 0°C. C: Tg was 0°C or higher and lower than 20°C. D: Tg was 20° C. or higher. [Evaluation criteria for Tm] A: Did not have a clear peak top temperature. B: Tm was -20°C or higher and less than 20°C. C: Tm was 20°C or higher and less than 60°C. D: Tm was 60° C. or higher.
• the viscosity obtained was evaluated according to the following evaluation criteria. [Evaluation Criteria] A: The viscosity at 25° C. was less than 10 Pa ⁇ s. B: The viscosity at 25° C. was 10 Pa ⁇ s or more and less than 50 Pa ⁇ s. C: The viscosity at 25° C. was 50 Pa ⁇ s or more and less than 100 Pa ⁇ s. D: The viscosity at 25° C. was 100 Pa ⁇ s or more.
• the viscosity after 5 minutes was taken as " ⁇ 1" and the viscosity after 60 minutes was taken as " ⁇ 2", and the value calculated by ⁇ 2/ ⁇ 1 was determined as the viscosity increase rate.
• the obtained viscosity increase rates were evaluated according to the following evaluation criteria. The lower the viscosity increase rate, the more excellent the storage stability. [Evaluation Criteria] A: The viscosity increase rate was less than 3.0 times. B: The viscosity increase rate was 3.0 times or more and less than 10.0 times. C: The viscosity increase rate was 10.0 times or more and less than 40.0 times. D: The viscosity increase rate was 10.0 times or more.
• a test piece was prepared by fixing a glass plate instead of a semiconductor element on a glass substrate (26 mm wide x 75 mm long) with a gap of 25 ⁇ m. Next, this test piece was placed on a hot plate set at 110° C., and an epoxy resin composition was applied to one end of the glass plate, and the time (seconds) required for the resin to pass through the gap and reach a point 20 mm away was measured. The obtained time was evaluated according to the following evaluation criteria. The better the flowability, the better the penetration. [Evaluation Criteria] A: The arrival time was less than 80 seconds. B: The arrival time was 80 seconds or more and less than 120 seconds. C: The arrival time was 120 seconds or more and less than 200 seconds. D: The arrival time was 200 seconds or more.
• Tg Tg was 120° C. or higher.
• B Tg was 100° C. or more but less than 120° C.
• C Tg was less than 100°C and 80°C or higher.
• D Tg was less than 80 degrees.
• reaction rate when cured at 180°C or 165°C The reaction rate when the epoxy resin composition was cured at 180°C or 165°C was measured by the following method. Using EXSTER6000 (Hitachi High-Tech Science Corporation), the temperature was raised from 25°C to 300°C at 5°C/min, and the total amount of heat generation observed in the temperature range from 100°C to 250°C was calculated. Furthermore, for Examples 1-1 to 1-11 and Comparative Example 1-1, the same measurement was performed after placing the composition in a small high-temperature chamber (manufactured by Espec Corporation) at 180°C for 2 hours, and the change in heat generation in the same temperature range was calculated as a percentage.
• Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 0.03 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.035 mol of butyl glycidyl ether (BGE), to obtain an epoxy resin curing agent (B).
• BGE butyl glycidyl ether
• the ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC/MS measurement.
• Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 4,4'-diaminodiphenylsulfone (44DAS) was changed to 1,3-bis(3-aminophenoxy)benzene (TPE-M), to obtain an amine adduct (B).
• the ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC/MS measurement.
• Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was changed to 4-aminophenyl-4'-aminobenzoate (APAB) and 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.03 mol to 0.04 mol, to obtain an amine adduct (C-1).
• the ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC/MS measurement.
• Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-4, except that 2-ethylhexyl glycidyl ether was changed to butyl glycidyl ether, to obtain an amine adduct (C-2).
• the ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC/MS measurement.
• Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was changed to 3,4'-oxydianiline (34ODA) and 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.03 mol to 0.045 mol, to obtain an amine adduct (D).
• the ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC/MS measurement.
• Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-4, except that 4-aminophenyl-4'-aminobenzoate (APAB) was changed to Kayahard AA, to obtain an amine adduct (E-1).
• the ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC/MS measurement.
• Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-7, except that 2-ethylhexyl glycidyl ether (2-EH) was changed to phenyl glycidyl ether (ph-GE), to obtain an amine adduct (E-2).
• the ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC/MS measurement.
• Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 4,4'-diaminodiphenyl sulfone (44DAS) was changed to Ethacure 100 Plus, and 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.03 mol to 0.025 mol, to obtain an amine adduct (F-1).
• the ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC/MS measurement.
• Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-9, except that 0.025 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.035 mol of phenyl glycidyl ether (ph-GE), to obtain an amine adduct (F-2).
• the ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC/MS measurement.
• Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-1, except that 4,4'-diaminodiphenylsulfone (44DAS) was changed to Ethacure 300, to obtain an amine adduct (G).
• the ratios of aromatic amine (A-1), aromatic amine adduct (A-2-1), and aromatic amine adduct (A-2-2X) contained in the obtained epoxy resin curing agent were determined by LC/MS measurement.
• Examples 1-1 to 1-11, Comparative Example 1-1 The components shown in Table 3 or 4 were placed in a plastic stirring vessel in the amounts shown in Table 3 or 4, and the mixture was stirred and mixed using a planetary centrifugal mixer ("ARE-310" manufactured by Thinky Corporation), followed by kneading using a three-roll mill to prepare an epoxy resin composition.
• the obtained epoxy resin composition was poured into a Teflon (registered trademark) metal frame and heated at 180° C. for 2 hours to prepare a cured product.
• the obtained cured product was used to evaluate Tg.
• Examples 1-12 to 1-16 The components shown in Table 3 or 4 were placed in a plastic stirring vessel in the amounts shown in Table 3 or 4, and the mixture was stirred and mixed using a planetary centrifugal mixer ("ARE-310" manufactured by Thinky Corporation), followed by kneading using a three-roll mill to prepare an epoxy resin composition.
• the obtained epoxy resin composition was poured into a Teflon metal frame and heated at 165° C. for 2 hours to prepare a cured product.
• the obtained cured product was used to evaluate Tg.
• the examples using the epoxy resin curing agent which includes an aromatic amine compound (A-1), an aromatic amine adduct (A-2) which is a reaction product of the aromatic amine compound and a reactive compound having a functional group capable of reacting with the aromatic amine compound, and an aromatic amine adduct (A-2-1) in which one molecule of the reactive compound is added to one molecule of the aromatic amine compound (A-1), and the ratio (A-1/A-2-1) of the aromatic amine compound to the aromatic amine adduct (A-2-1) obtained by liquid chromatography analysis (UV detector) is 0.50 to 2.00, were excellent in flowability and therefore excellent in permeability.
• the examples were able to obtain a cured product and were also excellent in viscosity stability. Therefore, the epoxy resin curing agent of the examples was able to achieve both curability and storage stability.
• the epoxy resin compositions described in Examples 1-2, 1-4 to 1-8, and 1-9 use an amine adduct in which the ratio (A-1/A-2-1) of the aromatic amine compound to the aromatic amine adduct (A-2-1) is 0.50 to 1.10, and therefore have excellent flowability and therefore excellent permeability.
• the epoxy resin compositions described in Examples 1-1, 1-3, 1-9, and 1-10 use an amine adduct in which the ratio (A-1/A-2-1) of the aromatic amine compound to the aromatic amine adduct (A-2-1) is 1.20 to 2.00, and therefore have excellent reactivity and therefore excellent heat resistance.
• Comparative Example 1-1 which did not use the aromatic amine adduct (A-2), which is a reaction product between the aromatic amine compound (A-1) and a reactive compound, had poor flowability and therefore poor penetration. This is presumably because the epoxy resin composition described in Comparative Example 1-1 did not contain the aromatic amine adduct (A-2) and therefore had poor viscosity stability.
• the epoxy resin compositions described in Examples 1-12 to 1-16 have sufficient curing properties even when the temperature is lowered from 180°C to 165°C by adding a curing catalyst to compensate for the reactivity of the amine adduct.
• the epoxy resin compositions of the examples can be suitably used as sealing materials, particularly underfill materials used for sealing semiconductor chips, etc.
• the epoxy resin curing agent obtained in Example 2 which uses an aromatic amine adduct (A-2), which is a reaction product between an aromatic amine compound and a reactive compound having a functional group capable of reacting with the aromatic amine compound (A-1), and in which the molecular weight of the reactive compound is less than 150, has a high Tg, and therefore has low fluidity when stored for a long period of time, such as one month, at room temperature, and there is room for further improvement in handleability when kneading with epoxy resin.
• A-2 aromatic amine adduct
• an epoxy resin curing agent using a reactive compound having a molecular weight greater than 150 has a low Tg, is fluid even when stored for a long period of time, such as one month, at room temperature, and has excellent handleability when kneading with epoxy resin.

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