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

• the present invention relates to a curing agent for epoxy resins, an epoxy resin composition, a cured product, a sealant, and an adhesive.
• Epoxy resins have a wide range of uses, including paints, electrical and electronic insulating materials, and adhesives, because the cured products have a variety of properties.
• 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 is solid, and there is room for improvement in terms of its penetration into 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 a curing agent for epoxy resins that has excellent permeability after being mixed with epoxy resins 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 curing agent for epoxy resins.
• a hardener for epoxy resins comprising:
• R ⁇ and R ⁇ each independently represent a monovalent organic group having 1 to 20 carbon atoms or a halogen
• c and d each independently represent an integer of 1 to 4
• Y represents a divalent organic group or a single bond.
• R ⁇ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and e is an integer of 1 to 4.
• R ⁇ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and e is an integer of 1 to 4.
• the epoxy resin curing agent according to ⁇ 1> which has a glass transition temperature (Tg) of 10° C. or lower as measured by differential scanning calorimetry (DSC analysis) at a heating rate of 5° C./min.
• Tg glass transition temperature
• DSC analysis differential scanning calorimetry
• a curing agent for epoxy resins which has a glass transition temperature (Tg) of 20°C or less as detected by differential scanning calorimetry (DSC analysis) at a heating rate of 5°C/min.
• DSC analysis differential scanning calorimetry
• R ⁇ and R ⁇ 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
• X represents a divalent organic group or a single bond.
• R ⁇ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and c is an integer of 1 to 4.
• Tm melting point
• the aromatic amine adduct (A-2) includes 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),
• the epoxy resin curing agent according to any one of ⁇ 1> to ⁇ 8>, wherein a 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 0.10 to 0.45.
• the aromatic amine adduct (A-2) includes 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),
• An epoxy resin composition comprising the epoxy resin curing agent according to any one of ⁇ 1> to ⁇ 11>, an epoxy resin (B), and an inorganic filler (C).
• the curing accelerator (D) 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.
• ⁇ 16> The epoxy resin composition according to any one of ⁇ 12> to ⁇ 15>, having a viscosity ( ⁇ 2) after standing at 110°C for 60 minutes of 0.01 Pa ⁇ s to 1.50 Pa ⁇ s. ⁇ 17>
• the ratio (thickening rate, ⁇ 2/ ⁇ 1) of the viscosity ( ⁇ 2) after standing at 110 ° C. for 60 minutes to the viscosity ( ⁇ 1) after standing at 110 ° C. for 5 minutes is 1.0 times or more and 40.0 times or less
• ⁇ 18> The epoxy resin composition according to any one of ⁇ 12> to ⁇ 17>, having a viscosity at 25°C of 50 Pa ⁇ s or less.
• ⁇ 19> A cured product of the epoxy resin composition according to any one of ⁇ 12> to ⁇ 18>.
• ⁇ 20> An encapsulant comprising the cured product according to ⁇ 19>.
• ⁇ 21> The encapsulant according to ⁇ 20>, which is an encapsulant for semiconductors.
• An adhesive comprising the epoxy resin composition according to any one of ⁇ 12> to ⁇ 18>.
• ⁇ 23> A semiconductor package comprising the cured product according to ⁇ 19>.
• ⁇ 24> A method for producing a semiconductor package, comprising the step of producing a semiconductor package using the epoxy resin composition according to ⁇ 12>.
• 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, sealant, 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).
• This embodiment includes the following first and second embodiments.
• the epoxy resin curing agent of the first embodiment comprises an aromatic amine compound (A-1) represented by the following formula (1), the following formula (2), or the following formula (3), an aromatic amine adduct (A-2) which is a reaction product of an aromatic amine compound (A-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (A-1); Includes.
• R ⁇ and R ⁇ each independently represent a monovalent organic group having 1 to 20 carbon atoms or a halogen
• c and d each independently represent an integer of 1 to 4
• Y represents a divalent organic group or a single bond.
• R ⁇ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and e is an integer of 1 to 4.
• the epoxy resin curing agent of the first 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 aromatic amine compound (A-1) is represented by formula (1), the following formula (2) or the following formula (3).
• the monovalent organic group having 1 to 20 carbon atoms preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms.
• Each of a and b is independently preferably an integer of 0 to 2, and more preferably 0 or 1.
• the divalent organic group having one or more aromatic rings preferably has one aromatic ring, and more preferably has one benzene ring.
• aromatic amine compound represented by formula (1) examples include, for example, 4-aminophenyl-4-aminobenzoate (APAB), 2-methyl-4-aminophenyl-4-aminobenzoate, 3-methyl-4-aminophenyl-4-aminobenzoate, 2-fluoro-4-aminophenyl-4-aminobenzoate, 3-fluoro-4-aminophenyl-4-aminobenzoate, 3-methyl-4-aminophenyl-3-methyl-4-aminobenzoate, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benz
• benzene bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,2-bis[
• R ⁇ and R ⁇ each independently represent a monovalent organic group having 1 to 20 carbon atoms or a halogen
• c and d each independently represent an integer of 1 to 4
• Y represents a divalent organic group or a single bond.
• the monovalent organic group having 1 to 20 carbon atoms preferably has 1 to 10 carbon atoms, more preferably has 1 to 5 carbon atoms, and further preferably has 1 to 3 carbon atoms.
• Each of c and d is independently preferably an integer of 0 to 2, and more preferably 0 or 1.
• the aromatic amine compound represented by formula (2) is a compound other than the aromatic amine compound represented by formula (1). Therefore, in Y in formula (2), the divalent organic group may be a divalent organic group that does not have an aromatic ring.
• Examples of the aromatic amine compound represented by formula (2) include m-tolidine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, 4,4'-diamino-3,3'-5,5'-tetraethyldiphenylmethane, and the like.
• aromatic amine compound represented by formula (2) 3,3'-diethyl-4,4'-diaminodiphenylmethane is more preferred as the aromatic amine compound represented by formula (2).
• R ⁇ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and e is an integer of 1 to 4.
• the monovalent organic group having 1 to 20 carbon atoms preferably has 1 to 10 carbon atoms, more preferably has 1 to 5 carbon atoms, and further preferably has 1 to 3 carbon atoms.
• e is preferably an integer of 1 to 3, and more preferably 1 or 2.
• Examples of the aromatic amine compound represented by formula (3) include diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene), dimethylthiotoluenediamine, and the like. It is preferable to use one or more compounds selected from the group consisting of these.
• diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene and 2,6-diamino-3,5-diethyltoluene) is preferred as the aromatic amine compound represented by formula (3).
• the aromatic amine adduct (A-2) is a reaction product between the aromatic amine compound (A-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (A-1).
• the reactive compound has a functional group capable of reacting with the aromatic amine compound (A-1).
• the reactive compound is preferably at least one compound selected from the group consisting of acid anhydrides, acid dianhydrides, carboxylic acid compounds, sulfonic acid compounds, isocyanate compounds, urea compounds, epoxy compounds, and alkyl halide compounds.
• carboxylic acid compounds include succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid.
• sulfonic acid compounds include ethanesulfonic acid and p-toluenesulfonic acid.
• isocyanate compound examples include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aliphatic triisocyanates, and polyisocyanates.
• aliphatic diisocyanate examples include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.
• alicyclic diisocyanate examples include isophorone diisocyanate, 4-4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis(isocyanatomethyl)-cyclohexane, and 1,3-bis(2-isocyanatopropyl-2yl)-cyclohexane.
• aromatic diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate.
• Examples of the aliphatic triisocyanate include 1,3,6-triisocyanate methylhexane, and 2-isocyanatoethyl 2,6-diisocyanatohexanoate.
• Examples of the polyisocyanate include polymethylene polyphenyl polyisocyanate and polyisocyanates derived from the above diisocyanate compounds.
• Polyisocyanates derived from the above diisocyanates include isocyanurate type polyisocyanates, biuret type polyisocyanates, urethane type polyisocyanates, allophanate type polyisocyanates, carbodiimide type polyisocyanates, and the like.
• Examples of the urea compound include urea, methyl urea, dimethyl urea, ethyl urea, and t-butyl urea.
• epoxy compound either a monoepoxy compound, a polyepoxy compound, or a mixture thereof is used.
• monoepoxy compounds include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxylyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl hexoate, and glycidyl benzoate.
• polyfunctional epoxy compounds include bisphenol-type epoxy compounds obtained by glycidylating bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, and tetrafluorobisphenol A; epoxy compounds obtained by glycidylating dihydric phenols such as biphenol, dihydroxynaphthalene, and 9,9-bis(4-hydroxyphenyl)fluorene; epoxy compounds obtained by glycidylating trisphenols such as 1,1,1-tris(4-hydroxyphenyl)methane and 4,4-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol; and epoxy compounds obtained by glycidylating tetraki
• novolac-type epoxy compounds obtained by glycidylating novolacs such as phenol novolac, cresol novolac, bisphenol A novolac, brominated phenol novolac, and brominated bisphenol A novolac; aliphatic ether-type epoxy compounds obtained by glycidylating polyhydric alcohols such as glycerin and polyethylene glycol; ether ester-type epoxy compounds obtained by glycidylating hydroxycarboxylic acids such as p-oxybenzoic acid and ⁇ -oxynaphthoic acid; ester-type epoxy compounds obtained by glycidylating polycarboxylic acids such as phthalic acid and terephthalic acid; glycidyl-type epoxy compounds such as epoxy compounds obtained by glycidylating amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol, and epoxy compounds obtained by glycidylating amine-type epoxy compounds such as
• epoxy compounds are preferred as reactive compounds, and epoxy compounds having one glycidyl group in the molecule are more preferred.
• the total chlorine content of the epoxy compound is preferably 400 ppm or less, more preferably 300 ppm or less, even more preferably 200 ppm or less, particularly preferably 180 ppm or less, even more preferably 150 ppm or less, even more preferably 100 ppm or less, particularly preferably 80 ppm or less, and even more preferably 50 ppm or less.
• the total chlorine amount refers to the total amount of organic chlorine and inorganic chlorine contained in the compound, and is a value based on the mass of the compound.
• the chlorine contained in 1,2-chlorohydrin groups is generally called hydrolyzable chlorine, and the amount of hydrolyzable chlorine in the epoxy compound used in the first embodiment is preferably 50 ppm or less, more preferably 0.01 to 20 ppm, and even more preferably 0.05 to 10 ppm. If the amount of hydrolyzable chlorine is 50 ppm or less, it is advantageous for achieving both high curability and storage stability, and is preferable because it shows excellent electrical properties.
• examples of the method when it is desired to reduce the total chlorine content of an epoxy compound, examples of the method include a method in which a dechlorination reaction is carried out using a base catalyst in an aprotic solvent and then the epoxy compound is purified by washing with water, and a method in which a dechlorination reaction is carried out using a metal amide compound such as a bis(trialkylsilyl)amide metal salt as a catalyst and then the epoxy compound is purified by washing with water.
• a metal amide compound such as a bis(trialkylsilyl)amide metal salt
• the aromatic amine adduct (A-2) is a reaction product between the aromatic amine compound (A-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (A-1).
• the aromatic amine adduct (A-2) used in the first embodiment can be obtained, for example, by reacting 1 to 5 moles of an aromatic amine compound (A-1) with 1 to 5 moles of a reactive compound (e.g., an epoxy compound) in the presence of a solvent as required, at a temperature of, for example, 50 to 250° C. for 0.1 to 24 hours, and removing, as required, the unreacted aromatic amine compound (A-1) and the solvent.
• a reactive compound e.g., an epoxy compound
• 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
• the epoxy resin curing agent of the first embodiment preferably has a glass transition temperature (Tg) of 10° C. or lower, as detected by differential scanning calorimetry (DSC analysis) measured at a heating rate of 5° C./min.
• Tg glass transition temperature
• DSC analysis differential scanning calorimetry
• the Tg is more preferably 10° C. or less, further preferably 5° C. or less, and particularly preferably 0° C. or less.
• the Tg is preferably ⁇ 50° C. or higher, more preferably ⁇ 45° C. or higher, and even more preferably ⁇ 40° 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 first embodiment preferably has at least one melting point (Tm) of 60° C. or lower, as detected by differential scanning calorimetry (DSC analysis) measured at a heating rate of 5° C./min.
• Tm melting point
• DSC analysis differential scanning calorimetry
• Tm is more preferably 60° C. or less, further preferably 50° C. or less, and particularly preferably 40° C. or less.
• Tm is preferably ⁇ 40° C. or higher, more preferably ⁇ 20° C. or higher, and even more preferably ⁇ 10° C. or higher.
• the epoxy resin curing agent of the first embodiment has no detectable melting point (Tm) in the range of -20°C to 60°C in differential scanning calorimetry (DSC analysis) measured in a temperature range of -50°C to 200°C at a heating rate of 5°C/min.
• Tm melting point
• DSC analysis differential scanning calorimetry
• 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 curing agent of the first 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) preferably 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 preferably 0.10 to 0.45.
• (A-1/A-2-1) is 0.10 or more, the curability is excellent. From the above viewpoints, (A-1/A-2-1) is more preferably 0.10 or more, even more preferably 0.12 or more, and particularly preferably 0.15 or more.
• (A-1/A-2-1) when (A-1/A-2-1) is 0.45 or less, the penetration is more excellent. From the above viewpoints, (A-1/A-2-1) is more preferably 0.45 or less, even more preferably 0.42 or less, and particularly preferably 0.40 or less. Therefore, by making (A-1/A-2-1) 0.10 to 0.45, both the curability and excellent permeability can be achieved.
• the aromatic amine adduct (A-2) preferably 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 preferably 0.50 to 2.00.
• (A-1/A-2-1) is more preferably 0.5 or more, even more preferably 0.75 or more, and particularly preferably 1.2 or more.
• (A-1/A-2-1) is 2.0 or less, the permeability and storage stability are excellent.
• (A-1/A-2-1) is more preferably 2.0 or less, even more preferably 1.9 or less, and particularly preferably 1.8 or less. Therefore, by making (A-1/A-2-1) 0.50 to 2.00, the composition exhibits excellent heat resistance when cured with an epoxy resin, and can also exhibit excellent permeability and storage stability.
• the epoxy resin composition of the first embodiment contains the epoxy resin curing agent of the first 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 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; 1,4-cyclohexanedimethanol diglycidyl ether; and products of epoxidation reaction of pent
• bisphenol type epoxy resins for example, bisphenol type epoxy resins, glycidylamine type epoxy resins obtained by reacting p-aminophenol with epichlorohydrin, 1,4-cyclohexanedimethanol diglycidyl ether, products of epoxidation reaction of pentaerythritol tetraallyl ether with hydrogen peroxide, etc. are preferable. Furthermore, from the viewpoints of heat resistance, adhesiveness and fluidity, for example, the above-mentioned glycidylamine type epoxy resins are preferable.
• 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. 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. From the viewpoints of heat resistance, adhesion and flowability, it is preferable to use a bisphenol type epoxy resin and a glycidylamine type epoxy resin in combination.
• 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.
• There 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.
• 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 sol-gel silica and fused silica are 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 and sol-gel silica, are 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 40% by mass to 70% by mass based on the total amount of the epoxy resin composition.
• the content of the inorganic filler 40% 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 the first 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 first embodiment preferably further contains a curing accelerator (D).
• the curing accelerator (D) is preferably at least one selected from the group consisting of compounds (D-1) represented by formula (4), formula (5), or formula (6), and 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 in addition to the danger of explosion, 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 such as toxicity.
• 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.
• monocarboxylate ester compounds 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 pressure 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.
• compound (D-1) is preferably such that n in formula (5) and formula (6) 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 first 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 permeability. From the viewpoint of suppressing bleeding, the epoxy resin composition of the first 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 e.g., "TV-20” manufactured by Toki Sangyo Co., Ltd.
• the epoxy resin composition of the first embodiment has a viscosity ( ⁇ 2) 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 first 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 the first 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. Also, the same measurement may 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 the first 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 first embodiment can be suitably used as an adhesive.
• the adhesive of the first embodiment includes the epoxy resin composition of the first embodiment.
• the cured product of the first embodiment is a cured product of the epoxy resin composition of the first embodiment.
• the cured product of the first embodiment can be suitably used as a sealant, and the sealant is preferably a semiconductor sealant.
• the sealing material of the first embodiment includes the cured product of the first embodiment.
• the cured product of the first embodiment can be suitably used as a semiconductor package.
• the semiconductor package of the first embodiment includes the cured product of the first embodiment.
• the method for producing a semiconductor package according to the first embodiment includes a step of producing a semiconductor package using the epoxy resin composition according to the first embodiment.
• the step of manufacturing a semiconductor package using the epoxy resin composition of the first embodiment may include the step of preparing the epoxy resin composition of the first embodiment.
• the epoxy resin composition of the first embodiment may be obtained, for example, by stirring and mixing the components contained in the epoxy resin composition of the first embodiment using a planetary centrifugal mixer (for example, "ARE-310" manufactured by Thinky Corporation) and then kneading the mixture using a three-roll mill.
• the process for manufacturing a semiconductor package using the epoxy resin composition of the first 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.
• the epoxy resin curing agent of the second embodiment contains an aromatic amine compound (A-1) and 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 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
• the epoxy resin curing agent of the second 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 the second embodiment 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
• Tg is more preferably 5° C. or less, further preferably 0° C. or less, and particularly preferably ⁇ 20° C. or less.
• Tg is preferably ⁇ 40° C. or higher, more preferably ⁇ 30° C. or higher, and even more preferably ⁇ 20° 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 aromatic amine compound (A-1) a compound that does not have a melting point in the range of ⁇ 20° C. to 60° C.
• Ethacure 100+ represented by formula (12) is an aromatic amine compound that is liquid at room temperature, and the amine adduct obtained by reacting it with a reactive compound is also liquid, and has a Tg of 10° C. or lower. It is also preferable to use a skeleton having a flexible substituent in the molecular skeleton as the aromatic amine compound (A-1), and to use a compound having an alkyl chain as the reactive compound.
• 4-aminophenyl-4-aminobenzoate has a flexible ester bond in the skeleton, and by reacting it with 2-ethylhexyl glycidyl ether, which is a reactive compound having an alkyl group, the Tg becomes 10°C or less.
• the Tg can be made 20°C or less by reacting more than 1 mol of a reactive compound with 1 mol of the aromatic amine compound (A-1).
• the epoxy resin curing agent of the second embodiment contains an aromatic amine compound (A-1).
• the aromatic amine compound (A-1) is preferably an aromatic amine compound represented by the following formula (11) or (12):
• R ⁇ and R ⁇ 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
• X represents a divalent organic group or a single bond.
• the monovalent organic group having 1 to 20 carbon atoms preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms.
• Each of a and b is independently preferably an integer of 0 to 2, and more preferably 0 or 1.
• the divalent organic group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms.
• Examples of the aromatic amine represented by formula (11) include, for example, 4-aminophenyl-4-aminobenzoate (APAB), 2-methyl-4-aminophenyl-4-aminobenzoate, 3-methyl-4-aminophenyl-4-aminobenzoate, 2-fluoro-4-aminophenyl-4-aminobenzoate, 3-fluoro-4-aminophenyl-4-aminobenzoate, 3-methyl-4-aminophenyl-3-methyl-4-aminobenzoate, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and the like.
• APAB 4-aminophenyl-4-aminobenzoate
• 2-methyl-4-aminophenyl-4-aminobenzoate 3-methyl-4-aminophenyl-4-aminobenzoate
• R ⁇ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and c is an integer of 1 to 4.
• the monovalent organic group having 1 to 20 carbon atoms preferably has 1 to 10 carbon atoms, more preferably has 1 to 5 carbon atoms, and further preferably has 1 to 3 carbon atoms.
• c is preferably an integer of 1 to 3, and more preferably 1 or 2.
• Examples of the aromatic amine represented by formula (12) include diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene), dimethylthiotoluenediamine, and the like. It is preferable to use one or more selected from these. Among these, from the viewpoint of achieving both curability and stability when formed into a composition with an epoxy resin, diethyltoluenediamine (2,4-diamino-3,5-diethyltoluene, 2,6-diamino-3,5-diethyltoluene) is preferred as the aromatic amine represented by formula (12).
• the aromatic amine adduct (A-2) is a reaction product between the aromatic amine compound (A-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (A-1).
• the reactive compound has a functional group capable of reacting with the aromatic amine compound (A-1).
• the functional group include a carboxyl group, a sulfo group, an isocyanato group, a carbonyl group, and an epoxy group.
• the reactive compound has a functional group capable of reacting with the aromatic amine compound (A-1).
• the reactive compound is preferably at least one compound selected from the group consisting of acid anhydrides, acid dianhydrides, carboxylic acid compounds, sulfonic acid compounds, isocyanate compounds, urea compounds, epoxy compounds, and alkyl halides.
• carboxylic acid compounds include succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid.
• sulfonic acid compounds include ethanesulfonic acid and p-toluenesulfonic acid.
• isocyanate compound examples include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aliphatic triisocyanates, and polyisocyanates.
• aliphatic diisocyanate examples include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.
• alicyclic diisocyanate examples include isophorone diisocyanate, 4-4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis(isocyanatomethyl)-cyclohexane, and 1,3-bis(2-isocyanatopropyl-2yl)-cyclohexane.
• aromatic diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate.
• Examples of the aliphatic triisocyanate include 1,3,6-triisocyanate methylhexane, and 2-isocyanatoethyl 2,6-diisocyanatohexanoate.
• Examples of the polyisocyanate include polymethylene polyphenyl polyisocyanate and polyisocyanates derived from the above diisocyanate compounds.
• Examples of polyisocyanates derived from the above diisocyanates include isocyanurate type polyisocyanates, biuret type polyisocyanates, urethane type polyisocyanates, allophanate type polyisocyanates, carbodiimide type polyisocyanates, and the like.
• urea compounds include urea, methyl urea, dimethyl urea, ethyl urea, and t-butyl urea.
• the epoxy compound either a monoepoxy compound, a polyepoxy compound, or a mixture thereof is used.
• the monoepoxy compound include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxylyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl hexoate, and glycidyl benzoate.
• polyfunctional epoxy compounds include bisphenol-type epoxy compounds obtained by glycidylating bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, and tetrafluorobisphenol A; epoxy compounds obtained by glycidylating dihydric phenols such as biphenol, dihydroxynaphthalene, and 9,9-bis(4-hydroxyphenyl)fluorene; epoxy compounds obtained by glycidylating trisphenols such as 1,1,1-tris(4-hydroxyphenyl)methane and 4,4-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol; and epoxy compounds obtained by glycidylating tetraki
• novolac-type epoxy compounds obtained by glycidylating novolacs such as phenol novolac, cresol novolac, bisphenol A novolac, brominated phenol novolac, and brominated bisphenol A novolac; aliphatic ether-type epoxy compounds obtained by glycidylating polyhydric alcohols such as glycerin and polyethylene glycol; ether ester-type epoxy compounds obtained by glycidylating hydroxycarboxylic acids such as p-oxybenzoic acid and ⁇ -oxynaphthoic acid; ester-type epoxy compounds obtained by glycidylating polycarboxylic acids such as phthalic acid and terephthalic acid; glycidyl-type epoxy compounds such as epoxy compounds obtained by glycidylating amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol, and epoxy compounds obtained by glycidylating amine-type epoxy compounds such as
• epoxy compounds are preferred as reactive compounds, and epoxy compounds having one glycidyl group in the molecule are more preferred.
• the total chlorine content of the epoxy compound is preferably 400 ppm or less, more preferably 300 ppm or less, even more preferably 200 ppm or less, particularly preferably 180 ppm or less, even more preferably 171 ppm or less, even more preferably 100 ppm or less, particularly preferably 80 ppm or less, and even more preferably 50 ppm or less.
• the total chlorine amount refers to the total amount of organic chlorine and inorganic chlorine contained in the compound, and is a value based on the mass of the compound.
• the chlorine contained in 1,2-chlorohydrin groups is generally called hydrolyzable chlorine, and the amount of hydrolyzable chlorine in the epoxy compound used in the second embodiment is preferably 50 ppm or less, more preferably 0.01 to 20 ppm, and even more preferably 0.05 to 10 ppm. If the amount of hydrolyzable chlorine is 50 ppm or less, it is advantageous for achieving both high curability and storage stability, and is preferable because it shows excellent electrical properties.
• examples of the method when it is desired to reduce the total chlorine content of an epoxy compound, examples of the method include a method in which a dechlorination reaction is carried out using a base catalyst in an aprotic solvent and then the epoxy compound is purified by washing with water, and a method in which a dechlorination reaction is carried out using a metal amide compound such as a bis(trialkylsilyl)amide metal salt as a catalyst and then the epoxy compound is purified by washing with water.
• a metal amide compound such as a bis(trialkylsilyl)amide metal salt
• the aromatic amine adduct (A-2) is a reaction product between the aromatic amine compound (A-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (A-1).
• the aromatic amine adduct (A-2) used in the second embodiment can be obtained, for example, by reacting 1 to 5 moles of an aromatic amine compound (A-1) with 1 to 5 moles of a reactive compound (e.g., an epoxy compound) in the presence of a solvent as required, at a temperature of, for example, 50 to 250° C. for 0.1 to 10 hours, and removing, as required, the unreacted aromatic amine compound (A-1) and the solvent.
• a reactive compound e.g., an epoxy compound
• 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
• the epoxy resin curing agent of the second embodiment preferably has at least one melting point (Tm) of 60° C. or less 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 60° C. or less, 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.
• the epoxy resin curing agent of the second embodiment has no melting point (Tm) detected in the range of -20°C to 60°C in differential scanning calorimetry (DSC analysis) measured in a temperature range of -50°C to 200°C and at a heating rate of 5°C/min.
• Tm melting point
• DSC analysis differential scanning calorimetry
• Ethacure 100+ represented by formula (12) is an aromatic amine compound that is liquid and amorphous at room temperature, and the amine adduct obtained by reacting it with a reactive compound is also liquid and amorphous, so that Tm is not observed in the range of ⁇ 20 to 60° C.
• a skeleton having a flexible substituent in the molecular skeleton as the aromatic amine compound (A-1), and to use a compound having an alkyl chain as the reactive compound.
• 4-aminophenyl-4-aminobenzoate has a flexible ester bond in the skeleton, and when reacted with 2-ethylhexyl glycidyl ether, which is a reactive compound having an alkyl group, the Tm becomes 60° C. or less.
• the Tm can also be made 60° C. or less by reacting 1 mol or more of 2-ethylhexyl glycidyl ether as a reactive compound with 1 mol of the aromatic amine compound (A-1).
• 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 curing agent of the second 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) preferably 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 preferably 0.10 to 0.45.
• (A-1/A-2-1) is more preferably 0.1 or more, even more preferably 0.12 or more, and particularly preferably 0.15 or more.
• (A-1/A-2-1) is 0.45 or less, the penetration is more excellent.
• (A-1/A-2-1) is more preferably 0.45 or less, even more preferably 0.42 or less, and particularly preferably 0.40 or less. Therefore, by making (A-1/A-2-1) 0.10 to 0.45, both the curability and excellent permeability can be more satisfactorily achieved.
• 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.
• (A-1/A-2-1) is 0.50 or more, the heat resistance of the cured product with the epoxy resin is excellent.
• (A-1/A-2-1) is more preferably 0.5 or more, even more preferably 0.75 or more, and particularly preferably 1.2 or more.
• (A-1/A-2-1) is 2.0 or less, the permeability and storage stability are excellent.
• (A-1/A-2-1) is more preferably 2.0 or less, even more preferably 1.9 or less, and particularly preferably 1.8 or less. Therefore, by making (A-1/A-2-1) 0.50 to 2.00, the heat resistance when cured with the epoxy resin is excellent, and the penetrability and storage stability can be more satisfactorily achieved.
• the epoxy resin composition of the second embodiment contains the epoxy resin curing agent of the second embodiment, an epoxy resin (B), and an inorganic filler (C).
• the epoxy resin composition of the second embodiment preferably has a viscosity at 25°C of 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 permeability.
• the epoxy resin composition of the second embodiment preferably has a viscosity at 25°C of 0.1 Pa ⁇ s or more, more preferably 1 Pa ⁇ s or more, and even more preferably 2 Pa ⁇ s or more, from the viewpoint of suppressing bleeding.
• an E-type viscometer e.g., "TV-20” manufactured by Toki Sangyo Co., Ltd.
• the epoxy resin composition of the second 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 1.3 Pa ⁇ s, and even more preferably 0.01 Pa ⁇ s to 1.0 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 second embodiment preferably has a viscosity increase rate after being left at 110°C for 60 minutes of 1.0 times or more and 40.0 times or less, more preferably 1 times or more and 30 times or less, and even more preferably 1 times or more and 20 times or less.
• 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 the second 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 is cured at 165°C or 180°C is calculated by, for example, using an EXSTER6000 (Hitachi High-Tech Science Corporation), raising the temperature from 25°C to 300°C at a rate of 5°C/min, 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 epoxy resin composition and cured product of the second 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 second embodiment can be suitably used as an adhesive.
• the adhesive of the second embodiment includes the epoxy resin composition of the second embodiment.
• the cured product of the second embodiment is a cured product of the epoxy resin composition of the second embodiment. Details of specific aspects, preferred aspects, etc. of the cured product in the second embodiment are similar to those of specific aspects, preferred aspects, etc. of the cured product in the first embodiment.
• 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 calorimeter 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).
• the 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 (JIS K6240).
• Tg and Tm were evaluated according to the following evaluation criteria.
• 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 obtained viscosity increase rates were evaluated according to the following evaluation criteria. [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 40.0 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. [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 165°C The reaction rate when the epoxy resin composition was cured at 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 sample 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 3,4'-oxydianiline (34ODA) was changed to 1,3-bis(3-aminophenoxy)benzene (TPE-M), to obtain an epoxy resin curing agent (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 3,4'-oxydianiline (34ODA) was changed to 4-aminophenyl-4'-aminobenzoate (APAB), to obtain an epoxy resin curing agent (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 performed 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 epoxy resin curing agent (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 3,4'-oxydianiline (34ODA) was changed to m-tolidine (m-TB), to obtain an epoxy resin curing agent (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 1-1, except that 3,4'-oxydianiline (34ODA) was changed to Kayahard AA, to obtain an epoxy resin curing agent (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 performed under the same conditions as in Synthesis Example 1-7, except that 2-ethylhexyl glycidyl ether was changed to butyl glycidyl ether, to obtain an epoxy resin curing agent (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 3,4'-oxydianiline (34ODA) was changed to Ethacure 100 Plus, to obtain an epoxy resin curing agent (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 2-ethylhexyl glycidyl ether was changed to phenyl glycidyl ether, to obtain an epoxy resin curing agent (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 3,4'-oxydianiline (34ODA) was changed to DMTDA, to obtain an epoxy resin curing agent (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.
• Synthesis and purification were performed under the same conditions as in Synthesis Example 1-4, except that the amount of 2-ethylhexyl glycidyl ether was changed from 0.05 mol to 0.03 mol, to obtain an epoxy resin curing agent (C-3).
• 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 performed under the same conditions as in Synthesis Example 1-5, except that the amount of butyl glycidyl ether was changed from 0.05 mol to 0.035 mol, to obtain an epoxy resin curing agent (C-4).
• 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 the amount of 2-ethylhexyl glycidyl ether was changed from 0.05 mol to 0.025 mol, to obtain an epoxy resin curing agent (E-3).
• 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 performed under the same conditions as in Synthesis Example 1-8, except that the amount of phenyl glycidyl ether was changed from 0.05 mol to 0.04 mol, to obtain an epoxy resin curing agent (E-4).
• 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 performed under the same conditions as in Synthesis Example 1-9, except that the amount of 2-ethylhexyl glycidyl ether was changed from 0.05 mol to 0.025 mol, to obtain an epoxy resin curing agent (F-3).
• 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 the amount of 2-ethylhexyl glycidyl ether was changed from 0.05 mol to 0.03 mol of butyl glycidyl ether, to obtain an epoxy resin curing agent (F-4).
• 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, Examples 1-15 to 1-20, Comparative Example 1-1) The components shown in Tables 4 to 6 were placed in a plastic stirring vessel in the amounts shown in Tables 4 to 6, and the mixture was stirred and mixed using a planetary centrifugal mixer ("ARE-310" manufactured by Thinky Corporation), followed by kneading with a three-roll mill to prepare epoxy resin compositions.
• 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 1-14, Examples 1-21 to 1-24, Comparative Example 1-1) The components shown in Tables 4 to 6 were placed in a plastic stirring vessel in the amounts shown in Tables 4 to 6, and the mixture was stirred and mixed using a planetary centrifugal mixer ("ARE-310" manufactured by Thinky Corporation), followed by kneading with a three-roll mill to prepare epoxy resin compositions.
• 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 epoxy resin compositions described in Examples 1-12 to 1-14 and Examples 1-21 to 1-24 have sufficient curing properties even when the temperature is lowered from 180°C to 165°C by adding a curing accelerator (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 flowability is poor, and therefore the penetration is poor.
• the Tg and Tm of the epoxy resin curing agent are relatively high, so that the viscosity of the epoxy resin composition is poor, and as a result, the flowability is reduced.
• an aromatic amine compound other than the aromatic amine compound (A-1) in the first embodiment is used, the viscosity stability is excellent but the curability is poor and the Tg may be low.
• the reason for this is that, for example, the use of an amine having an electron-withdrawing group such as a sulfonyl group (4,4'-diaminodiphenylsulfone, etc.) as the aromatic amine compound reduces the reactivity and compatibility with the epoxy resin. Furthermore, when an aromatic amine compound other than the aromatic amine compound (A-1) in the first embodiment is used, although the viscosity of the epoxy resin composition is low, the viscosity stability is poor and flowability may decrease.
• an aromatic amine compound other than the aromatic amine compound (A-1) in the first embodiment is used, although the viscosity of the epoxy resin composition is low, the viscosity stability is poor and flowability may decrease.
• the reason for this is that, for example, when an aromatic amine having a functional group such as a methylene group and no substituent on the side chain (4,4'-diaminodiphenylmethane, etc.) is used as the aromatic amine compound, the reactivity of the aromatic amine compound used is too high.
• 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 sample amount of 10 mg 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 of the DSC curve (JIS K7121-1987), and the Tg was taken as the peak top temperature of 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 ⁇ 20° C. or lower. B: Tg was greater than -20°C and less than 5°C. C: Tg was more than 5° C. and not more than 20° C. D: Tg was greater than 20°C. [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 60°C or lower. D: Tm was greater than 60°C.
• 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.
• 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. [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 165°C The reaction rate when the epoxy resin composition was cured at 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, 1-15 to 1-24, and Comparative Example 1-1, the same measurement was performed after placing them 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 0.05 mol of 3,4'-oxydianiline (34ODA) was changed to 0.055 mol of 1,3-bis(3-aminophenoxy)benzene (TPE-M), to obtain an epoxy resin curing agent (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 1-4, except that 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.06 mol of butyl glycidyl ether (BGE), to obtain an epoxy resin curing agent (C-2).
• 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 3,4'-oxydianiline (34ODA) was changed to m-tolidine (m-TB) and 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.05 mol to 0.075 mol, to obtain an epoxy resin curing agent (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 1-7, except that 0.05 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.065 mol of phenyl glycidyl ether (ph-GE), to obtain an epoxy resin curing agent (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 1-9, except that 0.05 mol of 2-ethylhexyl glycidyl ether (2-EH) was changed to 0.060 mol of phenyl glycidyl ether (ph-GE), to obtain an epoxy resin curing agent (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 3,4'-oxydianiline (34ODA) was changed to Ethacure 300, and 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.05 mol to 0.055 mol, to obtain an epoxy resin curing agent (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.
• Synthesis and purification were carried out under the same conditions as in Synthesis Example 1-4, except that the amount of 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.05 mol to 0.75 mol, to obtain an epoxy resin curing agent (C-3).
• 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 1-5, except that butyl glycidyl ether (BGE) was changed from 0.05 mol to 0.075 mol, to obtain an epoxy resin curing agent (C-4).
• 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 1-7, except that the amount of 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.05 mol to 0.03 mol, to obtain an epoxy resin curing agent (E-3).
• 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 1-8, except that the amount of phenyl glycidyl ether (ph-GE) was changed from 0.05 mol to 0.035 mol, to obtain an epoxy resin curing agent (E-4).
• 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 the amount of 2-ethylhexyl glycidyl ether (2-EH) was changed from 0.05 mol to 0.025 mol, to obtain an epoxy resin curing agent (F-3).
• 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 butyl glycidyl ether (BGE) was changed from 0.05 mol to 0.035 mol, to obtain an epoxy resin curing agent (F-4).
• 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.
• Examples 1-1 to 1-7, Examples 1-11 to 1-17, Comparative Example 1-1) The components shown in Tables 8 to 10 were placed in a plastic stirring vessel in the amounts shown in Tables 8 to 10, and the mixture was stirred and mixed using a planetary centrifugal mixer ("ARE-310" manufactured by Thinky Corporation), followed by kneading with a three-roll mill to prepare epoxy resin compositions.
• 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 1-8 to 1-10, Examples 1-18 to 1-20 The components shown in Tables 8 to 10 were placed in a plastic stirring vessel in the amounts shown in Tables 8 to 10, and the mixture was stirred and mixed using a planetary centrifugal mixer ("ARE-310" manufactured by Thinky Corporation), followed by kneading with a three-roll mill to prepare epoxy resin compositions.
• 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 containing an aromatic amine compound (A-1), 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, and having a glass transition temperature (Tg) of 20° C. or less as detected by differential scanning calorimetry (DSC analysis) at a heating rate of 5° C./min, were excellent in flowability, curability and storage stability. Therefore, the epoxy resin curing agents of the examples were excellent in permeability and were able to achieve both curability and storage stability.
• Comparative Example 1-1 which uses a curing agent whose glass transition temperature (Tg) detected by differential scanning calorimetry (DSC) at a heating rate of 5°C/min is not 20°C or lower, had poor flowability and therefore poor penetration. This is thought to be because the affinity with the epoxy resin is poor, and as a result, the viscosity of the epoxy resin composition is poor, resulting in a decrease in flowability.
• Tg glass transition temperature
• the epoxy resin compositions described in Examples 1-8 to 1-10 and 1-18 to 1-20 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 curing agent has excellent reactivity but has a high viscosity and poor affinity with epoxy resins, resulting in poor curability when used as an epoxy resin composition, and the reaction does not proceed sufficiently even after thermal curing, resulting in a low Tg.
• a curing agent for epoxy resins comprising: an aromatic amine compound (A-1) represented by the following formula (1), (2) or (3); and an aromatic amine adduct (A-2) which is a reaction product of the aromatic amine compound (A-1) and a reactive compound having a functional group capable of reacting with the aromatic amine compound (A-1).
• R ⁇ and R ⁇ each independently represent a monovalent organic group having 1 to 20 carbon atoms or a halogen
• c and d each independently represent an integer of 1 to 4
• Y represents a divalent organic group or a single bond.
• R ⁇ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and e is an integer of 1 to 4.
• R ⁇ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and e is an integer of 1 to 4.
• the epoxy resin curing agent according to ⁇ 1> which has a glass transition temperature (Tg) of 10° C. or lower as measured by differential scanning calorimetry (DSC analysis) at a heating rate of 5° C./min.
• Tg glass transition temperature
• DSC analysis differential scanning calorimetry
• ⁇ 4> The epoxy resin curing agent according to any one of ⁇ 1> to ⁇ 3>, which has no detectable melting point (Tm) in the range of -20°C to 60°C in differential scanning calorimetry (DSC analysis) measured in a temperature range of -50°C to 200°C at a heating rate of 5°C/min.
• Tm melting point
• DSC analysis differential scanning calorimetry
• 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 (A-1) to the aromatic amine adduct (A-2-1), obtained by liquid chromatography analysis (UV detector), is 0.10 to 0.45.
• ⁇ 6> The epoxy resin curing agent according to any one of ⁇ 1> to ⁇ 5>, 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 (A-1) to the aromatic amine adduct (A-2-1), obtained by liquid chromatography analysis (UV detector), is 0.5 to 2.0.
• the reactive compound is a 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 ⁇ 7>, an epoxy resin (B), and an inorganic filler (C).
• the curing accelerator (D) 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.
• ⁇ 12> The epoxy resin composition according to any one of ⁇ 8> to ⁇ 11>, having a viscosity ( ⁇ 2) of 0.01 Pa ⁇ s to 1.50 Pa ⁇ s after standing at 110° C. for 60 minutes.
• ⁇ 13> The epoxy resin composition according to ⁇ 12>, in which the ratio (thickening rate, ⁇ 2/ ⁇ 1) of the viscosity ( ⁇ 2) after standing at 110° C. for 60 minutes to the viscosity ( ⁇ 1) after standing at 110° C. for 5 minutes is 1.0 to 40.0 times, and the reaction rate when cured at 165° C. is 80% to 99%.
• ⁇ 14> A cured product of the epoxy resin composition according to any one of ⁇ 8> to ⁇ 13>.
• ⁇ 15> An encapsulant comprising the cured product according to ⁇ 14>.
• ⁇ 16> The encapsulant according to ⁇ 15>, which is an encapsulant for semiconductors.
• ⁇ 17> An adhesive comprising the epoxy resin composition according to any one of ⁇ 8> 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 by using the epoxy resin composition according to any one of ⁇ 8> to ⁇ 13>.
• a curing agent for epoxy resins comprising: an aromatic amine compound (A-1); and 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, the curing agent having a glass transition temperature (Tg) of 5°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
• 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 (A-1) to the aromatic amine adduct (A-2-1), obtained by liquid chromatography analysis (UV detector), is 0.10 to 0.45.
• 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 (A-1) to the aromatic amine adduct (A-2-1), obtained by liquid chromatography analysis (UV detector), is 0.50 to 2.00.
• R ⁇ and R ⁇ 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
• X represents a divalent organic group or a single bond.
• R ⁇ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and c is an integer of 1 to 4.
• R ⁇ represents a monovalent organic group having 1 to 20 carbon atoms or a halogen; and c is an integer of 1 to 4.
• An epoxy resin composition comprising the epoxy resin curing agent according to any one of ⁇ 1> to ⁇ 7>, an epoxy resin (B), and an inorganic filler (C).
• C an inorganic filler
• D curing accelerator
• 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.
• ⁇ 12> The epoxy resin composition according to any one of ⁇ 8> to ⁇ 11>, having a viscosity of 0.01 Pa ⁇ s to 1.50 Pa ⁇ s after standing at 110° C. for 60 minutes.
• ⁇ 13> The epoxy resin composition according to ⁇ 12>, having a viscosity increase rate of 1.0 to 40.0 times after standing at 110°C for 60 minutes, and a reaction rate of 80 to 99% when cured at 165°C.
• ⁇ 14> The epoxy resin composition according to any one of ⁇ 8> to ⁇ 13>, having a viscosity of 50 Pa ⁇ s or less at 25° C.
• ⁇ 16> An encapsulant comprising the cured product according to ⁇ 15>.
• ⁇ 17> The encapsulant according to ⁇ 16>, which is an encapsulant for semiconductors.
• An adhesive comprising the epoxy resin composition according to any one of ⁇ 8> to ⁇ 14>.
• ⁇ 19> A semiconductor package comprising the cured product according to ⁇ 15>.
• ⁇ 20> A method for producing a semiconductor package, comprising the step of producing a semiconductor package using the epoxy resin composition according to ⁇ 14>.

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