WO2014103552A1 - Liquid epoxy resin composition - Google Patents

Liquid epoxy resin composition Download PDF

Info

Publication number
WO2014103552A1
WO2014103552A1 PCT/JP2013/080870 JP2013080870W WO2014103552A1 WO 2014103552 A1 WO2014103552 A1 WO 2014103552A1 JP 2013080870 W JP2013080870 W JP 2013080870W WO 2014103552 A1 WO2014103552 A1 WO 2014103552A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
epoxy resin
component
mass
parts
Prior art date
Application number
PCT/JP2013/080870
Other languages
French (fr)
Japanese (ja)
Inventor
洋平 細野
Original Assignee
ナミックス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ナミックス株式会社 filed Critical ナミックス株式会社
Priority to KR1020157007533A priority Critical patent/KR102072259B1/en
Priority to CN201380051978.4A priority patent/CN104684957B/en
Publication of WO2014103552A1 publication Critical patent/WO2014103552A1/en
Priority to PH12015501209A priority patent/PH12015501209A1/en

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • 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
    • C08G59/182—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 using pre-adducts of epoxy compounds with 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
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
    • 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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • 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
    • C08K5/55—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H01L21/563—Encapsulation of active face of flip-chip device, e.g. underfilling or underencapsulation of flip-chip, encapsulation preform on chip or mounting substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a liquid epoxy resin composition, and in particular, to a liquid epoxy resin composition that is excellent in fluidity and has a low linear expansion coefficient and can be used as an adhesive for an underfill material or electronic component.
  • flip-chip bonding has been used as a semiconductor chip mounting method that can cope with higher wiring density and higher frequency of electronic devices.
  • flip chip mounting since the semiconductor chip and the substrate are directly connected, the stress caused by the difference in the linear expansion coefficient between the silicon chip and the substrate may cause cracks in the connection portion, resulting in poor connection reliability.
  • a technique of filling a liquid sealing material called an underfill material between a semiconductor chip and a wiring board is used. By using the underfill material, it is possible to improve connection reliability against thermal stress such as heat cycle and connection reliability against physical stress such as impact and bending.
  • the linear expansion coefficient of the silicon chip is 4 ppm / ° C.
  • the linear expansion coefficient of the substrate for example, a glass epoxy substrate
  • the underfill material is mixed with an inorganic filler in order to absorb the difference in linear expansion coefficient, and a silica filler is usually used as the inorganic filler.
  • the underfill material uses an epoxy-imidazole curing system as a low-temperature curable resin, and a silica filler is added to the resin system for the purpose of reducing the linear expansion coefficient of the above-mentioned underfill material.
  • a silica filler is added to the resin system for the purpose of reducing the linear expansion coefficient of the above-mentioned underfill material.
  • the fluidity of the underfill material deteriorates.
  • it is considered that the dispersion state of the resin component and the silica filler in the underfill material is not uniform.
  • Patent Documents 1 and 2 For the purpose of improving the deterioration of fluidity of the underfill material when this silica filler is added, a sealing epoxy resin composition containing a phosphoric ester has been reported (Patent Documents 1 and 2).
  • An object of the present invention is to provide a liquid epoxy resin composition having a long pot life due to good fluidity of the epoxy resin composition even when it contains an inorganic filler, and suppressing thickening during storage.
  • This invention relates to the liquid epoxy resin composition which solved the said problem by having the following structures.
  • [1] Including (A) liquid epoxy resin, (B) amine compound epoxy adduct curing agent or microencapsulated imidazole compound curing agent, (C) inorganic filler, (D) triisopropyl borate and (E) phenol resin , Liquid epoxy resin composition: The component (C) is 20 to 65 parts by mass, the component (D) is 0.02 to 0.30 parts by mass, and the component (E) is 0.1 parts per 100 parts by mass.
  • a liquid epoxy resin composition characterized by having a viscosity of 3 to 15.0.
  • An underfill material comprising the liquid epoxy resin composition according to [1].
  • [3] An adhesive comprising the liquid epoxy resin composition according to [1].
  • [4] A semiconductor device comprising a cured product of the underfill material according to [2].
  • [5] A semiconductor device comprising a cured product of the adhesive according to [3].
  • a highly reliable semiconductor device can be obtained by an appropriate thermal expansion coefficient of a cured epoxy resin composition containing an inorganic filler.
  • the liquid epoxy resin composition of the present invention includes (A) a liquid epoxy resin, (B) an amine compound epoxy adduct curing agent or a microencapsulated imidazole compound curing agent, (C) an inorganic filler, (D) including triisopropyl borate and (E) phenolic resin, Liquid epoxy resin composition:
  • the component (C) is 20 to 65 parts by mass, the component (D) is 0.02 to 0.15 parts by mass, and the component (E) is 0.1. It is 3 to 15.0.
  • Component (A) imparts adhesiveness and curability to the resin composition, and imparts durability and heat resistance to the cured resin composition.
  • component (A) liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, liquid naphthalene type epoxy resin, liquid aminophenol type epoxy resin, liquid hydrogenated bisphenol type epoxy resin, liquid alicyclic epoxy resin, liquid Examples include alcohol ether type epoxy resin, liquid cycloaliphatic type epoxy resin, liquid fluorene type epoxy resin, liquid siloxane type epoxy resin, etc., liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, liquid naphthalene type epoxy resin From the viewpoints of adhesiveness, curability, durability, and heat resistance.
  • the epoxy equivalent is preferably 80 to 250 g / eq from the viewpoint of viscosity adjustment.
  • Commercially available products include Nippon Steel Chemical's bisphenol F type epoxy resin (product name: YDF8170), DIC's bisphenol A type epoxy resin (product name: EXA-850CRP), and Nippon Steel Chemical's bisphenol F type epoxy resin (product name: YDF870GS). ), DIC naphthalene type epoxy resin (product name: HP4032D), Mitsubishi Chemical aminophenol type epoxy resin (grade: JER630, JER630LSD), Momentive Performance siloxane epoxy resin (product name: TSL9906), Nippon Steel Chemical Co., Ltd. Examples thereof include 1,4-cyclohexanedimethanol diglycidyl ether (product name: ZX1658GS) and the like.
  • a component may be individual or may use 2 or more types together.
  • the component can be cured at a low temperature of about 80 to 100 ° C.
  • the epoxy adduct of the amine compound (B) is a compound having an amino group synthesized by a reaction between the amine compound and the epoxy resin.
  • the amine compound is not particularly limited as long as it has at least one active hydrogen capable of addition reaction with an epoxy group in the molecule.
  • amine compounds include aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4′-diamino-dicyclohexylmethane; 4,4′-diaminodiphenylmethane
  • Aromatic amine compounds such as 2-methylaniline; imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole; imidazoline compounds such as imidazoline, 2-methylimidazoline, 2-ethylimidazoline, etc. Can be mentioned.
  • Examples of the epoxy compound include 1,2-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyoctane, styrene oxide, n-butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, glycidyl acetate, and the like. It is done.
  • an imidazole compound curing accelerator microencapsulated with a urethane resin or the like is preferable from the viewpoint of storage stability, and in liquid epoxy resins such as liquid bisphenol A type A microencapsulated imidazole compound accelerator that is dispersed and masterbatched is more preferable from the viewpoint of workability, curing speed, and storage stability.
  • imidazole curing agents examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,4- Diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, And 3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, and the like.
  • component (B) Commercially available products of component (B) include Ajinomoto Fine Techno's Amine Adduct Latent Curing Agent (Product Name: Amicure PN-23, Amicure PN-40), T & K TOKA Latent Curing Agent (Product Name: Fujicure FX-1000). And a microencapsulated imidazole compound latent curing agent (product names: NovaCure HX3941HP, NovaCure HX3088, NovaCure HX3722) manufactured by Asahi Kasei E-Materials.
  • a component may be individual or may use 2 or more types together.
  • the linear expansion coefficient of the resin composition can be controlled by the component (C).
  • the component (C) include silica fillers such as colloidal silica, hydrophobic silica, fine silica, and nano silica, acrylic beads, glass beads, urethane beads, bentonite, acetylene black, and ketjen black.
  • the average particle diameter of component (C) (or the average maximum diameter if not granular) is not particularly limited, but is 0.01 to 50 ⁇ m to uniformly disperse the filler in the resin composition.
  • the average particle size of the component (C) is more preferably 0.6 to 10 ⁇ m.
  • a component may be individual or may use 2 or more types together.
  • (D) component is represented by chemical formula (1):
  • Triisopropyl borate represented by the formula, the wettability between the resin component and the silica filler in the resin composition is improved, the dispersion state of the resin component and the silica filler is improved, and the liquid epoxy resin composition It can suppress thickening during storage and prolong pot life.
  • the component (D) for example, a reagent commercially available from Wako Pure Chemical Industries may be used.
  • the phenol resin used as the component (E) acts as a curing retarder when contained in a specific amount in the resin composition.
  • the phenol resin include phenol novolac, cresol novolac, and allylphenol. Phenol novolac is preferred because it is liquid at 20 ° C.
  • Meiwa Kasei phenol novolak product name: MEH8005
  • the component (B) is preferably 5 to 35 parts by mass and more preferably 7 to 30 parts by mass with respect to 100 parts by mass of the resin composition from the viewpoint of good reactivity and reliability.
  • the component (C) is 20 to 65 parts by mass, preferably 30 to 60 parts by mass, and more preferably 30 to 40 parts by mass with respect to 100 parts by mass of the resin composition.
  • the content is 30 to 40 parts by mass, the linear expansion coefficient can be lowered and the deterioration of the injection property can be avoided.
  • the component (C) is 20 to 65 parts by mass, preferably 30 to 60 parts by mass, more preferably 30 to 40 parts by mass with respect to 100 parts by mass of the cured product of the resin composition. .
  • the resin composition has a small mass loss upon curing of about 1 to 2% by mass, the preferable content of the component (C) in the cured product is the same as the content in the resin composition. is there.
  • the quantitative analysis of the component (C) is performed by mass spectrometry.
  • Component (D) is 0.02 to 0.30 parts by mass, preferably 0.02 to 0.15 parts by mass, and 0.02 to 0.06 parts per 100 parts by mass of the resin composition. It is more preferable that it is a mass part. When it is 0.02 part by mass or more, the injectability is good, and when it is 0.30 part by mass or less, the strength of the resin composition after curing is sufficient.
  • the component (D) is 0.02 to 0.30 parts by mass, preferably 0.02 to 0.15 parts by mass, with respect to 100 parts by mass of the cured resin composition. It is more preferable that the amount be 02 to 0.06 parts by mass.
  • the quantitative analysis of the component (D) is performed by mass spectrometry.
  • the component (E) is preferably 0.3 to 15.0 parts by mass with respect to 100 parts by mass of the resin composition.
  • the component (E) is less than 0.3 parts by mass, appearance defects such as color unevenness occur in the cured resin composition, and when it exceeds 15 parts by mass, the curability deteriorates and the curing takes place in the required time. Since it is insufficient, the strength of the resin composition after curing is reduced.
  • the component (E) is preferably 0.3 to 15.0 parts by mass with respect to 100 parts by mass of the cured resin composition.
  • the quantitative analysis of the component (E) is performed by mass spectrometry.
  • the resin composition preferably further contains a coupling agent as component (F) from the viewpoint of adhesion.
  • component (F) include 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxy Silane, vinyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (Triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane and the like are mentioned, and 3-glycidoxypropyltrimethoxysilane and 3-aminopropyltrimethoxysilane are preferable from the viewpoint of adhesion.
  • Examples of commercially available products include KBM403, KBE903, and KBE
  • the component (F) is preferably contained in an amount of 0.05 to 15 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition. Adhesiveness improves that it is 0.05 mass part or more, and foaming of a resin composition is suppressed as it is 15 mass parts or less.
  • a leveling agent, a colorant, an ion trapping agent, an antifoaming agent, a flame retardant, other additives, etc. are further blended as necessary within the range not impairing the object of the present invention. Can do.
  • the resin composition of the present invention can be obtained, for example, by stirring, melting, mixing, and dispersing components (A) to (E) and other additives simultaneously or separately, with heat treatment as necessary. Can do.
  • the mixing, stirring, dispersing and the like devices are not particularly limited, and a raikai machine equipped with a stirring and heating device, a three-roll mill, a ball mill, a planetary mixer, a bead mill and the like can be used. . Moreover, you may use combining these apparatuses suitably.
  • the resin composition of the present invention preferably has a viscosity at a temperature of 25 ° C. of 1000 to 80,000 mPa ⁇ s from the viewpoint of injectability.
  • the viscosity is measured with an E-type viscometer (model number: TVE-22H) manufactured by Toki Sangyo Co., Ltd.
  • the resin composition of the present invention is formed and applied at a desired position of an electronic component such as a substrate or an optical semiconductor by a dispenser, printing or the like.
  • an electronic component such as a substrate or an optical semiconductor
  • a dispenser printing or the like.
  • the resin composition is used as an underfill material, it is formed between a substrate such as a flexible wiring substrate and a semiconductor element so that at least a part thereof is in contact with the wiring of the substrate.
  • the curing of the resin composition of the present invention is preferably 80 to 300 ° C., and curing within 200 seconds is preferable from the viewpoint of improving productivity.
  • the resin composition of the present invention is suitable as an adhesive for electronic parts such as underfill materials and optical semiconductors.
  • a semiconductor device including a cured product of an underfill material or a cured product of an adhesive is highly reliable because the inorganic filler is uniformly dispersed.
  • the viscosity of the resin composition immediately after production (hereinafter referred to as initial viscosity, unit: mPa ⁇ s) was measured under the condition of 10 revolutions per minute using a Toki Sangyo E-type viscometer (model number: TVE-22H). It was measured.
  • the initial viscosity is preferably 1000 to 80000 mPa ⁇ s, more preferably 1000 to 8000 mPa ⁇ s.
  • maintaining a resin composition at 25 degreeC for 48 hours was measured similarly, and the viscosity increase rate (unit:%) was computed.
  • Viscosity increase rate [(viscosity after 48 hours) ⁇ (initial viscosity)] / (initial viscosity) ⁇ 100 Calculated with Tables 1 to 4 show the measurement results.
  • the variation index of the resin composition was measured using an E-type viscometer (model number: TVE-22H) manufactured by Toki Sangyo Co., Ltd.
  • the tremor index is a ratio obtained by dividing the measured value obtained under the condition of 1 revolution per minute by the measured value obtained under the condition of 10 revolutions per minute, that is, (viscosity at 1 revolution per minute) / (every time. (Viscosity at 10 revolutions per minute).
  • An appropriate range of the thymometric index is 0.8 to 1.0. Tables 1 to 4 show the measurement results.
  • FIG. 1 the schematic diagram explaining the evaluation method of the injectability of a resin composition is shown.
  • a test piece was prepared in which a gap 40 of 50 ⁇ m was provided on a substrate 20 and a glass plate 30 was fixed instead of a semiconductor element.
  • a glass plate 30 was fixed instead of a semiconductor element.
  • an FR4 substrate was used as the substrate 20.
  • this test piece is placed on a hot plate set to 50 ° C., and the produced resin composition 10 is applied to one end side of the glass plate 30 as shown in FIG. ), The time until the gap 40 was filled with the resin composition 11 was measured.
  • the appropriate range of injection time is within 1000 seconds.
  • Tables 1 to 4 show the injectability evaluation results.
  • Comparative Example 2 The comparative example 2 with too few components had a high change index. Further, Comparative Example 3 having too much component (D) was not cured even at 100 ° C. for 90 minutes. In Comparative Example 4 having too much component (C), the viscosity was too high to be measured. The comparative example 5 which does not contain the (B) component solidified during the thickening test. In Comparative Example 6 in which the amount of the component (E) is too small, poor appearance due to uneven color occurred. Comparative Example 7 having too much (E) component had a high initial viscosity and a high viscosity increase rate, and was uncured at 80 ° C. for 90 minutes.
  • the viscosity increase rate was too high.
  • Comparative Example 13 had a high fluctuation index, and the injection test was terminated midway.
  • Comparative Examples 18 and 20 using a curing agent in place of the component (B) the rate of increase in viscosity was too high and did not cure even at 100 ° C. for 90 minutes.
  • the comparative example 19 with too much (E) component also had a too high viscosity increase rate, and did not harden
  • the resin composition of the present invention has good fluidity even if it contains an inorganic filler, and can suppress the thickening of the resin composition during storage, thereby prolonging the pot life.
  • the resin composition of the present invention is particularly useful as an underfill material or an adhesive for electronic parts.

Landscapes

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

Abstract

The purpose of the present invention is to provide a liquid epoxy resin composition which exhibits good fluidity even if an inorganic filler is contained therein and has a long pot life by being suppressed in increase in viscosity during storage. A liquid epoxy resin composition which is characterized by containing (A) a liquid epoxy resin, (B) an epoxy adduct curing agent of an amine compound, (C) an inorganic filler, (D) triisopropyl borate and (E) a phenolic resin. This liquid epoxy resin composition is also characterized in that 20-65 parts by mass of the component (C), 0.02-0.15 part by mass of the component (D) and 0.3-15.0 parts by mass of the component (E) are contained per 100 parts by mass of the liquid epoxy resin composition.

Description

液状エポキシ樹脂組成物Liquid epoxy resin composition
　本発明は、液状エポキシ樹脂組成物に関し、特に、流動性に優れ、かつ低線膨張係数であることを特徴としたアンダーフィル材や電子部品用接着剤として使用可能な液状エポキシ樹脂組成物に関する。 The present invention relates to a liquid epoxy resin composition, and in particular, to a liquid epoxy resin composition that is excellent in fluidity and has a low linear expansion coefficient and can be used as an adhesive for an underfill material or electronic component.
　近年、電子機器のさらなる配線等の高密度化、高周波化に対応可能な半導体チップの実装方式として、フリップチップボンディングが利用されている。フリップチップ実装では、半導体チップと基板を直接接続するため、シリコンチップと基板の線膨張係数の違いに起因する応力により、接続部にクラックが発生するおそれがあり、接続信頼性不良の原因となる。その対策として、アンダーフィル材と呼ばれる液状封止材を半導体チップと配線基板の間に充填する技術が用いられている。アンダーフィル材を用いることにより、ヒートサイクル等の熱的応力に対する接続信頼性、及び、衝撃や折り曲げ等の物理的応力に対する接続信頼性を向上することが可能となる。 In recent years, flip-chip bonding has been used as a semiconductor chip mounting method that can cope with higher wiring density and higher frequency of electronic devices. In flip chip mounting, since the semiconductor chip and the substrate are directly connected, the stress caused by the difference in the linear expansion coefficient between the silicon chip and the substrate may cause cracks in the connection portion, resulting in poor connection reliability. . As a countermeasure, a technique of filling a liquid sealing material called an underfill material between a semiconductor chip and a wiring board is used. By using the underfill material, it is possible to improve connection reliability against thermal stress such as heat cycle and connection reliability against physical stress such as impact and bending.
　ここで、シリコンチップの線膨張係数は４ｐｐｍ／℃であり、基板、例えば、ガラスエポキシ基板の線膨張係数は２０ｐｐｍ／℃である。アンダーフィル材は、一般に、この線膨張係数の差を吸収するために無機フィラーを混合しており、無機フィラーとしては、シリカフィラーが、通常用いられている。 Here, the linear expansion coefficient of the silicon chip is 4 ppm / ° C., and the linear expansion coefficient of the substrate, for example, a glass epoxy substrate, is 20 ppm / ° C. In general, the underfill material is mixed with an inorganic filler in order to absorb the difference in linear expansion coefficient, and a silica filler is usually used as the inorganic filler.
　また、アンダーフィル材には、低温硬化可能な樹脂として、エポキシ－イミダゾール硬化系が使用されているが、この樹脂系に、上述のアンダーフィル材の線膨張係数を下げる目的でシリカフィラーを添加した際に、アンダーフィル材の流動性が劣化する、という問題がある。この流動性劣化の原因としては、アンダーフィル材中での樹脂成分とシリカフィラーとの分散状態が不均一であることが考えられる。 The underfill material uses an epoxy-imidazole curing system as a low-temperature curable resin, and a silica filler is added to the resin system for the purpose of reducing the linear expansion coefficient of the above-mentioned underfill material. However, there is a problem that the fluidity of the underfill material deteriorates. As a cause of this fluidity deterioration, it is considered that the dispersion state of the resin component and the silica filler in the underfill material is not uniform.
　このシリカフィラーを添加した際のアンダーフィル材の流動性の劣化改善を目的として、リン酸エステルを含有する封止用エポキシ樹脂組成物が報告されている（特許文献１、特許文献２）。 For the purpose of improving the deterioration of fluidity of the underfill material when this silica filler is added, a sealing epoxy resin composition containing a phosphoric ester has been reported (Patent Documents 1 and 2).
特開２００３－２８９１２３号公報JP 2003-289123 A 特開２０１１－２４６５４５号公報JP 2011-246545 A
　しかしながら、エポキシ樹脂組成物にリン酸エステルを含有させると、エポキシ樹脂組成物の保存中での粘度上昇が大きくなり、ポットライフが短くなる、という問題がある。このシリカフィラーを添加したエポキシ樹脂組成物でのポットライフに関する問題は、アンダーフィル材用途以外の光半導体等の電子部品用の接着剤として使用するときにも問題となる。 However, when a phosphoric acid ester is contained in the epoxy resin composition, there is a problem that the increase in viscosity during storage of the epoxy resin composition is increased and the pot life is shortened. The problem regarding the pot life in the epoxy resin composition to which the silica filler is added also becomes a problem when used as an adhesive for electronic components such as optical semiconductors other than underfill materials.
　本発明は、無機フィラーを含有していてもエポキシ樹脂組成物の流動性が良く、また、保存中での増粘抑制によりポットライフが長い液状エポキシ樹脂組成物を提供することを目的とする。 An object of the present invention is to provide a liquid epoxy resin composition having a long pot life due to good fluidity of the epoxy resin composition even when it contains an inorganic filler, and suppressing thickening during storage.
　本発明は、以下の構成を有することによって上記問題を解決した液状エポキシ樹脂組成物に関する。
〔１〕（Ａ）液状エポキシ樹脂、（Ｂ）アミン化合物のエポキシアダクト硬化剤またはマイクロカプセル化イミダゾール化合物硬化剤、（Ｃ）無機フィラー、（Ｄ）ホウ酸トリイソプロピルおよび（Ｅ）フェノール樹脂を含み、
液状エポキシ樹脂組成物：１００質量部に対して、（Ｃ）成分が２０～６５質量部であり、（Ｄ）成分が０．０２～０．３０質量部であり、（Ｅ）成分が０．３～１５．０であることを特徴とする、液状エポキシ樹脂組成物。
〔２〕上記〔１〕記載の液状エポキシ樹脂組成物を含む、アンダーフィル材。
〔３〕上記〔１〕記載の液状エポキシ樹脂組成物を含む、接着剤。
〔４〕上記〔２〕記載のアンダーフィル材の硬化物を含む、半導体装置。
〔５〕上記〔３〕記載の接着剤の硬化物を含む、半導体装置。 This invention relates to the liquid epoxy resin composition which solved the said problem by having the following structures.
[1] Including (A) liquid epoxy resin, (B) amine compound epoxy adduct curing agent or microencapsulated imidazole compound curing agent, (C) inorganic filler, (D) triisopropyl borate and (E) phenol resin ,
Liquid epoxy resin composition: The component (C) is 20 to 65 parts by mass, the component (D) is 0.02 to 0.30 parts by mass, and the component (E) is 0.1 parts per 100 parts by mass. A liquid epoxy resin composition characterized by having a viscosity of 3 to 15.0.
[2] An underfill material comprising the liquid epoxy resin composition according to [1].
[3] An adhesive comprising the liquid epoxy resin composition according to [1].
[4] A semiconductor device comprising a cured product of the underfill material according to [2].
[5] A semiconductor device comprising a cured product of the adhesive according to [3].
　本発明〔１〕によれば、無機フィラーを含有していても流動性が良く、かつ保存中の増粘の抑制によりポットライフが長い液状エポキシ樹脂組成物を提供することができる。 According to the present invention [1], it is possible to provide a liquid epoxy resin composition having a good potability even when an inorganic filler is contained, and having a long pot life by suppressing thickening during storage.
　本発明〔４〕および〔５〕によれば、無機フィラーを含有する硬化したエポキシ樹脂組成物の適度な熱膨張係数により、高信頼性の半導体装置を得ることができる。 According to the present invention [4] and [5], a highly reliable semiconductor device can be obtained by an appropriate thermal expansion coefficient of a cured epoxy resin composition containing an inorganic filler.
液状エポキシ樹脂組成物の注入性の評価方法を説明する模式図である。It is a schematic diagram explaining the injection | pouring property evaluation method of a liquid epoxy resin composition.
　本発明の液状エポキシ樹脂組成物（以下、樹脂組成物という）は、（Ａ）液状エポキシ樹脂、（Ｂ）アミン化合物のエポキシアダクト硬化剤またはマイクロカプセル化イミダゾール化合物硬化剤、（Ｃ）無機フィラー、（Ｄ）ホウ酸トリイソプロピルおよび（Ｅ）フェノール樹脂を含み、
液状エポキシ樹脂組成物：１００質量部に対して、（Ｃ）成分が２０～６５質量部であり、（Ｄ）成分が０．０２～０．１５質量部であり、（Ｅ）成分が０．３～１５．０であることを特徴とする。 The liquid epoxy resin composition of the present invention (hereinafter referred to as resin composition) includes (A) a liquid epoxy resin, (B) an amine compound epoxy adduct curing agent or a microencapsulated imidazole compound curing agent, (C) an inorganic filler, (D) including triisopropyl borate and (E) phenolic resin,
Liquid epoxy resin composition: The component (C) is 20 to 65 parts by mass, the component (D) is 0.02 to 0.15 parts by mass, and the component (E) is 0.1. It is 3 to 15.0.
　（Ａ）成分は、樹脂組成物に、接着性、硬化性を付与し、硬化後の樹脂組成物に、耐久性、耐熱性を付与する。（Ａ）成分としては、液状ビスフェノールＡ型エポキシ樹脂、液状ビスフェノールＦ型エポキシ樹脂、液状ナフタレン型エポキシ樹脂、液状アミノフェノール型エポキシ樹脂、液状水添ビスフェノール型エポキシ樹脂、液状脂環式エポキシ樹脂、液状アルコールエーテル型エポキシ樹脂、液状環状脂肪族型エポキシ樹脂、液状フルオレン型エポキシ樹脂、液状シロキサン系エポキシ樹脂等が挙げられ、液状ビスフェノールＡ型エポキシ樹脂、液状ビスフェノールＦ型エポキシ樹脂、液状ナフタレン型エポキシ樹脂が、接着性、硬化性、耐久性、耐熱性の観点から好ましい。また、エポキシ当量は、粘度調整の観点から、８０～２５０ｇ／ｅｑが好ましい。市販品としては、新日鐵化学製ビスフェノールＦ型エポキシ樹脂（品名：ＹＤＦ８１７０）、ＤＩＣ製ビスフェノールＡ型エポキシ樹脂（品名：ＥＸＡ－８５０ＣＲＰ）、新日鐵化学製ビスフェノールＦ型エポキシ樹脂（品名：ＹＤＦ８７０ＧＳ）、ＤＩＣ製ナフタレン型エポキシ樹脂（品名：ＨＰ４０３２Ｄ）、三菱化学製アミノフェノール型エポキシ樹脂（グレード：ＪＥＲ６３０、ＪＥＲ６３０ＬＳＤ）、モメンティブ・パフォーマンス製シロキサン系エポキシ樹脂（品名：ＴＳＬ９９０６）、新日鐵化学株式会社製１，４－シクロヘキサンジメタノールジグリシジルエーテル（品名：ＺＸ１６５８ＧＳ）等が挙げられる。（Ａ）成分は、単独でも２種以上を併用してもよい。 Component (A) imparts adhesiveness and curability to the resin composition, and imparts durability and heat resistance to the cured resin composition. As component (A), liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, liquid naphthalene type epoxy resin, liquid aminophenol type epoxy resin, liquid hydrogenated bisphenol type epoxy resin, liquid alicyclic epoxy resin, liquid Examples include alcohol ether type epoxy resin, liquid cycloaliphatic type epoxy resin, liquid fluorene type epoxy resin, liquid siloxane type epoxy resin, etc., liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, liquid naphthalene type epoxy resin From the viewpoints of adhesiveness, curability, durability, and heat resistance. The epoxy equivalent is preferably 80 to 250 g / eq from the viewpoint of viscosity adjustment. Commercially available products include Nippon Steel Chemical's bisphenol F type epoxy resin (product name: YDF8170), DIC's bisphenol A type epoxy resin (product name: EXA-850CRP), and Nippon Steel Chemical's bisphenol F type epoxy resin (product name: YDF870GS). ), DIC naphthalene type epoxy resin (product name: HP4032D), Mitsubishi Chemical aminophenol type epoxy resin (grade: JER630, JER630LSD), Momentive Performance siloxane epoxy resin (product name: TSL9906), Nippon Steel Chemical Co., Ltd. Examples thereof include 1,4-cyclohexanedimethanol diglycidyl ether (product name: ZX1658GS) and the like. (A) A component may be individual or may use 2 or more types together.
　（Ｂ）成分は、８０～１００℃程度の低温での硬化を可能にする。（Ｂ）成分のアミン化合物のエポキシアダクトは、アミン化合物とエポキシ樹脂との反応により合成されるアミノ基を有する化合物である。 (B) The component can be cured at a low temperature of about 80 to 100 ° C. The epoxy adduct of the amine compound (B) is a compound having an amino group synthesized by a reaction between the amine compound and the epoxy resin.
　アミン化合物としては、エポキシ基と付加反応しうる活性水素を分子内に１個以上有するものであればよく、特に限定されない。アミン化合物としては、ジエチレントリアミン、トリエチレンテトラミン、ｎ－プロピルアミン、２－ヒドロキシエチルアミノプロピルアミン、シクロヘキシルアミン、４，４'－ジアミノ－ジシクロヘキシルメタン等の脂肪族アミン化合物；４，４'－ジアミノジフェニルメタン、２－メチルアニリン等の芳香族アミン化合物；イミダゾール、２－メチルイミダゾール、２－エチルイミダゾール、２－イソプロピルイミダゾール等のイミダゾール化合物；イミダゾリン、２－メチルイミダゾリン、２－エチルイミダゾリン等のイミダゾリン化合物等が挙げられる。 The amine compound is not particularly limited as long as it has at least one active hydrogen capable of addition reaction with an epoxy group in the molecule. Examples of amine compounds include aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4′-diamino-dicyclohexylmethane; 4,4′-diaminodiphenylmethane Aromatic amine compounds such as 2-methylaniline; imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole; imidazoline compounds such as imidazoline, 2-methylimidazoline, 2-ethylimidazoline, etc. Can be mentioned.
　エポキシ化合物としては、１，２－エポキシブタン、１，２－エポキシへキサン、１，２－エポキシオクタン、スチレンオキシド、ｎ－ブチルグリシジルエーテル、ヘキシルグリシジルエーテル、フェニルグリシジルエーテル、グリシジルアセタート等が挙げられる。 Examples of the epoxy compound include 1,2-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyoctane, styrene oxide, n-butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, glycidyl acetate, and the like. It is done.
　（Ｂ）成分のマイクロカプセル化イミダゾール化合物硬化剤としては、ウレタン樹脂などでマイクロカプセル化されたイミダゾール化合物硬化促進剤が、保存安定性の観点から好ましく、液状ビスフェノールＡ型等の液状エポキシ樹脂中に分散され、マスターバッチ化された、マイクロカプセル化イミダゾール化合物硬化促進剤が、作業性、硬化速度、保存安定性の点からより好ましい。イミダゾール硬化剤としては、２－メチルイミダゾール、２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、２，４－ジアミノ－６－〔２’－メチルイミダゾリル－（１’）］エチル－ｓ－トリアジン、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール、２，３－ジヒドロ－１Ｈ－ピロロ［１，２－ａ］ベンズイミダゾール等を挙げることができ、２，４－ジアミノ－６－〔２’－メチルイミダゾリル－（１’）］エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－ウンデシルイミダゾリル－（１）－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－エチル－４’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン等が、硬化速度、作業性、耐湿性の観点から好ましい。 As the microencapsulated imidazole compound curing agent of component (B), an imidazole compound curing accelerator microencapsulated with a urethane resin or the like is preferable from the viewpoint of storage stability, and in liquid epoxy resins such as liquid bisphenol A type A microencapsulated imidazole compound accelerator that is dispersed and masterbatched is more preferable from the viewpoint of workability, curing speed, and storage stability. Examples of imidazole curing agents include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,4- Diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, And 3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, and the like. 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 2 , 4-Diamino-6- [2'-undecylimidazolyl- (1) -ethyl-s-triazine, 2, - diamino-6- [2'-ethyl-4'-methylimidazolyl- - (1 ')] - ethyl -s- triazine, and curing rate, workability, preferable from the viewpoint of moisture resistance.
　（Ｂ）成分の市販品としては、味の素ファインテクノ製アミンアダクト系潜在性硬化剤（品名：アミキュアＰＮ－２３、アミキュアＰＮ－４０）、Ｔ＆Ｋ　ＴＯＫＡ製潜在性硬化剤（品名：フジキュアーＦＸ－１０００）、旭化成イーマテリアルズ製マイクロカプセル化イミダゾール化合物潜在性硬化剤（製品名：ノバキュアＨＸ３９４１ＨＰ、ノバキュアＨＸ３０８８、ノバキュアＨＸ３７２２）が挙げられる。（Ｂ）成分は、単独でも２種以上を併用してもよい。 Commercially available products of component (B) include Ajinomoto Fine Techno's Amine Adduct Latent Curing Agent (Product Name: Amicure PN-23, Amicure PN-40), T & K TOKA Latent Curing Agent (Product Name: Fujicure FX-1000). And a microencapsulated imidazole compound latent curing agent (product names: NovaCure HX3941HP, NovaCure HX3088, NovaCure HX3722) manufactured by Asahi Kasei E-Materials. (B) A component may be individual or may use 2 or more types together.
　（Ｃ）成分により、樹脂組成物の線膨張係数を制御することができる。（Ｃ）成分としては、コロイダルシリカ、疎水性シリカ、微細シリカ、ナノシリカ等のシリカフィラー、アクリルビーズ、ガラスビーズ、ウレタンビーズ、ベントナイト、アセチレンブラック、ケッチェンブラック等が挙げられる。また、（Ｃ）成分の平均粒径（粒状でない場合は、その平均最大径）は、特に限定されないが、０．０１～５０μｍであることが、樹脂組成物中に充填剤を均一に分散させるうえで好ましく、また、樹脂組成物をアンダーフィル材として使用した際の注入性に優れる等の理由から好ましい。０．０１μｍ未満だと、樹脂組成物の粘度が上昇して、アンダーフィル材として使用した際に注入性が悪化するおそれがある。５０μｍ超だと、樹脂組成物中に充填剤を均一に分散させることが困難になるおそれがある。また、硬化後の樹脂組成物の熱ストレスから、銅製ワイヤーを保護する観点から、（Ｃ）成分の平均粒径は、０．６～１０μｍであると、より好ましい。市販品としては、アドマテックス製高純度合成球状シリカ（品名：ＳＯ－Ｅ５、平均粒径：２μｍ；品名：ＳＥ－２３００、平均粒径：０．６μｍ）、龍森製シリカ（品名：ＦＢ７ＳＤＸ、平均粒径：１０μｍ）、マイクロン製シリカ（品名：ＴＳ－１０－０３４Ｐ、平均粒径：２０μｍ）等が挙げられる。ここで、充填剤の平均粒径は、動的光散乱式ナノトラック粒度分析計により測定する。（Ｃ）成分は、単独でも２種以上を併用してもよい。 (C) The linear expansion coefficient of the resin composition can be controlled by the component (C). Examples of the component (C) include silica fillers such as colloidal silica, hydrophobic silica, fine silica, and nano silica, acrylic beads, glass beads, urethane beads, bentonite, acetylene black, and ketjen black. In addition, the average particle diameter of component (C) (or the average maximum diameter if not granular) is not particularly limited, but is 0.01 to 50 μm to uniformly disperse the filler in the resin composition. Moreover, it is preferable for reasons such as excellent injectability when the resin composition is used as an underfill material. When it is less than 0.01 μm, the viscosity of the resin composition increases, and the injectability may deteriorate when used as an underfill material. If it exceeds 50 μm, it may be difficult to uniformly disperse the filler in the resin composition. Further, from the viewpoint of protecting the copper wire from the heat stress of the cured resin composition, the average particle size of the component (C) is more preferably 0.6 to 10 μm. Commercially available products include high purity synthetic spherical silica manufactured by Admatechs (product name: SO-E5, average particle size: 2 μm; product name: SE-2300, average particle size: 0.6 μm), Tatsumori silica (product name: FB7SDX, Average particle size: 10 μm), Micron silica (product name: TS-10-034P, average particle size: 20 μm), and the like. Here, the average particle diameter of the filler is measured by a dynamic light scattering nanotrack particle size analyzer. (C) A component may be individual or may use 2 or more types together.
　（Ｄ）成分は、化学式（１）： (D) component is represented by chemical formula (1):
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
で表されるホウ酸トリイソプロピルであり、樹脂組成物中の樹脂成分とシリカフィラーとの濡れ性を高くし、樹脂成分とシリカフィラーとの分散状態を改善させ、かつ、液状エポキシ樹脂組成物の保存中の増粘を抑制し、ポットライフを長くすることができる。（Ｄ）成分は、例えば、和光純薬工業から市販されている試薬を使用すればよい。 Triisopropyl borate represented by the formula, the wettability between the resin component and the silica filler in the resin composition is improved, the dispersion state of the resin component and the silica filler is improved, and the liquid epoxy resin composition It can suppress thickening during storage and prolong pot life. As the component (D), for example, a reagent commercially available from Wako Pure Chemical Industries may be used.
　（Ｅ）成分は、エポキシ樹脂組成物の保存中での増粘を抑制する。（Ｅ）成分として使用されるフェノール樹脂は、樹脂組成物中で特定量含有されることにより、硬化遅延剤として作用する。フェノール樹脂としては、フェノールノボラック、クレゾールノボラック、アリルフェノール等が挙げられる。２０℃で液状であるので、フェノールノボラックが好ましい。市販品としては、明和化成製フェノールノボラック（品名：ＭＥＨ８００５）が挙げられる。 (E) component suppresses thickening of the epoxy resin composition during storage. The phenol resin used as the component (E) acts as a curing retarder when contained in a specific amount in the resin composition. Examples of the phenol resin include phenol novolac, cresol novolac, and allylphenol. Phenol novolac is preferred because it is liquid at 20 ° C. As a commercial item, Meiwa Kasei phenol novolak (product name: MEH8005) is mentioned.
　（Ｂ）成分は、良好な反応性、信頼性の観点から、樹脂組成物：１００質量部に対して、５～３５質量部であると好ましく、７～３０質量部であると、より好ましい。 The component (B) is preferably 5 to 35 parts by mass and more preferably 7 to 30 parts by mass with respect to 100 parts by mass of the resin composition from the viewpoint of good reactivity and reliability.
　（Ｃ）成分は、樹脂組成物：１００質量部に対して、２０～６５質量部であり、好ましくは３０～６０質量部、より好ましくは、３０～４０質量部含有される。３０～４０質量部であると、線膨張係数を下げられ、かつ注入性の悪化をさけることができる。 The component (C) is 20 to 65 parts by mass, preferably 30 to 60 parts by mass, and more preferably 30 to 40 parts by mass with respect to 100 parts by mass of the resin composition. When the content is 30 to 40 parts by mass, the linear expansion coefficient can be lowered and the deterioration of the injection property can be avoided.
　また、（Ｃ）成分は、樹脂組成物の硬化物：１００質量部に対して、２０～６５質量部であり、好ましくは３０～６０質量部、より好ましくは、３０～４０質量部含有される。ここで、樹脂組成物は、硬化時の質量減少が約１～２質量％と少ないため、硬化物中での好ましい（Ｃ）成分の含有量は、樹脂組成物中での含有量と同様である。ここで、（Ｃ）成分の定量分析は、質量分析法で行う。 Further, the component (C) is 20 to 65 parts by mass, preferably 30 to 60 parts by mass, more preferably 30 to 40 parts by mass with respect to 100 parts by mass of the cured product of the resin composition. . Here, since the resin composition has a small mass loss upon curing of about 1 to 2% by mass, the preferable content of the component (C) in the cured product is the same as the content in the resin composition. is there. Here, the quantitative analysis of the component (C) is performed by mass spectrometry.
　（Ｄ）成分は、樹脂組成物：１００質量部に対して、０．０２～０．３０質量部であり、０．０２～０．１５質量部であると好ましく、０．０２～０．０６質量部であると、より好ましい。０．０２質量部以上であると、注入性が良好であり、０．３０質量部以下であると、硬化後の樹脂組成物の強度が十分である。 Component (D) is 0.02 to 0.30 parts by mass, preferably 0.02 to 0.15 parts by mass, and 0.02 to 0.06 parts per 100 parts by mass of the resin composition. It is more preferable that it is a mass part. When it is 0.02 part by mass or more, the injectability is good, and when it is 0.30 part by mass or less, the strength of the resin composition after curing is sufficient.
　また、（Ｄ）成分は、樹脂組成物の硬化物：１００質量部に対して、０．０２～０．３０質量部であり、０．０２～０．１５質量部であると好ましく、０．０２～０．０６質量部であると、より好ましい。ここで、（Ｄ）成分の定量分析は、質量分析法で行う。 The component (D) is 0.02 to 0.30 parts by mass, preferably 0.02 to 0.15 parts by mass, with respect to 100 parts by mass of the cured resin composition. It is more preferable that the amount be 02 to 0.06 parts by mass. Here, the quantitative analysis of the component (D) is performed by mass spectrometry.
　（Ｅ）成分は、樹脂組成物：１００質量部に対して、０．３～１５．０質量部であると好ましい。（Ｅ）成分が０．３質量部未満では、硬化後の樹脂組成物に色むら等の外観不良が発生し、１５質量部を超えると、硬化性が低下してしまい、所要時間で硬化が不十分のため、硬化後の樹脂組成物の強度が低下してしまう。 The component (E) is preferably 0.3 to 15.0 parts by mass with respect to 100 parts by mass of the resin composition. When the component (E) is less than 0.3 parts by mass, appearance defects such as color unevenness occur in the cured resin composition, and when it exceeds 15 parts by mass, the curability deteriorates and the curing takes place in the required time. Since it is insufficient, the strength of the resin composition after curing is reduced.
　また、（Ｅ）成分は、樹脂組成物の硬化物：１００質量部に対して、０．３～１５．０質量部であると好ましい。ここで、（Ｅ）成分の定量分析は、質量分析法で行う。 The component (E) is preferably 0.3 to 15.0 parts by mass with respect to 100 parts by mass of the cured resin composition. Here, the quantitative analysis of the component (E) is performed by mass spectrometry.
　樹脂組成物は、さらに、（Ｆ）成分であるカップリング剤を含有すると、密着性の観点から好ましく、（Ｆ）成分としては、３－グリシドキシプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、ビニルトリメトキシシラン、ｐ－スチリルトリメトキシシラン、３－メタクリロキシプロピルメチルトリメトキシシラン、３－アクリロキシプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン、３－メルカプトプロピルトリメトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィド、３－イソシアネートプロピルトリエトキシシラン等が挙げられ、３－グリシドキシプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシランが、密着性の観点から好ましい。市販品としては、信越化学工業製ＫＢＭ４０３、ＫＢＥ９０３、ＫＢＥ９１０３等が挙げられる。（Ｆ）成分は、単独でも２種以上を併用してもよい。 The resin composition preferably further contains a coupling agent as component (F) from the viewpoint of adhesion. Examples of component (F) include 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxy Silane, vinyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (Triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane and the like are mentioned, and 3-glycidoxypropyltrimethoxysilane and 3-aminopropyltrimethoxysilane are preferable from the viewpoint of adhesion. Examples of commercially available products include KBM403, KBE903, and KBE9103 manufactured by Shin-Etsu Chemical. (F) A component may be individual or may use 2 or more types together.
　（Ｆ）成分は、樹脂組成物：１００質量部に対して、好ましくは０．０５～１５質量部、より好ましくは０．１～１０質量部含有される。０．０５質量部以上であると、密着性が向上し、１５質量部以下であると、樹脂組成物の発泡が抑制される。 The component (F) is preferably contained in an amount of 0.05 to 15 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin composition. Adhesiveness improves that it is 0.05 mass part or more, and foaming of a resin composition is suppressed as it is 15 mass parts or less.
　本発明の樹脂組成物には、本発明の目的を損なわない範囲で、更に必要に応じ、レベリング剤、着色剤、イオントラップ剤、消泡剤、難燃剤、その他の添加剤等を配合することができる。 In the resin composition of the present invention, a leveling agent, a colorant, an ion trapping agent, an antifoaming agent, a flame retardant, other additives, etc. are further blended as necessary within the range not impairing the object of the present invention. Can do.
　本発明の樹脂組成物は、例えば、（Ａ）成分～（Ｅ）成分およびその他添加剤等を同時にまたは別々に、必要により加熱処理を加えながら、撹拌、溶融、混合、分散させることにより得ることができる。これらの混合、撹拌、分散等の装置としては、特に限定されるものではないが、撹拌、加熱装置を備えたライカイ機、３本ロールミル、ボールミル、プラネタリーミキサー、ビーズミル等を使用することができる。また、これら装置を適宜組み合わせて使用してもよい。 The resin composition of the present invention can be obtained, for example, by stirring, melting, mixing, and dispersing components (A) to (E) and other additives simultaneously or separately, with heat treatment as necessary. Can do. The mixing, stirring, dispersing and the like devices are not particularly limited, and a raikai machine equipped with a stirring and heating device, a three-roll mill, a ball mill, a planetary mixer, a bead mill and the like can be used. . Moreover, you may use combining these apparatuses suitably.
　本発明の樹脂組成物は、温度：２５℃での粘度が１０００～８００００ｍＰａ・ｓであると、注入性の観点から好ましい。ここで、粘度は、東機産業社製Ｅ型粘度計（型番：ＴＶＥ－２２Ｈ）で測定する。 The resin composition of the present invention preferably has a viscosity at a temperature of 25 ° C. of 1000 to 80,000 mPa · s from the viewpoint of injectability. Here, the viscosity is measured with an E-type viscometer (model number: TVE-22H) manufactured by Toki Sangyo Co., Ltd.
　本発明の樹脂組成物は、ディスペンサー、印刷等で、基板や光半導体等の電子部品の所望の位置に形成・塗布される。ここで、樹脂組成物がアンダーフィル材として使用される場合には、フレキシブル配線基板等の基板と半導体素子との間に、少なくとも一部が基板の配線上に接するように形成する。 The resin composition of the present invention is formed and applied at a desired position of an electronic component such as a substrate or an optical semiconductor by a dispenser, printing or the like. Here, when the resin composition is used as an underfill material, it is formed between a substrate such as a flexible wiring substrate and a semiconductor element so that at least a part thereof is in contact with the wiring of the substrate.
　本発明の樹脂組成物の硬化は、８０～３００℃が好ましく、また、２００秒以内で硬化させると、生産性向上の観点から好ましい。 The curing of the resin composition of the present invention is preferably 80 to 300 ° C., and curing within 200 seconds is preferable from the viewpoint of improving productivity.
　本発明の樹脂組成物は、アンダーフィル材や、光半導体等の電子部品用の接着剤として適している。また、アンダーフィル材の硬化物、または接着剤の硬化物を含む、半導体装置は、無機フィラーが均一に分散されているので、高信頼性である。 The resin composition of the present invention is suitable as an adhesive for electronic parts such as underfill materials and optical semiconductors. In addition, a semiconductor device including a cured product of an underfill material or a cured product of an adhesive is highly reliable because the inorganic filler is uniformly dispersed.
　本発明について、実施例により説明するが、本発明はこれらに限定されるものではない。なお、以下の実施例において、部、％はことわりのない限り、質量部、質量％を示す。 The present invention will be described with reference to examples, but the present invention is not limited thereto. In the following examples, parts and% indicate parts by mass and mass% unless otherwise specified.
〔実施例１～１７、比較例１～２０〕
　表１～表４に示す配合で、樹脂組成物を作製した。作製した樹脂組成物は、すべて液状であった。 [Examples 1 to 17, Comparative Examples 1 to 20]
Resin compositions were prepared with the formulations shown in Tables 1 to 4. The prepared resin compositions were all liquid.
〔粘度の評価〕
　作製した直後の樹脂組成物の粘度（以下、初期粘度という。単位：ｍＰａ・ｓ）を、東機産業社製Ｅ型粘度計（型番：ＴＶＥ－２２Ｈ）を用い、毎分１０回転の条件で測定した。初期粘度は、１０００～８００００ｍＰａ・ｓであると好ましく、１０００～８０００ｍＰａ・ｓであると、より好ましい。また、樹脂組成物を２５℃で４８時間保持した後の粘度も同様に測定し、粘度増加率（単位：％）を算出した。ここで、粘度増加率は、下記式：
　粘度増加率＝〔（４８時間後の粘度）－（初期粘度）〕／（初期粘度）×１００
で算出した。表１～表４に、測定結果を示す。 [Evaluation of viscosity]
The viscosity of the resin composition immediately after production (hereinafter referred to as initial viscosity, unit: mPa · s) was measured under the condition of 10 revolutions per minute using a Toki Sangyo E-type viscometer (model number: TVE-22H). It was measured. The initial viscosity is preferably 1000 to 80000 mPa · s, more preferably 1000 to 8000 mPa · s. Moreover, the viscosity after hold | maintaining a resin composition at 25 degreeC for 48 hours was measured similarly, and the viscosity increase rate (unit:%) was computed. Here, the viscosity increase rate is expressed by the following formula:
Viscosity increase rate = [(viscosity after 48 hours) − (initial viscosity)] / (initial viscosity) × 100
Calculated with Tables 1 to 4 show the measurement results.
〔揺変指数の評価〕
　樹脂組成物の揺変指数を、東機産業社製Ｅ型粘度計（型番：ＴＶＥ－２２Ｈ）を用いて測定した。揺変指数は、毎分１回転の条件で求められた測定値を、毎分１０回転の条件で求められた測定値で除した比率、すなわち、（毎分１回転での粘度）／（毎分１０回転での粘度）がから求めた。揺変指数の適正範囲は、０．８～１．０である。表１～表４に、測定結果を示す。 [Evaluation of tremor index]
The variation index of the resin composition was measured using an E-type viscometer (model number: TVE-22H) manufactured by Toki Sangyo Co., Ltd. The tremor index is a ratio obtained by dividing the measured value obtained under the condition of 1 revolution per minute by the measured value obtained under the condition of 10 revolutions per minute, that is, (viscosity at 1 revolution per minute) / (every time. (Viscosity at 10 revolutions per minute). An appropriate range of the thymometric index is 0.8 to 1.0. Tables 1 to 4 show the measurement results.
〔樹脂組成物の注入性の評価〕
　図１に、樹脂組成物の注入性の評価方法を説明する模式図を示す。まず、図１（Ａ）に示すように、基板２０上に５０μｍのギャップ４０を設けて、半導体素子の代わりにガラス板３０を固定した試験片を作製した。但し、基板２０としては、ＦＲ４基板を使用した。次に、この試験片を５０℃に設定したホットプレート上に置き、図１（Ｂ）に示すように、ガラス板３０の一端側に、作製した樹脂組成物１０を塗布し、図１（Ｃ）に示すように、ギャップ４０が樹脂組成物１１で満たされるまでの時間を測定した。注入時間の適性範囲は、１０００秒以内である。表１～表４に、注入性の評価結果を示す。 [Evaluation of injectability of resin composition]
In FIG. 1, the schematic diagram explaining the evaluation method of the injectability of a resin composition is shown. First, as shown in FIG. 1A, a test piece was prepared in which a gap 40 of 50 μm was provided on a substrate 20 and a glass plate 30 was fixed instead of a semiconductor element. However, as the substrate 20, an FR4 substrate was used. Next, this test piece is placed on a hot plate set to 50 ° C., and the produced resin composition 10 is applied to one end side of the glass plate 30 as shown in FIG. ), The time until the gap 40 was filled with the resin composition 11 was measured. The appropriate range of injection time is within 1000 seconds. Tables 1 to 4 show the injectability evaluation results.
〔硬化物外観〕
　樹脂組成物の注入性の評価した試験片をオーブンへ入れ、１２０℃で３分間加熱し、エポキシ樹脂組成物を硬化させた。加熱後の硬化物外観を目視観察した。硬化物にしわ・柚子肌等の外観不良や色むらが認められなかった場合を○とし、硬化物にしわ・柚子肌等の外観不良や色むらが認められた場合を×とした。表１～表４に、硬化物外観の評価結果を示す。 [Appearance of cured product]
The test piece evaluated for the injectability of the resin composition was placed in an oven and heated at 120 ° C. for 3 minutes to cure the epoxy resin composition. The appearance of the cured product after heating was visually observed. The case where the cured product had no appearance defects or color irregularities such as wrinkles or cocoon skin was rated as “◯”, and the case where the cured product showed poor appearance or color irregularities such as wrinkles or cocoon skin was marked as “X”. Tables 1 to 4 show the evaluation results of the appearance of the cured product.
〔硬化した樹脂組成物の強度評価〕
　ガラスエポキシ基板に評価用試料を印刷し、該試料上に２ｍｍ×２ｍｍのシリコンチップを載置した。これを、８０±２℃の熱風乾燥機で９０分間加熱硬化、または１００±２℃の熱風乾燥機で９０分間加熱硬化させた。これを試験片とし、ｄａｇｅ社製万能型ボンドテスター（型番：ＤＡＧＥ４０００）を用いてシリコンチップに荷重をかけ、チップが剥離した時の強度（剥離強度）を測定した。ｎ＝１０とし、その平均値を強度とした。なお、１００Ｎ未満の場合は、未硬化とした。表１～表４に、強度の評価結果を示す。 [Evaluation of strength of cured resin composition]
An evaluation sample was printed on a glass epoxy substrate, and a 2 mm × 2 mm silicon chip was placed on the sample. This was heat-cured for 90 minutes with a hot air dryer at 80 ± 2 ° C. or heat-cured for 90 minutes with a hot air dryer at 100 ± 2 ° C. Using this as a test piece, a load was applied to the silicon chip using a universal bond tester (model number: DAGE4000) manufactured by dage, and the strength (peeling strength) when the chip peeled was measured. n = 10, and the average value was defined as the strength. In addition, when less than 100N, it was set as uncured. Tables 1 to 4 show the strength evaluation results.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表１～表３からわかるように、実施例１～１７の全てで、初期粘度が使用可能範囲内であり、４８時間後の粘度増加率も４．３％以下であった。揺片指数も所望範囲内であり、注入時間も所望範囲内であった。また、１００℃で硬化し、硬化後の樹脂組成物の強度も良好であった。特に、（Ｄ）成分が０．０２～０．１２質量部の実施例１～４、７～１７は、８０℃の低温でも硬化した。これに対して、（Ｄ）成分を含まない比較例１は、揺変指数が高く、注入試験が途中で終了してしまった。（Ｄ）成分が少なすぎる比較例２は、揺変指数が高かった。さらに、（Ｄ）成分が多すぎる比較例３は、１００℃、９０分でも硬化しなかった。（Ｃ）成分が多すぎる比較例４は、粘度が高すぎて測定できなかった。（Ｂ）成分を含まない比較例５は、増粘試験中に固化した。（Ｅ）成分が少なすぎる比較例６は、色むらによる外観不良が発生した。（Ｅ）成分が多すぎる比較例７は、初期粘度が高めで、粘度増加率が高く、８０℃、９０分で未硬化であった。（Ｄ）成分とは炭素数が異なるホウ酸トリ－ｎ－ヘキサデシルを使用した比較例８～１２は、いずれも揺変指数が高く、注入試験が途中で終了してしまった。表４からわかるように、（Ｄ）成分の代わりにテトラ－ｎ－ブチルホスホニウムベンゾトリアゾレートを使用した比較例１３～１７は、いずれも粘度増加率が高過ぎた。さらに、比較例１３は、揺変指数が高く、注入試験が途中で終了してしまった。（Ｂ）成分の代わりの硬化剤を使用した比較例１８、２０は、粘度増加率が高過ぎ、かつ１００℃×９０分でも硬化しなかった。（Ｅ）成分が多すぎる比較例１９も、粘度増加率が高過ぎ、かつ１００℃×９０分でも硬化しなかった。 As can be seen from Tables 1 to 3, in all of Examples 1 to 17, the initial viscosity was within the usable range, and the rate of increase in viscosity after 48 hours was 4.3% or less. The flicker index was also within the desired range and the injection time was also within the desired range. Moreover, it hardened | cured at 100 degreeC and the intensity | strength of the resin composition after hardening was also favorable. In particular, Examples 1 to 4 and 7 to 17 having a component (D) of 0.02 to 0.12 parts by mass were cured even at a low temperature of 80 ° C. On the other hand, the comparative example 1 which does not contain the (D) component has a high fluctuation index, and the injection | pouring test was complete | finished on the way. (D) The comparative example 2 with too few components had a high change index. Further, Comparative Example 3 having too much component (D) was not cured even at 100 ° C. for 90 minutes. In Comparative Example 4 having too much component (C), the viscosity was too high to be measured. The comparative example 5 which does not contain the (B) component solidified during the thickening test. In Comparative Example 6 in which the amount of the component (E) is too small, poor appearance due to uneven color occurred. Comparative Example 7 having too much (E) component had a high initial viscosity and a high viscosity increase rate, and was uncured at 80 ° C. for 90 minutes. In Comparative Examples 8 to 12 using tri-n-hexadecyl borate having a carbon number different from that of component (D), the thixotropic index was high, and the injection test was terminated halfway. As can be seen from Table 4, in Comparative Examples 13 to 17 in which tetra-n-butylphosphonium benzotriazolate was used instead of the component (D), the viscosity increase rate was too high. Further, Comparative Example 13 had a high fluctuation index, and the injection test was terminated midway. In Comparative Examples 18 and 20 using a curing agent in place of the component (B), the rate of increase in viscosity was too high and did not cure even at 100 ° C. for 90 minutes. The comparative example 19 with too much (E) component also had a too high viscosity increase rate, and did not harden | cure even at 100 degreeC x 90 minutes.
　本発明の樹脂組成物は、無機フィラーを含有していても流動性が良く、かつ樹脂組成物の保存時の増粘を抑制し、ポットライフを長くすることができる。本発明の樹脂組成物は、特に、アンダーフィル材や電子部品用接着剤として有用である。 The resin composition of the present invention has good fluidity even if it contains an inorganic filler, and can suppress the thickening of the resin composition during storage, thereby prolonging the pot life. The resin composition of the present invention is particularly useful as an underfill material or an adhesive for electronic parts.
　　１０　　樹脂組成物
　　２０　　基板
　　３０　　ガラス板
　　４０　　ギャップ 10 resin composition 20 substrate 30 glass plate 40 gap

Claims (5)

  1. 　（Ａ）液状エポキシ樹脂、（Ｂ）アミン化合物のエポキシアダクト硬化剤またはマイクロカプセル化イミダゾール化合物硬化剤、（Ｃ）無機フィラー、（Ｄ）ホウ酸トリイソプロピルおよび（Ｅ）フェノール樹脂を含み、
    液状エポキシ樹脂組成物：１００質量部に対して、（Ｃ）成分が２０～６５質量部であり、（Ｄ）成分が０．０２～０．３０質量部であり、（Ｅ）成分が０．３～１５．０であることを特徴とする、液状エポキシ樹脂組成物。     (A) liquid epoxy resin, (B) amine compound epoxy adduct curing agent or microencapsulated imidazole compound curing agent, (C) inorganic filler, (D) triisopropyl borate and (E) phenol resin,
    Liquid epoxy resin composition: The component (C) is 20 to 65 parts by mass, the component (D) is 0.02 to 0.30 parts by mass, and the component (E) is 0.1 parts per 100 parts by mass. A liquid epoxy resin composition characterized by having a viscosity of 3 to 15.0.
  2. 　請求項１記載の液状エポキシ樹脂組成物を含む、アンダーフィル材。 An underfill material comprising the liquid epoxy resin composition according to claim 1.
  3. 　請求項１記載の液状エポキシ樹脂組成物を含む、接着剤。 An adhesive comprising the liquid epoxy resin composition according to claim 1.
  4. 　請求項２記載のアンダーフィル材の硬化物を含む、半導体装置。 A semiconductor device comprising a cured product of the underfill material according to claim 2.
  5. 　請求項３記載の接着剤の硬化物を含む、半導体装置。 A semiconductor device comprising a cured product of the adhesive according to claim 3.
PCT/JP2013/080870 2012-12-27 2013-11-15 Liquid epoxy resin composition WO2014103552A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020157007533A KR102072259B1 (en) 2012-12-27 2013-11-15 Liquid epoxy resin composition
CN201380051978.4A CN104684957B (en) 2012-12-27 2013-11-15 Liquid epoxy resin composition
PH12015501209A PH12015501209A1 (en) 2012-12-27 2015-05-29 Liqiud epoxy resin composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-286122 2012-12-27
JP2012286122A JP6013906B2 (en) 2012-12-27 2012-12-27 Liquid epoxy resin composition

Publications (1)

Publication Number Publication Date
WO2014103552A1 true WO2014103552A1 (en) 2014-07-03

Family

ID=51020647

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/080870 WO2014103552A1 (en) 2012-12-27 2013-11-15 Liquid epoxy resin composition

Country Status (6)

Country Link
JP (1) JP6013906B2 (en)
KR (1) KR102072259B1 (en)
CN (1) CN104684957B (en)
PH (1) PH12015501209A1 (en)
TW (1) TWI602874B (en)
WO (1) WO2014103552A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018180955A1 (en) * 2017-03-27 2018-10-04 セメダイン株式会社 Low-temperature heat-curable adhesive composition for structure
CN114761459A (en) * 2019-12-12 2022-07-15 松下知识产权经营株式会社 Resin composition for sealing and semiconductor device

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110476243A (en) * 2017-03-31 2019-11-19 日立化成株式会社 The manufacturing method of electronic circuit protection materials, electronic circuit protection materials sealing material, encapsulating method and semiconductor device
JP2020166108A (en) * 2019-03-29 2020-10-08 日東電工株式会社 Optical/electrical composite transmission module
CN114806473A (en) * 2022-04-21 2022-07-29 广东施奈仕实业有限公司 Cold-heat-resistant low-moisture-absorption epoxy underfill adhesive and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11302507A (en) * 1998-02-17 1999-11-02 Toray Ind Inc Epoxy resin composition for fiber-reinforced composite material, intermediate substrate for fiber-reinforced composite material and fiber-reinforced composite material
JP2007246713A (en) * 2006-03-16 2007-09-27 Sumitomo Bakelite Co Ltd One-pack type epoxy resin composition
JP2009084384A (en) * 2007-09-28 2009-04-23 Sumitomo Bakelite Co Ltd One-component epoxy resin composition
JP2011016967A (en) * 2009-07-10 2011-01-27 Panasonic Electric Works Co Ltd Thermosetting resin composition and circuit board

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003289123A (en) 2000-09-25 2003-10-10 Hitachi Chem Co Ltd Use of epoxy resin molding material for sealing
JP2011246545A (en) 2010-05-25 2011-12-08 Hitachi Chem Co Ltd Epoxy resin composition for sealing and electronic part device
JP4965715B1 (en) * 2011-02-03 2012-07-04 ナミックス株式会社 Epoxy resin composition and semiconductor sealing material using the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11302507A (en) * 1998-02-17 1999-11-02 Toray Ind Inc Epoxy resin composition for fiber-reinforced composite material, intermediate substrate for fiber-reinforced composite material and fiber-reinforced composite material
JP2007246713A (en) * 2006-03-16 2007-09-27 Sumitomo Bakelite Co Ltd One-pack type epoxy resin composition
JP2009084384A (en) * 2007-09-28 2009-04-23 Sumitomo Bakelite Co Ltd One-component epoxy resin composition
JP2011016967A (en) * 2009-07-10 2011-01-27 Panasonic Electric Works Co Ltd Thermosetting resin composition and circuit board

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018180955A1 (en) * 2017-03-27 2018-10-04 セメダイン株式会社 Low-temperature heat-curable adhesive composition for structure
JP2018162392A (en) * 2017-03-27 2018-10-18 セメダイン株式会社 Low-temperature heating-curable adhesive composition for structures
RU2727518C1 (en) * 2017-03-27 2020-07-22 Семедин Ко., Лтд. Heat-curable at low temperature adhesive composition for structures
US11680193B2 (en) 2017-03-27 2023-06-20 Cemedine Co., Ltd. Low-temperature heat-curable adhesive composition for structure
CN114761459A (en) * 2019-12-12 2022-07-15 松下知识产权经营株式会社 Resin composition for sealing and semiconductor device

Also Published As

Publication number Publication date
TWI602874B (en) 2017-10-21
CN104684957B (en) 2017-02-22
JP6013906B2 (en) 2016-10-25
KR102072259B1 (en) 2020-01-31
PH12015501209B1 (en) 2015-08-10
CN104684957A (en) 2015-06-03
JP2014125631A (en) 2014-07-07
TW201430043A (en) 2014-08-01
KR20150100609A (en) 2015-09-02
PH12015501209A1 (en) 2015-08-10

Similar Documents

Publication Publication Date Title
JP6534189B2 (en) Resin composition
JP5968137B2 (en) Liquid encapsulant and electronic parts using it
JP6742027B2 (en) Resin composition
JP6013906B2 (en) Liquid epoxy resin composition
CN106687496A (en) Liquid epoxy resin composition, semiconductor sealing agent, semiconductor device, and method for producing liquid epoxy resin composition
JP2023078194A (en) Resin composition and cured material thereof, adhesive agent for electronic component, semiconductor device, as well as electronic component
JP5593259B2 (en) Liquid epoxy resin composition
JP6549555B2 (en) Conductive adhesive and semiconductor device
JP6071612B2 (en) Liquid resin composition, flip chip mounting body and method for producing the same
JP5886051B2 (en) Resin composition
JP5937855B2 (en) Resin composition
JP2013253195A (en) Epoxy resin composition
JPWO2018159564A1 (en) Resin composition
JP5788765B2 (en) Resin composition
JP2013118276A (en) Semiconductor device
JP6758051B2 (en) Liquid epoxy resin compositions, semiconductor encapsulants, and semiconductor devices
JP6653152B2 (en) Epoxy resin composition
JP4906152B1 (en) Liquid resin composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13868632

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20157007533

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 12015501209

Country of ref document: PH

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13868632

Country of ref document: EP

Kind code of ref document: A1