WO2014103552A1 - 液状エポキシ樹脂組成物 - Google Patents
液状エポキシ樹脂組成物 Download PDFInfo
- 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
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- Prior art keywords
- resin composition
- epoxy resin
- component
- mass
- parts
- Prior art date
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Classifications
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- 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
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- 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
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- 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
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- 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
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- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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- 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
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- 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
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- 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
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- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- 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
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
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- 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.
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Abstract
Description
〔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。
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。
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。
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。
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。
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。
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。
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。
20 基板
30 ガラス板
40 ギャップ
Claims (5)
- (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。 - 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。
- 請求項1記載の液状エポキシ樹脂組成物を含む、接着剤。
- 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。
- 請求項3記載の接着剤の硬化物を含む、半導体装置。
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Cited By (2)
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---|---|---|---|---|
WO2018180955A1 (ja) * | 2017-03-27 | 2018-10-04 | セメダイン株式会社 | 低温加熱硬化型構造用接着剤組成物 |
CN114761459A (zh) * | 2019-12-12 | 2022-07-15 | 松下知识产权经营株式会社 | 密封用树脂组合物及半导体装置 |
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MY177304A (en) * | 2017-03-31 | 2020-09-11 | Hitachi Chemical Co Ltd | Protective material for electronic circuit, sealing material for protective material for electronic circuit, sealing method, and method for manufacturing semiconductor device |
JP2020166108A (ja) * | 2019-03-29 | 2020-10-08 | 日東電工株式会社 | 光電気複合伝送モジュール |
CN114806473A (zh) * | 2022-04-21 | 2022-07-29 | 广东施奈仕实业有限公司 | 一种耐冷热低吸湿环氧底部填充胶及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11302507A (ja) * | 1998-02-17 | 1999-11-02 | Toray Ind Inc | 繊維強化複合材料用エポキシ樹脂組成物、繊維強化複合材料用中間基材および繊維強化複合材料 |
JP2007246713A (ja) * | 2006-03-16 | 2007-09-27 | Sumitomo Bakelite Co Ltd | 一液型エポキシ樹脂組成物 |
JP2009084384A (ja) * | 2007-09-28 | 2009-04-23 | Sumitomo Bakelite Co Ltd | 一液型エポキシ樹脂組成物 |
JP2011016967A (ja) * | 2009-07-10 | 2011-01-27 | Panasonic Electric Works Co Ltd | 熱硬化性樹脂組成物及び回路基板 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003289123A (ja) | 2000-09-25 | 2003-10-10 | Hitachi Chem Co Ltd | 封止用エポキシ樹脂成形材料の使用 |
JP2011246545A (ja) | 2010-05-25 | 2011-12-08 | Hitachi Chem Co Ltd | 封止用エポキシ樹脂組成物及び電子部品装置 |
JP4965715B1 (ja) * | 2011-02-03 | 2012-07-04 | ナミックス株式会社 | エポキシ樹脂組成物およびそれを用いた半導体封止材 |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11302507A (ja) * | 1998-02-17 | 1999-11-02 | Toray Ind Inc | 繊維強化複合材料用エポキシ樹脂組成物、繊維強化複合材料用中間基材および繊維強化複合材料 |
JP2007246713A (ja) * | 2006-03-16 | 2007-09-27 | Sumitomo Bakelite Co Ltd | 一液型エポキシ樹脂組成物 |
JP2009084384A (ja) * | 2007-09-28 | 2009-04-23 | Sumitomo Bakelite Co Ltd | 一液型エポキシ樹脂組成物 |
JP2011016967A (ja) * | 2009-07-10 | 2011-01-27 | Panasonic Electric Works Co Ltd | 熱硬化性樹脂組成物及び回路基板 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018180955A1 (ja) * | 2017-03-27 | 2018-10-04 | セメダイン株式会社 | 低温加熱硬化型構造用接着剤組成物 |
JP2018162392A (ja) * | 2017-03-27 | 2018-10-18 | セメダイン株式会社 | 低温加熱硬化型構造用接着剤組成物 |
RU2727518C1 (ru) * | 2017-03-27 | 2020-07-22 | Семедин Ко., Лтд. | Термоотверждаемая при низкой температуре адгезивная композиция для конструкций |
US11680193B2 (en) | 2017-03-27 | 2023-06-20 | Cemedine Co., Ltd. | Low-temperature heat-curable adhesive composition for structure |
CN114761459A (zh) * | 2019-12-12 | 2022-07-15 | 松下知识产权经营株式会社 | 密封用树脂组合物及半导体装置 |
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JP2014125631A (ja) | 2014-07-07 |
TW201430043A (zh) | 2014-08-01 |
CN104684957B (zh) | 2017-02-22 |
JP6013906B2 (ja) | 2016-10-25 |
KR102072259B1 (ko) | 2020-01-31 |
PH12015501209A1 (en) | 2015-08-10 |
TWI602874B (zh) | 2017-10-21 |
KR20150100609A (ko) | 2015-09-02 |
CN104684957A (zh) | 2015-06-03 |
PH12015501209B1 (en) | 2015-08-10 |
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