CN108137904B - Resin composition for underfill, electronic component device, and method for manufacturing electronic component device - Google Patents

Resin composition for underfill, electronic component device, and method for manufacturing electronic component device Download PDF

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CN108137904B
CN108137904B CN201680057967.0A CN201680057967A CN108137904B CN 108137904 B CN108137904 B CN 108137904B CN 201680057967 A CN201680057967 A CN 201680057967A CN 108137904 B CN108137904 B CN 108137904B
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resin composition
underfill
epoxy resin
electronic component
compound
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CN108137904A (en
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出口央视
堀浩士
野尻直幸
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Lishennoco Co ltd
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Showa Denko KK
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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
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Polymerisation Methods In General (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)

Abstract

Provided are an underfill resin composition having excellent flowability, filling properties, moldability, temperature cycle resistance and moisture resistance, an electronic component device sealed at least partially with the underfill resin composition and having high reliability, and a method for manufacturing the electronic component device. Specifically, the resin composition for underfill contains (a) an epoxy resin, (B) an aromatic amine compound, (C) an inorganic filler, and (D) an organic phosphorus compound.

Description

Resin composition for underfill, electronic component device, and method for manufacturing electronic component device
Technical Field
The invention relates to a resin composition for underfill, an electronic component device, and a method for manufacturing the electronic component device.
Background
Conventionally, in the field of sealing semiconductor devices (hereinafter, also referred to as chips) of electronic component devices such as transistors and ICs, resin sealing has become mainstream from the viewpoints of productivity, cost, and the like, and various resin compositions have been applied as sealing materials. Among them, resin compositions containing epoxy resins are widely used. This is because epoxy resins are excellent in balance among properties required for sealing materials, such as workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesiveness to an insert.
As surface mounting of semiconductor devices, so-called die mounting, in which a die is directly mounted on a wiring board, has become mainstream along with miniaturization and thinning of electronic component devices. Examples of the semiconductor device mounted on the die include cob (chip on board), cog (chip on glass), and tcp (tape Carrier package), and a liquid resin composition containing an epoxy resin is widely used as a sealing material for these semiconductor devices.
In a semiconductor device (flip chip) in which a semiconductor device is directly bump-connected to a wiring board (hereinafter also simply referred to as "board") using ceramic, glass/epoxy resin, glass/imide resin, or polyimide film as a substrate, a liquid resin composition containing an epoxy resin is used as an underfill material for filling a Gap (Gap) between the semiconductor device and the wiring board to which the bump is connected.
These liquid resin compositions containing epoxy resins play an important role in protecting electronic parts from damage due to temperature and humidity and mechanical external forces.
When flip-chip mounting is performed, thermal stress is generated at a joint portion due to a difference in thermal expansion coefficient between a device and a substrate, and therefore, it is an important problem to ensure connection reliability. In addition, the circuit formation surface of the die is not sufficiently protected, and moisture and ionic impurities are likely to infiltrate, and therefore, it is also an important problem to ensure moisture resistance reliability. Although round corners are formed on the side surfaces of the chip to protect the chip (japanese: フィレツト), there is a concern that: the resin cracks due to thermal stress caused by a difference in thermal expansion between the underfill and the chip, and the chip is broken. Depending on the choice of underfill material, when subjected to repeated thermal shock in a temperature cycle test or the like, the connection portion is insufficiently protected, and therefore, fatigue failure may occur in the joint portion under low cycles. In addition, if there are voids in the underfill material, the bumps are not sufficiently protected, and therefore, in this case, fatigue failure may occur in the joint portion even at low cycles.
Therefore, there is a high demand for an underfill resin composition having good flowability and temperature cyclability, and when an inorganic filler is highly filled for the purpose of improving temperature cyclability or the like, the underfill resin composition has a problem that the viscosity is significantly increased, the flowability is reduced, and the moldability is deteriorated.
As an invention for solving this problem, there are known: the underfill resin composition containing (a) 1 or more selected from a specific epoxy resin and a specific epoxy compound, (B) an amine-based curing agent, (C) an inorganic filler, and (D) specific silicone fine particles in predetermined amounts can reduce the viscosity of the resin composition and has excellent fluidity and temperature cycle resistance (for example, see patent document 1).
In addition, it is known that: by using silica having a specific particle diameter and amorphous silica having a specific particle diameter together, a resin composition for underfill having excellent flowability and temperature cycle resistance can be formed while achieving a low viscosity (see, for example, patent document 2).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2012-144661
Patent document 2: japanese laid-open patent publication No. 2012-149111
Disclosure of Invention
Problems to be solved by the invention
With the recent increase in integration and multi-functionalization of semiconductor devices, chip sizes have been increasing, while the diameter, pitch (japanese: ピツチ), and spacing of bumps have been decreasing due to the increase in the number of leads, and chip thicknesses have been decreasing due to the miniaturization of devices mounted thereon. Since the particle size of the inorganic filler that can be used is reduced due to the narrowing of the span and the narrowing of the interval, it has become difficult to highly fill the inorganic filler into the resin composition for underfill. In addition, since the use of a low-viscosity resin may cause a decrease in glass transition temperature (Tg) and a decrease in resin strength, it has been difficult to mix a large amount of the low-viscosity resin into the resin composition for underfill. Therefore, it is becoming increasingly difficult to achieve both high fluidity and reliability (e.g., temperature cycle resistance and moisture resistance).
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an underfill resin composition excellent in flowability, filling property, moldability, temperature cycle resistance and moisture resistance, an electronic component device sealed at least partially with the underfill resin composition and having high reliability, and a method for manufacturing the electronic component device.
Means for solving the problems
The present inventors have made intensive studies to solve the above problems, and as a result, have found that an underfill resin composition containing an epoxy resin, an aromatic amine compound, an inorganic filler and an organic phosphorus compound can realize high filling of the inorganic filler and low viscosity, and as a result, can satisfy flowability, filling property, moldability, temperature cycle resistance and moisture resistance. Further, it has been found that an electronic component device at least a part of which is sealed with the resin composition for underfill has high reliability.
That is, the present invention relates to the following [1] to [11 ].
[1] A resin composition for underfill, which comprises (A) an epoxy resin, (B) an aromatic amine compound, (C) an inorganic filler and (D) an organic phosphorus compound.
[2] The resin composition for underfill according to item [1] above, wherein the organic phosphorus compound (D) is at least 1 selected from the group consisting of phosphine compounds, phosphine oxide compounds, phosphonates, phosphites, phosphates, phosphorane compounds, phospholene compounds, phosphoyne compounds and copolymers having a phosphate group.
[3] The resin composition for underfill according to the above [1] or [2], wherein the (D) organic phosphorus compound is 1 or more selected from the group consisting of triphenylphosphine, tris (p-methoxyphenyl) phosphine, triphenylphosphine oxide and a copolymer having a phosphate group.
[4] The resin composition for underfill according to any one of the above [1] to [3], wherein the epoxy resin (A) is at least 1 selected from a bisphenol type epoxy resin and a glycidylamine type epoxy resin.
[5] The resin composition for underfill according to any one of the above [1] to [4], wherein the aromatic amine compound (B) is at least 1 selected from the group consisting of diethyltoluenediamine, 3 '-diethyl-4, 4' -diaminodiphenylmethane and dimethylthiotoluenediamine.
[6] The resin composition for underfill according to any one of the above [1] to [5], wherein the content of the (C) inorganic filler is 40 to 80% by mass based on the total amount of the resin composition for underfill.
[7] The resin composition for underfill according to any one of the above [1] to [6], wherein the content of the (C) inorganic filler is 60 to 75 mass% based on the total amount of the resin composition for underfill.
[8] The resin composition for underfill according to any one of the above [1] to [7], wherein the content of the (D) organic phosphorus compound is 0.001 to 10% by mass based on the (C) inorganic filler.
[9]According to the above [1]～[8]The resin composition for underfill according to any one of the above, wherein the shear rate is 32.5s at 110 ℃ with an E-type viscometer-1The viscosity measured under the condition (1) is 0.01 to 0.25 pas.
[10] An electronic component device, comprising: a support member, an electronic component arranged on the support member, and a connecting portion between the support member and the electronic component,
at least a part of the connecting portion is sealed with the resin composition for underfill described in any one of [1] to [9 ].
[11] A method for manufacturing an electronic component device in which a support member and an electronic component are electrically connected to each other through a connection portion, comprising the steps of:
sealing at least a part of the connection part with the resin composition for underfill according to any one of the above [1] to [9 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide an underfill resin composition excellent in flowability, filling property, moldability, temperature cycle resistance and moisture resistance, an electronic component device highly reliable in sealing at least a part thereof with the underfill resin composition, and a method for manufacturing the electronic component device.
Detailed Description
In the present specification, the term "step" is not limited to a separate step, and is also included in the term as long as the intended purpose of the step is achieved when the step is not clearly distinguished from other steps. In the present specification, the numerical range indicated by the term "to" means a range including the numerical values described before and after the term "to" as the minimum value and the maximum value, respectively.
In the present specification, the content of each component in the resin composition refers to the total content of a plurality of substances present in the resin composition, when the plurality of substances corresponding to each component are present in the resin composition, unless otherwise specified.
In the present specification, "normal temperature" means 25 ℃. The term "liquid" means a liquid at ordinary temperature unless otherwise specified, and means that the viscosity measured with an E-type viscometer at ordinary temperature is 1,000Pa · s or less. The term "solid" means solid at normal temperature, that is, solid unless otherwise specified.
[ resin composition for underfill ]
The resin composition for underfill of the present invention comprises (A) an epoxy resin, (B) an aromatic amine compound, (C) an inorganic filler, and (D) an organic phosphorus compound.
The respective components and physical properties of the resin composition for underfill of the present invention will be described in order below.
< epoxy resin (A) >
The epoxy resin (a) is not particularly limited as long as it is an epoxy resin generally used for resin compositions for underfill, and for example, an epoxy resin having 2 or more epoxy groups in 1 molecule is preferable.
(A) The epoxy resin may be in a solid state or a liquid state at room temperature, and is preferably in a liquid state at room temperature from the viewpoint of filling properties. As the epoxy resin, particularly an epoxy resin that is liquid at ordinary temperature (hereinafter, also referred to as "liquid epoxy resin"), a liquid epoxy resin that is generally used in a resin composition for underfill can be used. The viscosity of the liquid epoxy resin measured with an E-type viscometer at room temperature is preferably 0.0001 to 10 pas, for example.
Examples of the epoxy resin (a) include: diglycidyl ether type epoxy resins such as bisphenol a, bisphenol F, bisphenol AD, bisphenol S, and hydrogenated bisphenol a; a phenol resin obtained by epoxidizing a phenol resin obtained from phenols and aldehydes, such as an o-cresol novolac type epoxy resin; glycidyl ester type epoxy resins obtained by the reaction of epichlorohydrin with polybasic acids such as phthalic acid and dimer acid; glycidylamine-type epoxy resins obtained by the reaction of epichlorohydrin with an amine compound such as p-aminophenol, diaminodiphenylmethane or isocyanuric acid; linear aliphatic epoxy resins and alicyclic epoxy resins obtained by oxidizing an olefin bond with a peroxy acid such as peracetic acid. (A) The epoxy resin may be used alone in 1 kind, or 2 or more kinds may be used in combination.
Of these, bisphenol type epoxy resins are preferred from the viewpoint of fluidity, and glycidyl amine type epoxy resins are preferred from the viewpoint of heat resistance, adhesiveness and fluidity. Therefore, the (a) epoxy resin is preferably 1 or more selected from bisphenol type epoxy resins and glycidyl amine type epoxy resins.
In addition, as the bisphenol type epoxy resin, from the viewpoint of fluidity, 1 or more of diglycidyl ether type epoxy resin of bisphenol a (bisphenol a type epoxy resin) and diglycidyl ether type epoxy resin of bisphenol F (bisphenol F type epoxy resin) is preferable. When the bisphenol A-type epoxy resin and the bisphenol F-type epoxy resin are used in combination, the mass ratio thereof (bisphenol A-type epoxy resin: bisphenol F-type epoxy resin) is not particularly limited, but is, for example, preferably 5: 95 to 50: 50, more preferably 10: 90 to 40: 60, and further preferably 20: 80 to 40: 60, from the viewpoint of heat resistance, adhesiveness, and fluidity.
From the viewpoint of fluidity, both the bisphenol epoxy resin and the glycidylamine epoxy resin are preferably in a liquid state at room temperature.
The bisphenol epoxy resin and the glycidylamine epoxy resin may be used alone or in combination of 2 or more, and from the viewpoint of heat resistance, adhesiveness and fluidity, the bisphenol epoxy resin and the glycidylamine epoxy resin are preferably used in combination.
The total content of the bisphenol epoxy resin and the glycidylamine epoxy resin is not particularly limited, and is, for example, preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, and particularly preferably 80% by mass or more, relative to the total amount of the (a) epoxy resin, from the viewpoint of heat resistance, adhesiveness, and fluidity. The upper limit of the total content is not particularly limited, and may be determined within a range that can obtain desired properties and characteristics from the viewpoints of viscosity, glass transition temperature, heat resistance, and the like, and may be 100 mass%.
When the bisphenol epoxy resin and the glycidylamine epoxy resin are used in combination, the mass ratio (bisphenol epoxy resin: glycidylamine epoxy resin) is not particularly limited, but is, for example, preferably 20: 80 to 95: 5, more preferably 40: 60 to 90: 10, and still more preferably 60: 40 to 80: 20, from the viewpoint of heat resistance, adhesiveness, and fluidity.
In addition, an epoxy resin that is solid at normal temperature may be used in the resin composition for underfill of the present invention.
The content of the epoxy resin that is solid at room temperature is, for example, preferably 0 to 20 mass%, more preferably 0 to 10 mass%, and still more preferably 0 to 5 mass% with respect to the total amount of the epoxy resin (a) from the viewpoint of fluidity.
(A) The epoxy equivalent of the epoxy resin is not particularly limited, but is preferably 60 to 400g/mol, more preferably 70 to 300g/mol, and still more preferably 80 to 250g/mol, from the viewpoint of heat resistance.
The mass (g/eq) of the resin having an epoxy equivalent per epoxy group can be measured according to the method specified in JIS K7236. Specifically, the following is obtained: the epoxy resin was obtained by weighing 2g to 200ml of a beaker using an automatic titration apparatus "GT-200 type" of Mitsubishi Chemical Analytech Co., Ltd., after dissolving 90ml of methyl ethyl ketone dropwise in an ultrasonic cleaner, 10ml of glacial acetic acid and 1.5g of cetyltrimethylammonium bromide were added and titrated with 0.1mol/L perchloric acid/acetic acid solution.
The purity of the epoxy resin (A) is preferably high. In particular, the amount of hydrolyzable chlorine is preferably small because it is responsible for corrosion of aluminum wiring on devices such as IC (Integrated Circuit), and is preferably 500ppm or less, for example, from the viewpoint of obtaining a resin composition for underfill having excellent moisture resistance.
Here, the amount of hydrolyzable chlorine is measured as a value obtained by dissolving 1g of the sample epoxy resin in 30ml of dioxane, adding 5ml of 1N-KOH (potassium hydroxide) methanol solution, refluxing for 30 minutes, and then performing potentiometric titration.
The content of the epoxy resin (a) in the resin composition for underfill of the present invention is not particularly limited, and is, for example, preferably 40 to 90% by mass, more preferably 50 to 80% by mass, and further preferably 55 to 70% by mass, in the total amount of the resin composition excluding the inorganic filler (C), from the viewpoints of heat resistance, adhesiveness, and fluidity.
< (B) aromatic amine Compound >
The aromatic amine compound (B) is not particularly limited as long as it functions as a curing agent for the epoxy resin (a). When the aromatic amine compound is used, the heat resistance is excellent in cycle resistance and moisture resistance, and the reliability of the semiconductor device can be improved, as compared with amine-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and the like known as curing agents for epoxy resins.
(B) The aromatic amine compound is preferably a compound containing 1 or more (hereinafter also simply referred to as "amino group") selected from the group consisting of a primary amino group and a secondary amino group in 1 molecule, more preferably a compound having 2 to 4 amino groups, and even more preferably an aromatic diamine compound having 2 amino groups. The amino group is preferably a primary amino group.
(B) The aromatic amine compound may be in a solid state or a liquid state at room temperature, and is preferably in a liquid state at room temperature from the viewpoint of fluidity of the resin composition for underfill.
Examples of the aromatic amine compound which is liquid at ordinary temperature (also referred to as a liquid aromatic amine compound) include: diethyltoluenediamines such as 3, 5-diethyltoluene-2, 4-diamine and 3, 5-diethyltoluene-2, 6-diamine, 1-methyl-3, 5-diethyl-2, 4-diaminobenzene, 1-methyl-3, 5-diethyl-2, 6-diaminobenzene, 1, 3, 5-triethyl-2, 6-diaminobenzene, 3 ' -diethyl-4, 4 ' -diaminodiphenylmethane, 3, 5, 3 ', 5 ' -tetramethyl-4, 4 ' -diaminodiphenylmethane and dimethylthiotoluenediamine.
(B) The aromatic amine compound may be used alone in 1 kind, or 2 or more kinds may be used in combination.
Of these, from the viewpoint of storage stability, for example, 1 or more selected from diethyltoluenediamine, 3 '-diethyl-4, 4' -diaminodiphenylmethane and dimethylthiotoluenediamine, and 1 or more selected from diethyltoluenediamine and 3,3 '-diethyl-4, 4' -diaminodiphenylmethane are preferable.
From the viewpoint of storage stability, the content of diethyltoluenediamine in the aromatic amine compound (B) is preferably 20 to 70% by mass, more preferably 30 to 55% by mass.
As the liquid aromatic amine compound, a commercially available product can be used. As a commercially available liquid aromatic amine compound, for example: JER Cure W (trade name, product name.
The content of the other curing agent (B) may be, for example, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less based on 100 parts by mass of the aromatic amine compound (B), from the viewpoints of filling property, moldability, temperature cycle resistance, and moisture resistance, as long as the effects of the present invention are not impaired.
As the (B) aromatic amine compound, an aromatic amine compound (B) which is solid at room temperature may be used.
The content of the (B) aromatic amine compound which is solid at room temperature is, for example, preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and further preferably 0 to 5% by mass, based on the total amount of the (B) aromatic amine compound, from the viewpoint of fluidity.
(B) The active hydrogen equivalent of the aromatic amine compound is not particularly limited, but is, for example, preferably 10 to 200g/mol, more preferably 20 to 120g/mol, and still more preferably 30 to 75g/mol, from the viewpoints of filling property, moldability, temperature cycle resistance, and moisture resistance.
The equivalent ratio of the epoxy resin (a) to the aromatic amine compound (B) (the number of moles of epoxy groups in the epoxy resin (a)/the number of moles of active hydrogen in the aromatic amine compound (B)) in the resin composition for underfill of the present invention is not particularly limited, and is, for example, preferably 0.7 to 1.6, more preferably 0.8 to 1.4, and even more preferably 0.9 to 1.2, from the viewpoint of suppressing the unreacted components to a small amount.
< inorganic Filler >
The inorganic filler (C) is not particularly limited, and examples thereof include: silica such as fused silica and crystalline silica; alumina such as calcium carbonate, clay, and alumina; powders such as silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllium oxide, zirconium oxide, zircon, forsterite, steatite, spinel, mullite, and titanium dioxide, or beads obtained by spheroidizing them; glass fibers, and the like.
As the inorganic filler (C), an inorganic filler having a flame retardant effect may also be used. Examples of the inorganic filler having a flame retardant effect include: aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate and the like.
(C) The inorganic filler may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Among these, from the viewpoints of ease of handling, chemical stability, and material cost, for example, silica is preferable, and fused silica is more preferable. (C) The particle shape of the inorganic filler is not particularly limited, and may be an amorphous shape or a spherical shape, and spherical silica, particularly spherical fused silica, is preferably used from the viewpoint of flowability and permeability into fine gaps of the resin composition for an underfill.
The inorganic filler (C) may be surface-treated. (C) The inorganic filler may be surface-treated with a silane coupling agent. Examples of the silane coupling agent include: an aminosilicone-based coupling agent, an epoxysilane-based coupling agent, a phenylsilane-based coupling agent, an alkylsilane-based coupling agent, an alkenylsilane-based coupling agent, an alkynylsilane-based coupling agent, a haloalkylsilane-based coupling agent, a siloxane-based coupling agent, a hydrosilane-based coupling agent, a silazane-based coupling agent, an alkoxysilane-based coupling agent, a chlorosilicone-based coupling agent, a (meth) acrylic silane-based coupling agent, an aminosilicone-based coupling agent, an isocyanurate silane-based coupling agent, an ureidosilane-based coupling agent, a mercaptosilane-based coupling agent, a thioether silane-based coupling agent, an isocyanate silane-based coupling agent, and the like.
(C) The volume average particle size of the inorganic filler is not particularly limited, and is, for example, preferably 0.1 to 10 μm, more preferably 0.3 to 5 μm, and still more preferably 0.5 to 3 μm. By setting the volume average particle diameter of the inorganic filler (C) to 0.1 μm or more, the dispersibility of the epoxy resin (a) is improved, thixotropy is not easily imparted to the underfill resin composition, and the flow characteristics of the underfill resin composition tend to be improved. On the other hand, by setting the particle size to 10 μm or less, the inorganic filler (C) in the resin composition for underfill tends to be easily inhibited from settling, and the resin composition for underfill has improved permeability and fluidity to fine gaps, and tends to be inhibited from generating voids and unfilled portions.
The volume average particle diameter is a particle diameter of a point corresponding to 50% by volume when a cumulative frequency distribution curve based on the particle diameter is obtained by assuming that the total volume of the particles is 100%, and can be measured using a particle size distribution measuring apparatus using a laser diffraction scattering method or the like.
The content of the inorganic filler (C) in the resin composition for underfill of the present invention is not particularly limited, and is, for example, preferably 40 to 80 mass%, may be 50 to 75 mass%, and may be 60 to 75 mass% with respect to the total amount of the resin composition for underfill. By setting the content of the inorganic filler (C) to 40 mass% or more, the effect of reducing the thermal expansion coefficient and the effect of improving the temperature cycle resistance tend to be easily obtained; by setting the amount to 80% by mass or less, the increase in viscosity of the underfill resin composition is suppressed, and the flowability, permeability, and distribution tend to be good. In particular, from the viewpoint of the effect of improving the temperature cycle resistance, the lower limit of the content of the (C) inorganic filler is preferably higher. In the present invention, even if the content of the inorganic filler (C) is increased as described above, the viscosity of the resin composition for underfill can be maintained at a low level.
(D) organic phosphorus Compound
(D) An organophosphorus compound is a compound having an organic group and a phosphorus atom in a molecule. The organic group is preferably an aromatic hydrocarbon group having 6 to 14 carbon atoms from the viewpoint of fluidity, filling property, and temperature cycle resistance. Examples of the aromatic hydrocarbon group include: phenyl, naphthyl, anthracenyl, and the like. The aromatic hydrocarbon group may be substituted with 1 or more substituents selected from an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms.
By using (D) the organic phosphorus compound, there is an effect of reducing the viscosity of the resin composition for underfill. Although the exact reason for this effect is not clear, it is presumed that: (D) the organic phosphorus compound has an effect of adsorbing on the surface of the inorganic filler (C) and suppressing hydrogen bonding between the inorganic fillers. It is also presumed that: the steric effect of the main skeleton based on the organic phosphorus compound (D) improves the dispersion stability of the inorganic filler (C), thereby providing an effect of preventing the inorganic filler (C) from settling.
Examples of the organic phosphorus compound (D) include: phosphine compounds, phosphine oxide compounds, phosphonic acid esters, phosphorous acid esters, phosphoric acid esters, phosphorane compounds, phospholene compounds, copolymers having a phosphate group, and the like. Among them, the phosphine compound, the phosphine oxide compound, and the copolymer having a phosphate group are preferable from the viewpoints of the flowability, filling property, temperature cycle resistance, and moisture resistance of the resin composition for underfill.
(D) The organic phosphorus compounds can be used alone in 1, can also be used in combination with more than 2.
As the phosphine compound, for example: triphenylphosphine, diphenyl (p-tolyl) phosphine, tri (alkylphenyl) phosphine, tri (alkoxyphenyl) phosphine, tri (alkylalkoxyphenyl) phosphine, tri (dialkylphenyl) phosphine, tri (trialkylphenyl) phosphine, tri (tetraalkylphenyl) phosphine, tri (dialkoxyphenyl) phosphine, tri (trialkoxyphenyl) phosphine, tri (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylaryl phosphine, alkyldiaryl phosphine, and the like. Among them, triphenylphosphine and tris (alkoxyphenyl) phosphine are preferable from the viewpoints of fluidity, filling property, temperature cycle resistance and moisture resistance. As the tris (alkoxyphenyl) phosphine, for example, tris (p-methoxyphenyl) phosphine and the like are preferable.
Examples of the phosphine oxide compound include: diphenylphosphine oxide, diphenylvinylphosphine oxide, triphenylphosphine oxide, (2, 5-dihydroxyphenyl) diphenylphosphine oxide, (p-hydroxyphenyl) diphenylphosphine oxide, bis (p-hydroxyphenyl) phenylphosphine oxide, tris (p-hydroxyphenyl) phosphine oxide, and the like. Among them, triphenylphosphine oxide is preferable from the viewpoints of fluidity, filling property, temperature cycle resistance and moisture resistance.
The copolymer having a phosphate group is not particularly limited as long as it has a phosphate group in the molecule. A commercially available product can be used in a simple manner, and for example, BYK-W9010 (product name, BYK Chemie Japan) can be used.
The content of the organic phosphorus compound (D) in the resin composition for underfill of the present invention is not particularly limited, and is, for example, preferably 0.001 to 10 mass%, more preferably 0.01 to 5 mass%, and still more preferably 0.01 to 2 mass% with respect to the total amount of the inorganic filler (C).
< other ingredients >
The resin composition for underfill of the present invention may be a resin composition containing other components in addition to the components (a) to (D). Examples of the other components include known components that can be contained in the resin composition for underfill, and examples thereof include a flexibilizing agent, a curing accelerator, a coupling agent, an ion scavenger, a coloring agent, a diluent, a leveling agent, and an antifoaming agent.
(flexibilizers)
When the flexibilizer is used, the effect of improving the thermal shock resistance of the resin composition for underfill and the effect of reducing the stress on the semiconductor device can be obtained. The flexibilizer is not particularly limited, but rubber particles are preferred. Examples of the rubber particles include: rubber particles such as styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), Butadiene Rubber (BR), Urethane Rubber (UR), Acrylic Rubber (AR), and silicone rubber.
The flexibility agent can be used alone in 1, can also be used in more than 2 combinations.
Examples of the silicone rubber particles include: silicone rubber particles obtained by crosslinking a polyorganosiloxane such as linear polydimethylsiloxane, polymethylphenylsiloxane, or polydiphenylsiloxane; silicone rubber particles having surfaces of the silicone rubber particles coated with a silicone resin; core-shell polymer particles composed of a core of solid silicone particles obtained by emulsion polymerization or the like and a shell of an organic polymer such as an acrylic resin, and the like.
The shape of these silicone rubber particles may be amorphous or spherical, and spherical silicone rubber particles are preferably used in order to keep the viscosity of the resin composition for underfill low. The Silicone rubber particles are commercially available from Toray Dow Corning Silicone co.
The average primary particle diameter of the rubber particles is preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm. When the average primary particle diameter is 0.05 μm or more, the dispersibility of the resin composition for underfill tends to be improved; when the thickness is 10 μm or less, the stress reduction effect tends to be improved, and the permeability and fluidity into fine gaps as the resin composition for underfill are improved, so that the generation of voids and unfilled portions tends to be easily suppressed. In order to uniformly modify the resin composition for underfill, a mode in which the primary particle diameter of the rubber particles is small is advantageous.
When the underfill resin composition contains a flexibilizer, the content thereof is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and still more preferably 4 to 12% by mass of the entire underfill resin composition excluding the inorganic filler (C). When the content of the flexibilizer is 1 mass% or more, the low stress effect tends to be large; when the amount is 30% by mass or less, the viscosity of the resin composition for underfill is reduced, and moldability and fluidity tend to be improved.
(curing accelerators)
The resin composition for underfill of the present invention may be a resin composition containing a curing accelerator as necessary, from the viewpoint of accelerating the reaction between the epoxy resin (a) and the aromatic amine compound (B).
The curing accelerator is not particularly limited, and conventionally known curing accelerators can be used. Examples thereof include: cyclic amidine compounds such as 1, 8-diazabicyclo [5.4.0] undecene-7, 1, 5-diazabicyclo [4.3.0] nonene, 5, 6-dibutylamino-1, 8-diazabicyclo [5.4.0] undecene-7, and the like; tertiary amine compounds such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 4-diamino-6- (2 '-methylimidazolyl- (1')) -ethyl-s-triazine, and 2-heptadecylimidazole; and phenylboronates such as 2-ethyl-4-methylimidazolium tetraphenylborate and N-methylmorpholinium tetraphenylborate. Among these, from the viewpoint of transparency and curing acceleration effect, an imidazole compound is preferable, and 2-phenyl-4-methyl-5-hydroxymethylimidazole is more preferable.
Further, as the latent curing accelerator, there can be mentioned a core-shell particle in which a core containing a compound having an amino group which is solid at ordinary temperature is coated with a shell containing an epoxy compound which is solid at ordinary temperature. As commercial products of the core-shell particles, there can be used: amicure (registered trademark) (trade name, manufactured by sokoku corporation), Novacure (registered trademark) (trade name, manufactured by asahi chemicals corporation) in which a microencapsulated amine is dispersed in a bisphenol a type epoxy resin or a bisphenol F type epoxy resin, and the like.
The curing accelerator may be used alone in 1 kind, or 2 or more kinds may be used in combination.
When the resin composition for underfill of the present invention is a resin composition containing a curing accelerator, the content of the curing accelerator is not particularly limited as long as the curing accelerator is in an amount that exhibits the curing acceleration effects of the (a) epoxy resin and the (B) aromatic amine compound, and may be appropriately selected depending on the kind of the curing accelerator used, and the like. For example, the amount of the (A) epoxy resin is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 20 parts by mass, and still more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the (A) epoxy resin. When the content of the curing accelerator is 0.1 part by mass or more per 100 parts by mass of the epoxy resin (a), curability at low temperature tends to be good; when the amount is 40 parts by mass or less, the curing rate is easily controlled, and the storage stability such as pot life and pot life tends to be improved.
(coupling agent)
The resin composition for underfill of the present invention may be a resin composition containing a coupling agent as needed from the viewpoint of making the interfacial adhesion between the epoxy resin (a) and the inorganic filler (C) strong, the interfacial adhesion between the epoxy resin (a) and the constituent member of the electronic component strong, and the viewpoint of improving the filling property.
The coupling agent is not particularly limited, and conventionally known coupling agents can be used, and examples thereof include: silane-based compounds such as aminosilanes, epoxysilanes, mercaptosilanes, alkylsilanes, ureidosilanes, vinylsilanes having 1 or more kinds selected from primary, secondary and tertiary amino groups; a titanium-based compound; aluminum chelates; aluminum/zirconium-based compounds, and the like. Among these, from the viewpoint of reactivity with silica, for example, silane-based compounds are preferable, and epoxysilane is more preferable.
Examples of the epoxy silane include: beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane, etc. Among these, from the viewpoint of reactivity with silica, for example, γ -glycidyloxypropylmethyldimethoxysilane is preferable.
The coupling agent may be used alone in 1 kind, or 2 or more kinds may be used in combination.
When the resin composition for underfill of the present invention is a resin composition containing a coupling agent, the content of the coupling agent is not particularly limited, and is, for example, preferably 0.05 to 10 mass%, more preferably 0.1 to 5 mass%, and still more preferably 0.1 to 3 mass% with respect to the total amount of the resin composition for underfill, from the viewpoint of making the interfacial adhesion between the epoxy resin (a) and the inorganic filler (C) strong, and the interfacial adhesion between the epoxy resin (a) and the constituent member of the electronic component firm, and from the viewpoint of improving the filling property.
< ion scavenger >
The resin composition for underfill of the present invention may be a resin composition containing an ion scavenger as necessary, from the viewpoint of improving migration resistance, moisture resistance and high-temperature storage characteristics of a semiconductor device such as an IC.
The ion scavenger is not particularly limited, and examples thereof include those represented by the following composition formula (I) or (II).
Mg1-xAlx(OH)2(CO3)x/2·mH2O (I)
(X is more than 0 and less than or equal to 0.5, and m is a positive number)
BiOx(OH)y(NO3)z (II)
(0.9≤x≤1.1、0.6≤y≤0.8、0.2≤z≤0.4)
(2 x + y + z: 3.)
The compound represented by the above composition formula (I) or (II) can be obtained as a commercially available product. As a commercially available product constituting the compound represented by the formula (I), "DHT-4A" (product name, manufactured by Kyowa Kagaku K.K.) is available, for example. Further, as a commercially available product of the compound represented by the above composition formula (II), "IXE-500" (trade name, manufactured by Toyo Synthesis Co., Ltd.) is available, for example.
The ion scavenger may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The average particle size of the ion scavenger is not particularly limited, but is preferably 0.1 to 3 μm, and the maximum particle size is preferably 10 μm or less, for example.
When the resin composition for underfill of the present invention is a resin composition containing an ion scavenger, the content of the ion scavenger is, for example, preferably 0.1 to 3% by mass, and more preferably 0.3 to 1.5% by mass.
The resin composition for underfill of the present invention may contain other anion exchangers as necessary. The other anion exchanger is not particularly limited, and conventionally known anion exchangers can be used, and examples thereof include hydrous oxides of 1 or more elements selected from magnesium, aluminum, titanium, zirconium, antimony, and the like, and 1 kind thereof may be used alone or 2 or more kinds thereof may be used in combination.
The resin composition for underfill of the present invention can be prepared by any method among the methods capable of sufficiently dispersing and mixing the above-mentioned various components. For example, the components may be obtained by weighing predetermined amounts, mixing and kneading the components with a mixer such as a crusher, a mixing roll, or a planetary mixer, and defoaming the mixture as necessary.
The mixing and kneading conditions may be appropriately determined depending on the kind of the raw material and the like, and it is preferable to select conditions for sufficiently (preferably uniformly) mixing and dispersing the above components.
(viscosity of resin composition for underfill)
The resin composition for underfill of the present invention is preferably in a liquid state at room temperature. That is, the viscosity of the resin composition for underfill of the present invention measured with an E-type viscometer at room temperature is preferably 1,000Pa · s or less, for example. When the viscosity is 1,000Pa · s or less, fluidity and permeability that can cope with recent miniaturization of electronic parts, micro-span of connection terminals of semiconductor devices, and micro-wiring of wiring boards are easily secured.
The viscosity of the resin composition for underfill is also particularly important when underfill is performed, and from the same viewpoint as above, the viscosity of the resin composition for underfill, measured at a temperature (70 to 130 ℃) for underfill, for example, 110 ℃ by the method described in the examples, is, for example, preferably 500Pa · s or less, more preferably 100Pa · s or less, further preferably 10Pa · s or less, further preferably 3Pa · s or less, particularly preferably 0.25Pa · s or less, and most preferably 0.20Pa · s or less. The lower limit of the viscosity is not particularly limited, but is, for example, preferably 0.01Pa · s or more, more preferably 0.5Pa · s or more, and further preferably 0.1Pa · s or more, from the viewpoint of mountability. In particular, the viscosity is preferably 0.01 to 0.25 pas, more preferably 0.01 to 0.20 pas, and still more preferably 0.05 to 0.20 pas.
The viscosity can be appropriately adjusted according to the kind of the electronic component and the electronic component device to be sealed. The viscosity can be adjusted by controlling the kind, content, and the like of each component exemplified above, for example.
[ electronic component device ]
The electronic component device of the present invention comprises a support member, an electronic component disposed on the support member, and a connection portion between the support member and the electronic component, wherein at least a part of the connection portion is sealed with the underfill resin composition of the present invention. Since at least a part of the connecting portion is sealed with the underfill resin composition of the present invention, the electronic component device can be said to contain a cured product of the underfill resin composition of the present invention.
The preferred embodiments of the semiconductor device including the support member, the electronic component and the like constituting the electronic component device of the present invention are the same as those exemplified in the description of the use of the resin composition for underfill of the present invention.
The electronic component device of the present invention may be such that at least a part of the connection portion is sealed with the resin composition for underfill of the present invention, preferably 50% or more of the connection portion is sealed, more preferably 80% or more of the connection portion is sealed, and further preferably all of the connection portion is sealed. In addition, the gap between the support member and the electronic component may be filled with the underfill resin composition in an amount of preferably 80% by volume or more, more preferably 90% by volume or more, and still more preferably 100% by volume.
[ method for manufacturing electronic component device ]
A method for manufacturing an electronic component device according to the present invention is a method for manufacturing an electronic component device in which a support member and an electronic component are electrically connected to each other through a connection portion, the method including the steps of: and a step of sealing at least a part of the connection part with the underfill resin composition of the present invention.
The preferred embodiments of the semiconductor device provided with the support member, the electronic component and the like used in the method for producing the electronic component device of the present invention are the same as those of the semiconductor device exemplified in the description of the use of the resin composition for underfill of the present invention.
The method for sealing the connection between the support member and the electronic component using the resin composition for underfill of the present invention is not particularly limited, and conventionally known methods such as a dispensing method, an injection molding (japanese: injection molding) method, and a printing method can be applied.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The test methods of the characteristic tests performed in the examples and comparative examples are summarized below.
The specifications of the semiconductor devices used for the evaluation of the resin compositions for underfill obtained in examples and comparative examples are as follows.
Size of semiconductor device: 20 mm. times.20 mm. times.0.55 mm in thickness (daisy-chain connection and passivation of circuit: aluminum: polyimide film HD4000, manufactured by Hitachi Chemical DuPont MicroSystems)
Kind of bump: solder ball (Sn-Ag-Cu, diameter 80 μm, 7,744 pins)
Bump pitch: 190 μm
Kind of substrate (core): FR-5 (solder resist SR7200, manufactured by Hitachi chemical Co., Ltd., 60 mm. times.60 mm. times.0.8 mm in thickness)
Spacing between substrate and chip: 50 μm
[ sealing and curing conditions ]
The resin compositions for underfill, obtained in examples and comparative examples, 80mg were applied (underfill) in a dispensing manner at 110 ℃ to a gap between a substrate and a device of a semiconductor device, and then the gap was sealed by curing in air at 150 ℃ for 2 hours to produce a semiconductor device.
[ evaluation of physical Properties ]
The resin compositions for underfill obtained in examples and comparative examples were evaluated by the following tests. The evaluation results are shown in table 1.
(1) Viscosity at 110 ℃ C (evaluation of fluidity)
Using a model E viscometer "AR 2000" (manufactured by TA INSTRUMENT), 40mm parallel plates (interval: 500 μm) were used at a shear rate of 32.5s-1The viscosity of the resin composition for underfill was measured at 110 ℃. From the viewpoint of fluidity at narrow intervals, it is preferably 0.25 pas or less, more preferably 0.20 pas or less.
(2) Infiltration time (evaluation of filling Property)
The semiconductor device was placed on a hot plate heated to 110 ℃, 100mg of the resin composition for underfill was dropped to the side surface (side 1) of the chip by dispensing, and the time taken for the resin composition for underfill to permeate into the opposite side surface was measured. Preferably 110 seconds or less, more preferably 100 seconds or less.
(3) Presence or absence of voids (evaluation of moldability)
The inside of 10 sealed semiconductor devices was observed by an ultrasonic flaw detector "AT-5500" (manufactured by hitachi corporation), the presence or absence of voids was examined, and the number of semiconductor devices having voids (the number of semiconductor devices having voids/10) was measured. The smaller the number of semiconductor devices having voids, the more excellent the moldability.
(4) Evaluation of reliability
(4-1) resistance to temperature cycling
A semiconductor device produced by underfilling a resin composition for underfill was subjected to a conduction test 1,000 times per cycle by performing a 2,000-cycle treatment at-55 to 125 ℃ for 30 minutes of each thermal cycle, and the number of defective packages/the number of packages evaluated was evaluated by examining the disconnection defects of aluminum wiring and pads.
(4-2) moisture resistance
After a semiconductor device produced by underfilling the resin composition for underfill was treated for 200 hours under HAST conditions of 130 ℃ and 85% RH, the presence or absence of disconnection of aluminum wiring and pads was confirmed by a conduction test, and the number of defective packages was evaluated based on the number of packages evaluated.
Examples 1 to 8 and comparative examples 1 to 4
The components shown in table 1 were compounded in accordance with the compositions shown in table 1, and kneaded and dispersed by a three-roll mill and a vacuum breaker to prepare resin compositions for underfill in examples 1 to 8 and comparative examples 1 to 4. The unit of the compounding composition in table 1 is part by mass unless otherwise specified, and a blank indicates no compounding.
Note that abbreviations and the like in table 1 are as follows.
(epoxy resin)
Epoxy resin 1: liquid diepoxy resin having an epoxy equivalent of 160g/mol (product name "jER 806" manufactured by mitsubishi chemical corporation) obtained by epoxidizing bisphenol F
Epoxy resin 2: liquid diepoxy resin having an epoxy equivalent of 190g/mol obtained by epoxidizing bisphenol A (trade name "epoxy (registered trademark) R140P", manufactured by Mitsui chemical Co., Ltd.)
Epoxy resin 3: a3-functional liquid epoxy resin having an epoxy equivalent of 95g/mol (product name "JeR 630" manufactured by Mitsubishi chemical corporation) obtained by epoxidizing aminophenol
(aromatic amine Compound)
Aromatic amine compound 1: diethyltoluene diamine having an active hydrogen equivalent of 45g/mol (product name "JeR Cure W" manufactured by Mitsubishi chemical corporation)
Aromatic amine compound 2: diethyldiaminodiphenylmethane having an active hydrogen equivalent of 63g/mol (product name of Nippon Kayahard (registered trade name) A-A')
(curing agent)
Curing agent 3: liquid acid anhydride having acid anhydride equivalent of 168g/mol (acid anhydride, product name "HN 5500" manufactured by Hitachi chemical Co., Ltd.)
Curing agent 4: phenol curing agent having active hydrogen of 141g/mol (trade name "MEH 8000H" manufactured by Minghuai Kabushiki Kaisha)
(inorganic Filler)
Silica: spherical fused silica having a volume average particle diameter of 1 μm
(organic phosphorus Compound)
Organic phosphorus compound 1: triphenylphosphine (product name "TPP" of Beixing chemical industry Co., Ltd.)
Organophosphorus compound 2: tris (p-methoxyphenyl) phosphine (product of Beixing chemical Co., Ltd., trade name "TPTP")
Organic phosphorus compound 3: triphenylphosphine oxide (product name "TPPO" manufactured by Beixing chemical industry Co., Ltd.)
Organic phosphorus compound 4: copolymer having phosphate group (product name "BYK-W9010" manufactured by BYK Chemie Japan K.K., acid value: 129mgKOH/g, nonvolatile content: 100%)
(other Components)
Flexibilizing agents: spherical silicone rubber particles having a volume average particle diameter of 2 μm, the surfaces of which were modified with epoxy groups (trade name "EP-2601", manufactured by Toary Dow Corning Co., Ltd.)
Curing accelerators: 2-phenyl-4-methyl-5-hydroxymethylimidazole (product name "2P 4 MHZ" from Sizhou Kasei corporation)
Coupling agent: gamma-glycidoxypropyltrimethoxysilane (product of shin Etsu chemical Co., Ltd., trade name "KBM-403")
Ion scavenger: bismuth-based ion scavenger (trade name "IXE- -500" available from Toyo Synthesis Co., Ltd.)
The colorant: carbon Black (product name "MA-100" manufactured by Mitsubishi chemical corporation)
[ Table 1]
Figure BDA0001618137100000211
*1: the content relative to the total amount of the resin composition for underfill
*2: content relative to (C) inorganic filler
In comparative examples 1 and 2 in which the aromatic amine compound (B) was not used and instead the acid anhydride-based curing agent or the phenol-based curing agent was used, voids were generated and the temperature cycle resistance and the moisture resistance were not sufficient. In comparative example 2, the flowability at 110 ℃ was low, and the filling property was poor.
In comparative examples 3 and 4 in which the organic phosphorus compound (D) was not used, voids were generated, and the temperature cycle resistance was poor. In addition, in either of comparative examples 3 and 4, the flowability at 110 ℃ was low and the filling property was poor.
From a comparison of the results of examples 2 and 6 to 8, it is found that when triphenylphosphine (organic phosphorus compound 1) is used as the (D) organic phosphorus compound, the effect of the lowest viscosity is obtained and the filling property tends to be improved.
From the results of examples 1 to 5, it is understood that the effect of low viscosity is increased and filling property is also improved by increasing the amount of the organic phosphorus compound (D). In particular, in example 3, the inorganic filler was highly filled (70 mass%), but the viscosity was maintained low, and therefore, voids were not generated, and the heat resistance cycle and the moisture resistance were the most excellent.
Industrial applicability
The resin composition for underfill of the present invention can be applied to, for example, a semiconductor device in which an electronic component such as a semiconductor chip, an active device such as a transistor, a diode, or a thyristor, a capacitor, a resistor array, a coil, or a passive device such as a switch, is mounted on a lead frame, a wired carrier tape, a rigid or flexible wiring board, a glass, a silicon wafer, or a supporting member.
In particular, the resin composition for underfill of the present invention is suitable as a resin composition for underfill for flip chips which is excellent in reliability. Specifically, the present invention is suitable for a semiconductor device such as a flip Chip BGA/LGA or COF (Chip On Film) in which a semiconductor device is flip Chip bonded to a wiring formed On a rigid or flexible wiring board or glass by bump bonding.

Claims (10)

1. An underfill resin composition comprising (A) an epoxy resin, (B) an aromatic amine compound, (C) an inorganic filler, and (D) an organic phosphorus compound, wherein the epoxy resin (A) comprises a bisphenol epoxy resin and a glycidyl amine epoxy resin, and the mass ratio of the bisphenol epoxy resin to the glycidyl amine epoxy resin is bisphenol epoxy resin: the glycidyl amine type epoxy resin is 20: 80-95: 5,
the bisphenol-type epoxy resin is a combination of a bisphenol-A-type epoxy resin and a bisphenol-F-type epoxy resin, and the mass ratio of the bisphenol-A-type epoxy resin: bisphenol F type epoxy resin is 5: 95-50: 50.
2. the resin composition for underfill according to claim 1, wherein the (D) organophosphorus compound is 1 or more selected from the group consisting of a phosphine compound, a phosphine oxide compound, a phosphonate, a phosphite, a phosphate, a phosphorane compound, a phosphazene compound and a copolymer having a phosphate group.
3. The resin composition for underfill according to claim 1 or 2, wherein the (D) organophosphorus compound is 1 or more selected from triphenylphosphine, tris (p-methoxyphenyl) phosphine, triphenylphosphine oxide and a copolymer having a phosphate group.
4. The resin composition for underfill according to claim 1 or 2, wherein the aromatic amine compound (B) is at least 1 selected from the group consisting of diethyltoluenediamine, 3 '-diethyl-4, 4' -diaminodiphenylmethane, and dimethylthiotoluenediamine.
5. The resin composition for underfill according to claim 1 or 2, wherein the content of the (C) inorganic filler is 40 to 80 mass% with respect to the total amount of the resin composition for underfill.
6. The resin composition for underfill according to claim 1 or 2, wherein the content of the (C) inorganic filler is 60 to 75 mass% with respect to the total amount of the resin composition for underfill.
7. The resin composition for underfill according to claim 1 or 2, wherein the content of the (D) organic phosphorus compound is 0.001 to 10 mass% with respect to the (C) inorganic filler.
8. The resin composition for underfill according to claim 1 or 2, wherein the shear rate is 32.5s at 110 ℃ with an E-type viscometer－1The viscosity measured under the conditions (1) is 0.01 to 0.25 pas.
9. An electronic component device, comprising: a support member, an electronic component arranged on the support member, and a connecting portion between the support member and the electronic component,
at least a part of the connecting part is sealed with the resin composition for underfill according to any one of claims 1 to 8.
10. A method for manufacturing an electronic component device in which a support member and an electronic component are electrically connected to each other through a connection portion, comprising the steps of:
sealing at least a part of the joint with the resin composition for underfill according to any one of claims 1 to 8.
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