Liquid underfill resin composition, electronic component device, and method for manufacturing electronic component device

Abstract

To provide a liquid resin composition for underfill which is excellent in fluidity and is excellent in fracture toughness when formed into a cured product.SOLUTION: A liquid resin composition for underfill contains an epoxy resin, a curing agent, an inorganic filler, and a silicone compound containing a structural unit (A) represented by the following formula (A), a structural unit (B) represented by the following formula (B), and a structural unit (C) represented by the following formula (C): (A) -[R1-COO]-; (B) -[Si(R2)(R3)-O]-; and (C) -[R4A-O-R4B]-. R1 represents a C1-10 alkylene group; R2 and R3 each represent a C1-10 alkyl group, a C6-10 aryl group, a C1-10 alkoxy group, a C1-10 monovalent organic group having an epoxy group, a C1-10 monovalent organic group having a carboxy group, or a C3-500 polyalkylene ether group; and R4A and R4B each represent a C1-10 alkylene group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a liquid underfill resin composition, an electronic component device, and a method for manufacturing an electronic component device. [Background technology]

[0002] In the field of encapsulating semiconductor elements (hereinafter also referred to as chips) mounted on electronic component devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integration), resin encapsulation has traditionally been the mainstream due to its productivity, cost, and other factors. Epoxy resin compositions are widely used as encapsulating materials. This is because epoxy resins offer an excellent balance of various properties, including workability, moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to insert products.

[0003] Furthermore, underfill materials are widely used in electronic component devices in which semiconductor elements are bare-chip mounted, such as COB (Chip on Board), COG (Chip on Glass), and TCP (Tape Carrier Package). Furthermore, in semiconductor devices (also known as flip chips) in which semiconductor elements are directly bump-connected to wiring substrates made of ceramic, glass epoxy resin, glass imide resin, polyimide film, or the like, liquid resin compositions containing epoxy resins are used as underfill materials to fill the gaps between the bump-connected semiconductor elements and the wiring substrate. These liquid resin compositions containing epoxy resins play an important role in protecting electronic components from temperature, humidity, mechanical external forces, and the like.

[0004] When flip-chip mounting is performed, the semiconductor element and the wiring board have different thermal expansion coefficients, which can cause thermal stress at the joint between the semiconductor element and the wiring board, potentially reducing connection reliability. Furthermore, the bare chip's circuit-forming surface is not adequately protected, making it susceptible to the infiltration of moisture and ionic impurities, potentially reducing moisture resistance reliability.

[0005] Furthermore, when an underfill material is used to seal the gap between a semiconductor element and a wiring board, a fillet is usually formed on the side of the semiconductor element to protect the semiconductor element. However, thermal stress caused by the difference in thermal expansion between the wiring board and the semiconductor element can cause cracks in the fillet or even damage the semiconductor element.

[0006] Furthermore, depending on the underfill material selected, the connection may not be sufficiently protected when subjected to repeated thermal shocks in temperature cycles, etc., and the joint may suffer fatigue failure even at low cycles. Also, if voids are present due to insufficient underfill material, the bumps may not be sufficiently protected, and the joint may suffer fatigue failure at low cycles as well.

[0007] In light of this, there is a growing demand for liquid resin compositions for underfill that have high fracture toughness and excellent flowability when cured. However, when the inorganic filler content is increased to improve fracture toughness, the viscosity of the liquid epoxy resin encapsulant increases significantly, which can reduce flowability and deteriorate moldability. In this regard, a method has been reported for obtaining a liquid resin composition for underfill that provides a cured product with excellent fluidity and toughness by combining silica with specific particle sizes (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-149111 Summary of the Invention [Problem to be solved by the invention]

[0009] However, with the advancement of electronic component devices, further improvements in reliability are required, and even the method described in Patent Document 1 may not be able to provide sufficient reliability. As part of the reliability improvement, it is necessary to improve the fracture toughness of the cured product. Furthermore, with the increasing number of pins in electronic component devices, bumps are becoming smaller, with narrower pitches and narrower gaps, and so improved flowability is also required. The present disclosure has been made in consideration of the above-described conventional circumstances, and one aspect of the present disclosure has an object to provide an underfill liquid resin composition that has excellent fluidity and excellent fracture toughness when cured, as well as an electronic component device and a method for manufacturing an electronic component device that use the underfill liquid resin composition. [Means for solving the problem]

[0010] Specific means for achieving the above object are as follows. <1> Epoxy resin, A hardener; an inorganic filler; a silicone compound including a structural unit (A) represented by the following formula (A), a structural unit (B) represented by the following formula (B), and a structural unit (C) represented by the following formula (C); A liquid resin composition for underfill comprising:

[0011] [ka]

[0012] (In formula (A), R 1 represents an alkylene group having 1 to 10 carbon atoms.

[0013] [ka]

[0014] (In formula (B), R 2 and R 3each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a monovalent organic group having 1 to 10 carbon atoms and an epoxy group, a monovalent organic group having 1 to 10 carbon atoms and a carboxy group, or a polyalkylene ether group having 3 to 500 carbon atoms.

[0015] [ka]

[0016] (In formula (C), R 4A and R 4B each independently represents an alkylene group having 1 to 10 carbon atoms. <2> The number average molecular weight Mn of the silicone compound is 2,000 to 20,000. <1> The liquid resin composition for underfill according to claim 1. <3> The mass ratio of the structural unit (A) to the structural unit (B) contained in the silicone compound (structural unit (A) / structural unit (B)) is 3 / 7 to 7 / 3. <1> or <2> The liquid resin composition for underfill according to claim 1. <4> The content of the silicone compound is 1 part by mass to 50 parts by mass relative to 100 parts by mass of the epoxy resin. <1> ~ <3> 1. The liquid resin composition for underfill according to claim 1. <5> The silicone compound contains a triblock copolymer having a polymer block (A1) containing the structural unit (A), a polymer block (B) containing the structural unit (B), and a polymer block (A2) containing the structural unit (A). <1> ~ <4> 1. The liquid resin composition for underfill according to claim 1. <6> In the triblock copolymer, the polymer block (A1) and the polymer block (B) are bonded via the structural unit (C), and the polymer block (A2) and the polymer block (B) are bonded via the structural unit (C). <5> The liquid resin composition for underfill according to claim 1. <7> The silicone compound includes a compound represented by the following general formula (F): <1> ~ <6> 1. The liquid resin composition for underfill according to claim 1.

[0017] [ka]

[0018] (In general formula (F), l represents an integer of 1 to 200, and m1 + m2 represents an integer of 2 to 400. R 1 R each independently represents an alkylene group having 1 to 10 carbon atoms. 2 and R 3 R each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a monovalent organic group having 1 to 10 carbon atoms and an epoxy group, a monovalent organic group having 1 to 10 carbon atoms and a carboxy group, or a polyalkylene ether group having 3 to 500 carbon atoms. 4A and R 4B R each independently represents an alkylene group having 1 to 10 carbon atoms. 5 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. <8> The elastic modulus at 25°C when cured is 7.0 GPa or less <1> ~ <7> 1. The liquid resin composition for underfill according to claim 1. <9> When the cured product is measured by the compression method, the temperature is raised from 0°C to 300°C at a rate of 5°C / min, and the coefficient of linear expansion (CTE1) calculated as the slope of the tangent line from 10°C to 30°C is 35 ppm / °C or less. <1> ~ <8> 1. The liquid resin composition for underfill according to claim 1. <10> The content of the inorganic filler is 50% by mass to 75% by mass. <1> ~ <9> 1. The liquid resin composition for underfill according to claim 1. <11> The epoxy resin contains an epoxy resin having an epoxy equivalent of 300 g / eq to 600 g / eq. <1> ~ <10> 1. The liquid resin composition for underfill according to claim 1. <12> The epoxy resin having an epoxy equivalent of 300 g / eq to 600 g / eq has a polyether skeleton. <11> The liquid resin composition for underfill according to claim 1. <13> The present invention is used to seal the connection portion of an electronic component device including an electronic component and a support member electrically connected to the electronic component via the connection portion. <1> ~ <12> 1. The liquid resin composition for underfill according to claim 1. <14> Electronic components and a support member electrically connected to the electronic component via a connection portion; The connection portion is sealed. <1> ~ <13> a cured product of the liquid resin composition for underfill according to any one of the above items; An electronic component device comprising: <15> The connection portion between the electronic component and the support member electrically connected to the electronic component via the connection portion, <1> ~ <13> 10. A method for producing an electronic component device, comprising a step of encapsulating the device with the underfill liquid resin composition according to any one of claims 1 to 9. [Effects of the Invention]

[0019] According to one embodiment of the present disclosure, it is possible to provide an underfill liquid resin composition that has excellent fluidity and excellent fracture toughness when cured, as well as an electronic component device and a method for manufacturing an electronic component device that use the underfill liquid resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0020] Hereinafter, embodiments for carrying out the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0021] In the present disclosure, the term "process" includes not only a process that is independent of other processes, but also a process that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple substances corresponding to the component. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, the particles corresponding to each component may contain multiple types of particles. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component means the value for a mixture of the multiple types of particles present in the composition, unless otherwise specified. In the present disclosure, "(meth)acrylic" means at least one of acrylic and methacrylic.

[0022] <Liquid resin composition for underfill> The liquid resin composition for underfill of the present disclosure (hereinafter may be simply referred to as the "liquid resin composition") contains an epoxy resin, a curing agent, an inorganic filler, and a silicone compound (hereinafter may be referred to as the "specific silicone compound") containing a structural unit (A) represented by formula (A), a structural unit (B) represented by formula (B), and a structural unit (C) represented by formula (C).

[0023] [ka]

[0024] In formula (A), R 1 represents an alkylene group having 1 to 10 carbon atoms. In formula (B), R 2 and R 3each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a monovalent organic group having 1 to 10 carbon atoms and an epoxy group, a monovalent organic group having 1 to 10 carbon atoms and a carboxy group, or a polyalkylene ether group having 3 to 500 carbon atoms. In formula (C), R 4A and R 4B each independently represents an alkylene group having 1 to 10 carbon atoms.

[0025] In this disclosure, "liquid" means that the material is liquid at room temperature (25°C). Specifically, it means that the viscosity measured with an E-type viscometer at 25°C is 1000 Pa s or less.

[0026] As a result of intensive research, the present inventors have found that by including a specific silicone compound in a liquid resin composition, a liquid resin composition can be obtained that has high fracture toughness and excellent flowability when cured.

[0027] Each component contained in the liquid resin composition of the present disclosure will be described below. The liquid resin composition of the present disclosure contains an epoxy resin, a curing agent, an inorganic filler, and a specific silicone compound, and may further contain other components as necessary.

[0028] (Specific silicone compounds) The liquid resin composition of the present disclosure contains a specific silicone compound. The specific silicone compound contains the structural unit (A), the structural unit (B), and the structural unit (C), and can act as a component that reduces the elastic modulus of the cured product, that is, as a flexibilizer. R in formula (A) 1 represents an alkylene group having 1 to 10 carbon atoms, and from the viewpoint of dispersibility of the specific silicone compound, an alkylene group having 2 to 8 carbon atoms is preferred, an alkylene group having 3 to 7 carbon atoms is more preferred, and an alkylene group having 4 to 6 carbon atoms is even more preferred. R in formula (B) 2 and R 3each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a monovalent organic group having 1 to 10 carbon atoms and an epoxy group, a monovalent organic group having 1 to 10 carbon atoms and a carboxy group, or a polyalkylene ether group having 3 to 500 carbon atoms, and may be the same or different groups. The polyalkylene ether group includes a monovalent group containing at least one of a structural unit (D) represented by the following formula (D) and a structural unit (E) represented by the following formula (E).

[0029] [ka]

[0030] In formulas (D) and (E), n1+n2 represents an integer of 1 to 20, and either n1 or n2 may be 0. The terminal of the polyalkylene ether group may be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0031] From the viewpoint of the effect of reducing the elastic modulus by the specific silicone compound, R 2 and R 3 is preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and more preferably a methyl group.

[0032] R in formula (C) 4A and R 4B each independently represents an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and still more preferably an ethylene group or a trimethylene group; R 4A is a trimethylene group and R 4B is particularly preferably an ethylene group.

[0033] The specific silicone compound preferably contains a triblock copolymer having a polymer block (A1) containing a structural unit (A), a polymer block (B) containing a structural unit (B), and a polymer block (A2) containing a structural unit (A). In this case, in the triblock copolymer, the polymer block (A1) and the polymer block (B) may be bonded via the structural unit (C), and the polymer block (A2) and the polymer block (B) may be bonded via the structural unit (C). When the specific silicone compound contains a triblock copolymer, the proportion of the triblock copolymer in the specific silicone compound is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, and may be 100% by mass or less.

[0034] The specific silicone compound may include a compound represented by general formula (F). The compound represented by general formula (F) is composed of polymer blocks (A1) and (A2) containing a structural unit (A) that has high compatibility with epoxy resins, and a polymer block (B) that is a polysiloxane unit containing a structural unit (B) that exhibits a reduction in elastic modulus. When the specific silicone compound contains a compound represented by general formula (F), the proportion of the compound represented by general formula (F) in the specific silicone compound is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. The proportion of the compound represented by general formula (F) in the specific silicone compound may be 100% by mass or less.

[0035] [ka]

[0036] In the general formula (F), l represents an integer of 1 to 200, and m1+m2 represents an integer of 2 to 400. l is preferably an integer of 1 to 100, more preferably an integer of 10 to 90, still more preferably an integer of 20 to 80, and particularly preferably an integer of 30 to 50. From the viewpoint of the method for producing the specific silicone compound, it is preferable that m1 and m2 are approximately the same value. When m is m1+m2, m is an integer of 2 to 400, preferably an integer of 2 to 100, more preferably an integer of 5 to 80, still more preferably an integer of 10 to 60, particularly preferably an integer of 10 to 50, and extremely preferably an integer of 20 to 30.

[0037] In general formula (F), R 1 , R 2 and R 3 is R in formula (A) and formula (B) 1 , R 2 and R 3 The preferred specific examples thereof are the same as those of formula (A) and formula (B).

[0038] In general formula (F), R 4A and R 4B is R in formula (C) 4A and R 4B The preferred examples thereof are the same as those of formula (C). 4A and R 4B The number of carbon atoms may be the same in all compounds represented by general formula (F), or may have a distribution in the range of 1 to 10 among the molecules, particularly from the viewpoint of dispersibility. In general formula (F), R 5 R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 5 Examples of the alkyl group represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an s-butyl group. 5 is preferably a hydrogen atom. As the specific silicone compound described above, polycaprolactone-modified dimethyl silicone (product name "DBL-C32", product name "DBL-C31", etc.) manufactured by Gelest Co. is available. As the dispersibility of the liquid resin composition improves and the polysiloxane units containing the structural unit (B) are dispersed more finely, the elastic modulus of the cured product of the liquid resin composition tends to decrease, and stress tends to decrease.

[0039] From the viewpoint of reducing the elastic modulus, the number average molecular weight Mn of the specific silicone compound is preferably 2000 to 20000, more preferably 3000 to 15000, even more preferably 4000 to 12000, particularly preferably 4000 to 10000, and extremely preferably 5000 to 10000. When the number average molecular weight Mn is 2000 or more, peel strength against metal tends to be improved. Furthermore, when the number average molecular weight Mn is 20000 or less, a decrease in fluidity tends to be suppressed.

[0040] The number-average molecular weight Mn of a specific silicone compound is measured by gel permeation chromatography (GPC) and is calculated in terms of standard polystyrene. In the present disclosure, the number-average molecular weight Mn is measured using a GPC pump (Hitachi, Ltd., L-6200 model), columns (TSKgel-G5000HXL and TSKgel-G2000HXL, both manufactured by Tosoh Corporation), and a detector (Hitachi, Ltd., L-3300RI model) at a temperature of 30°C and a flow rate of 1.0 ml / min using tetrahydrofuran as an eluent.

[0041] The mass ratio of the structural unit (A) to the structural unit (B) contained in the specific silicone compound (structural unit (A) / structural unit (B)) is preferably 3 / 7 to 7 / 3, more preferably 4 / 6 to 6 / 4, and even more preferably 5 / 5, from the viewpoint of a balance between elastic modulus reduction, fluidity, and adhesiveness. When the mass ratio (structural unit (A) / structural unit (B)) is 3 / 7 or more, a decrease in adhesiveness tends to be suppressed. When the mass ratio (structural unit (A) / structural unit (B)) is 7 / 3 or less, a decrease in fluidity tends to be suppressed.

[0042] The mass ratio (structural unit (A) / structural unit (B)) is 1 It can be calculated based on the integral value of the protons derived from each structural unit determined by H-NMR measurement.

[0043] When the mass ratio of the structural unit (A) to the structural unit (B) is equal, if the number average molecular weight Mn of the specific silicone compound is about 6000, the specific silicone compound is a white solid, and if there is a large amount of the structural unit (A) at the same molecular weight, the specific silicone compound tends to become liquid.

[0044] The content of the specific silicone compound is preferably 1 to 50 parts by mass, more preferably 2 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, relative to 100 parts by mass of the epoxy resin. When the content of the specific silicone compound is 1 part by mass or more, the effect of the specific silicone compound as a flexibilizer tends to be easily exhibited. When the content of the specific silicone compound is 50 parts by mass or less, the flowability and flame retardancy tend to be improved.

[0045] [Epoxy resin] The liquid resin composition contains an epoxy resin. The epoxy resin may be any commonly used epoxy resin without any particular limitation, and is preferably an epoxy resin having two or more epoxy groups in one molecule.

[0046] As long as the liquid resin composition as a whole is liquid at room temperature, the epoxy resin may be solid or liquid at room temperature, or a combination of both. From the viewpoint of reducing the viscosity of the liquid resin composition, it is preferable to use an epoxy resin that is liquid at room temperature.

[0047] The liquid resin composition of the present disclosure may contain a solid epoxy resin as long as the desired effects are achieved. In this case, from the viewpoint of fluidity during molding, the content of the solid epoxy resin is preferably 20 mass% or less based on the total amount of the epoxy resin.

[0048] Epoxy resins include bisphenol-based epoxy resins such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and hydrogenated bisphenol A; triphenylmethane-based epoxy resins; naphthalene-based epoxy resins; epoxidized novolac resins of phenols and aldehydes, such as orthocresol novolac-based epoxy resins; glycidyl ester-based epoxy resins obtained by reacting epichlorohydrin with polybasic acids such as phthalic acid or dimer acid; glycidyl amine-based epoxy resins obtained by reacting epichlorohydrin with amine compounds such as p-aminophenol, diaminodiphenylmethane, or isocyanuric acid; linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; alicyclic epoxy resins; and epoxy resins with flexible backbones. The "flexible backbone" of an epoxy resin refers to a partial structure that imparts flexibility to the epoxy resin, such as an alkylene oxide group, a polyether group, a long-chain alkyl group, or a siloxane backbone. Examples of the alkylene oxide group include an ethylene oxide group and a propylene oxide group. The epoxy resins may be used alone or in combination of two or more.

[0049] The epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of a balance of various properties such as moldability, reflow resistance, and electrical reliability, it is preferably 80 g / eq to 1000 g / eq, more preferably 90 g / eq to 1000 g / eq, even more preferably 100 g / eq to 1000 g / eq, and particularly preferably 150 g / eq to 600 g / eq. In the present disclosure, the epoxy equivalent of the epoxy resin is a value measured by a method in accordance with JIS K 7236:2009.

[0050] The softening point or melting point of the epoxy resin is not particularly limited. From the viewpoints of moldability and reflow resistance, the softening point or melting point of the epoxy resin is preferably 40°C to 180°C, and from the viewpoint of handleability during preparation of the liquid resin composition, it is more preferably 50°C to 130°C. The melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method (ring and ball method) in accordance with JIS K 7234:1986.

[0051] The amount of hydrolyzable chlorine, which is one index of the purity of an epoxy resin, is preferably 500 ppm or less, more preferably 300 ppm or less, from the viewpoint of suppressing corrosion of wiring on semiconductor elements such as ICs and obtaining a liquid resin composition with excellent moisture resistance. The amount of hydrolyzable chlorine is measured by dissolving 1 g of epoxy resin in 30 ml of dioxane, adding 5 ml of 1N KOH methanol solution, refluxing for 30 minutes, and then determining the value by potentiometric titration.

[0052] The content of the epoxy resin in the liquid resin composition is not particularly limited, but from the viewpoints of viscosity, glass transition temperature, heat resistance, etc., it is preferably 0.5% by mass to 50% by mass, more preferably 2% by mass to 40% by mass, and even more preferably 2% by mass to 30% by mass.

[0053] The epoxy resin preferably contains at least one selected from the group consisting of naphthalene skeleton-containing epoxy resins, glycidylamine-type epoxy resins, and bisphenol-type epoxy resins. Among these, from the viewpoints of viscosity, usage history, and material cost, the epoxy resin preferably contains a bisphenol-type epoxy resin and a glycidylamine-type epoxy resin, from the viewpoint of fluidity, it is preferable to contain a liquid bisphenol-type epoxy resin, and from the viewpoints of heat resistance, adhesiveness, and fluidity, it is preferable to contain a liquid glycidylamine-type epoxy resin.

[0054] As the epoxy resin containing a naphthalene skeleton, 1,6-bis(glycidyloxy)naphthalene is preferred.

[0055] Examples of bisphenol type epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD ​​type epoxy resins, etc. From the viewpoint of reducing viscosity, the bisphenol type epoxy resin is preferably bisphenol F type epoxy resin.

[0056] The glycidylamine type epoxy resin may be bifunctional or trifunctional or higher. From the viewpoint of improving heat resistance after curing, trifunctional or higher glycidylamine type epoxy resins (having three or more epoxy groups in one molecule) are preferred. Examples of bifunctional glycidylamine type epoxy resins include N,N-diglycidylaniline and N,N-diglycidyl-o-toluidine. Examples of trifunctional or higher glycidylamine type epoxy resins include triglycidyl-p-aminophenol and 4,4'-methylenebis[N,N-bis(oxiranylmethyl)aniline]. Among these, triglycidyl-p-aminophenol is preferred from the viewpoint of viscosity at room temperature (25°C).

[0057] The epoxy equivalent (molecular weight / number of epoxy groups) of at least one epoxy resin selected from the group consisting of naphthalene skeleton-containing epoxy resins, glycidylamine-type epoxy resins, and bisphenol-type epoxy resins is not particularly limited. From the viewpoint of a balance of various properties such as moldability, reflow resistance, and electrical reliability, it is preferably 70 g / eq to 500 g / eq, more preferably 80 g / eq to 400 g / eq, and even more preferably 90 g / eq to 300 g / eq.

[0058] As the at least one epoxy resin selected from the group consisting of naphthalene skeleton-containing epoxy resins, glycidylamine-type epoxy resins, and bisphenol-type epoxy resins, commercially available epoxy resins include YDF8170C (trade name, manufactured by Nippon Steel Chemical & Material Co., Ltd.), jER630 (trade name, manufactured by Mitsubishi Chemical Corporation), and HP4032D (trade name, manufactured by DIC Corporation).

[0059] When the epoxy resin contains at least one epoxy resin selected from the group consisting of naphthalene skeleton-containing epoxy resins, glycidylamine type epoxy resins, and bisphenol type epoxy resins, the total content of the at least one epoxy resin selected from the group consisting of naphthalene skeleton-containing epoxy resins, glycidylamine type epoxy resins, and bisphenol type epoxy resins is not particularly limited, and is preferably 50 parts by mass to 100 parts by mass, and more preferably 70 parts by mass to 100 parts by mass, per 100 parts by mass of the total epoxy resins.

[0060] It is also preferable that the epoxy resin contains an epoxy resin with an epoxy equivalent of 300 g / eq to 600 g / eq. The epoxy resin with an epoxy equivalent of 300 g / eq to 600 g / eq is preferably an epoxy resin with an epoxy equivalent of 350 g / eq to 550 g / eq, and more preferably an epoxy resin with an epoxy equivalent of 400 g / eq to 500 g / eq. When the epoxy resin contains an epoxy resin with an epoxy equivalent of 300 g / eq to 600 g / eq, the temperature cycle resistance tends to be further improved. Although the reason for this is not entirely clear, it is presumed that the use of an epoxy resin with an epoxy equivalent of 300 g / eq to 600 g / eq reduces the density between crosslinks, thereby reducing the elastic modulus and improving toughness.

[0061] From the viewpoint of temperature cycle resistance, the epoxy resin having an epoxy equivalent of 300 g / eq to 600 g / eq is preferably at least one selected from the group consisting of epoxy resins having a polyether skeleton, epoxy resins having a fluorene structure, epoxy resins having a long-chain alkyl group, epoxy resins having a siloxane skeleton, epoxy resins having a bisphenol A skeleton, and epoxy resins having a bisphenol F skeleton.

[0062] Among these, the epoxy resin having an epoxy equivalent of 300 g / eq to 600 g / eq is preferably an epoxy resin having a polyether skeleton. When the epoxy resin has an epoxy equivalent of 300 g / eq to 600 g / eq and contains an epoxy resin having a polyether skeleton, the breaking energy tends to be improved and the temperature cycle resistance tends to be further improved. Although the reason for this is not entirely clear, it is presumed that the epoxy resin having a polyether skeleton has flexibility, resulting in a lower elastic modulus and improved toughness. The polyether skeleton is not particularly limited, and examples thereof include a polyalkylene oxide structure.

[0063] Examples of commercially available epoxy resins having an epoxy equivalent weight of 300 g / eq to 600 g / eq include YL7410 (trade name, manufactured by Mitsubishi Chemical Corporation), Epogosey PT (trade name, manufactured by Yokkaichi Synthetic Co., Ltd.), EXA4816 (trade name, manufactured by DIC Corporation), and CG400 (trade name, manufactured by Osaka Gas Chemicals Co., Ltd.). YL7410 is an epoxy resin having a polyether skeleton in the molecule, as disclosed in International Publication No. 2012 / 093510.

[0064] When the epoxy resin contains an epoxy resin with an epoxy equivalent weight of 300 g / eq to 600 g / eq, the content of the epoxy resin with an epoxy equivalent weight of 300 g / eq to 600 g / eq relative to the total amount of epoxy resin is not particularly limited. From the viewpoint of temperature cycle resistance, the content is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, per 100 parts by mass of the total epoxy resin. When the content of the epoxy resin with an epoxy equivalent weight of 300 g / eq to 600 g / eq is 0.1 to 40 parts by mass per 100 parts by mass of the total epoxy resin, temperature cycle resistance tends to be improved while maintaining the properties of the liquid resin composition, such as fluidity and thermal expansion coefficient, within desired ranges.

[0065] [Hardening agent] The liquid resin composition contains a curing agent. The curing agent can be any commonly used epoxy resin curing agent without any particular limitations. Examples include amine curing agents, phenolic curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents. Among these, from the viewpoint of workability, at least one selected from the group consisting of amine curing agents, phenolic curing agents, and acid anhydride curing agents is preferred, and amine curing agents are more preferred. The curing agent may be solid or liquid at room temperature, and is preferably liquid. One type of curing agent may be used alone, or two or more types may be used in combination.

[0066] Among these, from the viewpoint of excellent temperature cycle resistance, moisture resistance, etc., and improving the reliability of electronic component devices, the curing agent is preferably an aromatic amine, and more preferably an aromatic amine that is liquid at room temperature (also referred to as a liquid aromatic amine). Examples of liquid aromatic amines include ethyltoluenediamine, diethyltoluenediamine (3,5-diethyltoluene-2,4-diamine and 3,5-diethyltoluene-2,6-diamine, etc.), 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,5,3',5'-tetramethyl-4,4'-diaminodiphenylmethane, and dimethylthiotoluenediamine. The curing agents may be used alone or in combination of two or more.

[0067] Among these, from the viewpoint of storage stability, 3,3'-diethyl-4,4'-diaminodiphenylmethane, ethyltoluenediamine, and dimethylthiotoluenediamine are preferred, and the curing agent preferably contains one or a mixture of two or more of these as the main component.

[0068] Commercially available aromatic amines include, for example, liquid aromatic amines such as jER Cure W (trade name, manufactured by Mitsubishi Chemical Corporation), Kayahard AA, Kayahard AB, and Kayahard AS (trade names, manufactured by Nippon Kayaku Co., Ltd.), Thothamine HM-205 (trade name, manufactured by Nippon Steel Chemical & Material Co., Ltd.), Adeka Hardener EH-101 (trade name, manufactured by Adeka Corporation), Epomic Q-640 and Epomic Q-643 (trade names, manufactured by Mitsui Chemicals, Inc.), and DETDA80 (trade name, manufactured by Lonza).

[0069] When a liquid aromatic amine is used as the curing agent, a commonly used curing agent such as a phenolic curing agent, an acid anhydride curing agent, etc. may be used in combination with the liquid aromatic amine. Also, a solid curing agent may be used in combination with the liquid aromatic amine.

[0070] The functional group equivalent of the curing agent is not particularly limited. From the viewpoint of reactivity, the functional group equivalent is preferably 30 g / eq to 300 g / eq, and more preferably 35 g / eq to 200 g / eq.

[0071] The amount of curing agent to be blended relative to the epoxy resin is not particularly limited. In order to minimize the amount of unreacted components, the equivalent ratio of the epoxy resin to the curing agent, i.e., the ratio of the number of functional groups in the curing agent to the number of epoxy groups in the epoxy resin (number of functional groups in the curing agent / number of epoxy groups in the epoxy resin), is preferably 0.5 to 2.0, more preferably 0.6 to 1.8, and even more preferably 0.7 to 1.5.

[0072] [Inorganic filler] The liquid resin composition contains an inorganic filler. Examples of inorganic fillers include silica (e.g., spherical silica, crystalline silica), calcium carbonate, clay, alumina, silicon nitride, silicon carbide, boron nitride, calcium silicate, potassium titanate, aluminum nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, and titania powders, as well as beads and glass fibers formed from these materials. Furthermore, flame-retardant inorganic fillers such as aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdate may also be used. The inorganic fillers may be used alone or in combination of two or more. Among these, silica is preferred from the viewpoints of availability, chemical stability, and material cost. Spherical silica is more preferred from the viewpoints of fluidity and penetration of the liquid resin composition into fine gaps. Examples of spherical silica include silica obtained by a deflagration method and fused silica. The inorganic filler may be surface-treated in advance with various surface treatment agents, such as the coupling agents described below.

[0073] The volume average particle size of the inorganic filler is not particularly limited. For example, in the case of spherical silica, the volume average particle size is preferably 0.1 μm to 10 μm, more preferably 0.2 μm to 7 μm, even more preferably 0.3 μm to 5 μm, and particularly preferably 0.3 μm to 1.3 μm. A volume average particle size of 0.1 μm or more tends to provide excellent dispersibility in the liquid resin composition, to prevent the liquid resin composition from becoming thixotropic, and to provide excellent flow properties. A volume average particle size of 10 μm or less tends to reduce sedimentation of the inorganic filler in the liquid resin composition, to improve the permeability and flowability of the liquid resin composition into fine gaps, and to prevent voids and unfilled particles. The volume average particle size of the inorganic filler can be measured as the particle size (D50) at which the cumulative total from the smallest diameter side reaches 50% in the volume-based particle size distribution measured using a laser diffraction / scattering particle size distribution analyzer.

[0074] The content of the inorganic filler is not particularly limited, and is preferably 30% by mass or more of the total liquid resin composition, more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 55% by mass or more. The content of the inorganic filler is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less, of the entire liquid resin composition. When the content of the inorganic filler is 30% by mass or more, the thermal expansion coefficient is likely to be reduced, and when it is 80% by mass or less, an increase in the viscosity of the liquid resin composition is likely to be suppressed, and the fluidity, penetration, and dispensability tend to be improved.

[0075] In particular, the content of the inorganic filler is preferably 50% by mass to 75% by mass, and more preferably 55% by mass to 75% by mass, of the total liquid resin composition. Generally, increasing the content of the inorganic filler to adjust the linear expansion coefficient tends to increase the modulus of elasticity. However, since the liquid resin composition of the present disclosure contains a specific silicone compound, an increase in the content of the inorganic filler tends to be suppressed. Therefore, for example, the content of the inorganic filler may be 55% by mass or more, and the modulus of elasticity at room temperature (25°C) of the cured product described below may be 7.0 GPa or less.

[0076] [Coupling agent] The liquid resin composition may contain a coupling agent as needed. When the liquid resin composition contains a coupling agent, it tends to strengthen the interfacial adhesion between the epoxy resin and the inorganic filler, or between the epoxy resin and the constituent members of the electronic component. There are no particular limitations on the type of coupling agent, and conventionally known coupling agents can be used. Examples include silane compounds having primary and / or secondary and / or tertiary amino groups, various silane-based compounds such as epoxy silane, mercaptosilane, alkylsilane, ureidosilane, vinylsilane, and (meth)acrylic silane, titanium-based compounds, aluminum chelates, and aluminum / zirconium-based compounds. The coupling agents may be used alone or in combination of two or more.

[0077] As the coupling agent, for example, a monomer or an oligomer may be used. Monomer coupling agents include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloxypropyltrimethoxysilane, glycidoxyoctyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-anilinopropyltrimethoxysilane, 3-anilinopropyltriethoxysilane, [3-(N,N-dimethyl [3-(N,N-diethylamino)propyl]trimethoxysilane, [3-(N,N-dibutylamino)propyl]trimethoxysilane, [3-(methylamino)propyl]trimethoxysilane, [3-(ethylamino)propyl]trimethoxysilane, [3-(N,N-dimethylamino)propyl]triethoxysilane, [3-(N,N-diethylamino)propyl]triethoxysilane, [3-(N,N-dibutylamino)propyl]triethoxysilane, [3-(methylamino)propyl]triethoxysilane, [3-(ethylamino)propyl]triethoxysilane, [3-(N,N-dimethylamino)propyl]methyldimethoxysilane, [3-(N,Silane coupling agents such as [N-dibutylamino)propyl]methyldimethoxysilane, [3-(methylamino)propyl]methyldimethoxysilane, [3-(ethylamino)propyl]methyldimethoxysilane, N-[3-(trimethoxysilyl)propyl]ethylenediamine, N-[3-(dimethoxymethylsilyl)propyl]ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, 3-chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltrimethoxysilane, hexenyltrimethoxysilane, octenyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and methacryloxyoctyltrimethoxysilane; isopropyl triisostearoyl titanate, isopropyl tris(dioctylpyrophosphate)titanate Examples of titanate coupling agents include isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl phosphite) titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, bis(dioctyl pyrophosphate)ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tridodecyl benzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, and tetraisopropyl bis(dioctyl phosphite) titanate.

[0078] Furthermore, examples of the oligomer coupling agent include methyl-based, methyl / phenyl-based, propyl / phenyl-based, epoxy-modified, mercapto-modified, amine-modified, (meth)acrylic-modified, and polyester resin-modified alkoxy oligomers.

[0079] The content of the coupling agent in the liquid resin composition is not particularly limited. From the viewpoints of adhesiveness, fluidity, etc., the content of the coupling agent is preferably 0.01% by mass to 20% by mass, and more preferably 0.01% by mass to 10% by mass, based on the total amount of the epoxy resin.

[0080] Furthermore, in order to promote the condensation reaction of the coupling agent and the reaction between the silanol groups in the coupling agent and the silanol groups of an inorganic filler such as silica, thereby improving the dispersibility of the inorganic filler and reducing the viscosity of the liquid resin composition, a catalyst such as an acid that supplies protons, a Lewis acid, or the like may be added. Among these, from the viewpoint of storage stability, a chelating agent containing a metal species is preferred as the Lewis acid. Examples of the chelating agent containing a metal species include chelating agents containing aluminum, boron, cobalt, titanium, etc. The content of the Lewis acid is preferably 0.001 to 1.0 part by mass, more preferably 0.002 to 0.8 part by mass, and even more preferably 0.005 to 0.6 part by mass, relative to 100 parts by mass of the inorganic filler.

[0081] [Other ingredients] In addition to the above-mentioned components, the liquid resin composition may contain various additives such as a flexibilizer, a surfactant, a curing accelerator, an ion exchanger, etc. In addition to the additives exemplified below, the liquid resin composition may also contain various additives known in the art, as needed.

[0082] (flexible agent) The liquid resin composition may contain various flexibilizers other than the specific silicone compound from the viewpoints of improving thermal shock resistance and reducing stress on semiconductor elements. The type of flexibilizer is not particularly limited, and those commonly used in the relevant field, such as silicone rubber, acrylic elastomer, and phenoxy resin, may be used. Among these, rubber particles are preferred as the flexibilizer. Examples of rubber particles include particles of styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), butadiene rubber (BR), urethane rubber (UR), and acrylic rubber (AR). One type of flexibilizer may be used alone, or two or more types may be used in combination.

[0083] (surfactant) The liquid resin composition may contain a surfactant. One type of surfactant may be used alone, or two or more types may be used in combination. An example of the surfactant is a silicone-modified epoxy resin. The silicone-modified epoxy resin can be obtained as a reaction product between an organosiloxane having a functional group reactive with an epoxy group and an epoxy resin. The silicone-modified epoxy resin is preferably liquid at room temperature.

[0084] Examples of organosiloxanes having a functional group reactive with an epoxy group include dimethylsiloxane, diphenylsiloxane, and methylphenylsiloxane, each of which has one or more amino groups, carboxyl groups, hydroxyl groups, phenolic hydroxyl groups, mercapto groups, and the like per molecule. The weight-average molecular weight of the organosiloxane having a functional group reactive with an epoxy group is not particularly limited, but is preferably 500 to 5,000. When the weight-average molecular weight is 500 or more, compatibility with the resin system is not too high, and the additive effect is easily exerted. When the weight-average molecular weight is 5,000 or less, the silicone-modified epoxy resin is compatible with the resin component, and separation, exudation, and the like of the silicone-modified epoxy resin are suppressed when the liquid resin composition is cured, and adhesion and appearance tend not to be impaired.

[0085] The epoxy resin used to obtain the silicone-modified epoxy resin is not particularly limited as long as it is compatible with the resin component of the liquid resin composition, and any epoxy resin commonly used in liquid resin compositions can be used. Examples of epoxy resins for obtaining silicone-modified epoxy resins include glycidyl ether-type epoxy resins obtained by reacting bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalenediol, hydrogenated bisphenol A, or the like, with epichlorohydrin; novolac-type epoxy resins obtained by epoxidizing novolac resins obtained by condensing or co-condensing phenols and aldehydes, such as orthocresol novolac-type epoxy resins; glycidyl ester-type epoxy resins obtained by reacting polybasic acids such as phthalic acid and dimer acid with epichlorohydrin; glycidyl amine-type epoxy resins obtained by reacting polyamines such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin; linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; and alicyclic epoxy resins. The epoxy resins for obtaining silicone-modified epoxy resins may be used alone or in combination of two or more. Epoxy resins that are liquid at room temperature are preferred as epoxy resins for obtaining silicone-modified epoxy resins.

[0086] The content of the surfactant in the liquid resin composition is not particularly limited, and is preferably 0.01% by mass to 1.5% by mass, and more preferably 0.05% by mass to 1% by mass, based on the total mass of the liquid resin composition. If the content is 0.01% by mass or more, the surfactant tends to exert its effect more easily, and if it is 1.5% by mass or less, bleeding from the surface of the cured product during curing tends to be suppressed, and adhesive strength tends to be improved.

[0087] (curing accelerator) The liquid resin composition may contain a curing accelerator as needed. The type of curing accelerator is not particularly limited, and conventionally known accelerators can be used. Examples of the curing accelerator include cycloamidine compounds such as 1,8-diazabicyclo[5.4.0]undecene-7, 1,5-diazabicyclo[4.3.0]nonene, and 5,6-dibutylamino-1,8-diazabicyclo[5.4.0]undecene-7; tertiary amine compounds such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-ethyl-4-methyl-2 ... imidazole compounds such as 2-phenylimidazole, 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-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, and 2-heptadecylimidazole compounds having intramolecular polarization obtained by adding to these compounds quinone compounds such as maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone, diazophenylmethane, and phenolic resins; tetraphenylborate salts such as 2-ethyl-4-methylimidazolium tetraphenylborate and N-methylmorpholinium tetraphenylborate; and derivatives thereof. Alternatively, a curing accelerator having potentiality may be used. Examples of the curing accelerator having potentiality include core-shell particles formed by coating a shell of an epoxy compound that is solid at room temperature on a core of a compound having an amino group that is solid at room temperature. Examples of such core-shell particles include Amicure (trade name, manufactured by Ajinomoto Co., Inc.) which is a commercially available product, and Novacure (trade name, manufactured by Asahi Kasei Chemicals Corporation) in which microencapsulated amine is dispersed in a bisphenol A type epoxy resin or a bisphenol F type epoxy resin. The curing accelerator may be used alone or in combination of two or more kinds.

[0088] The content rate of the curing accelerator is not particularly limited as long as it is an amount that achieves the curing acceleration effect, and it is preferably 0.1% by mass to 40% by mass, more preferably 1% by mass to 20% by mass with respect to the epoxy resin. When the content rate of the curing accelerator is 0.1% by mass or more with respect to the epoxy resin, it tends to have excellent curability even in a short time, and when it is 40% by mass or less, it is easy to control the curing rate and tends to be easy to control the storage stability such as pot life and shell life.

[0089] (Ion exchanger) The liquid resin composition may contain an ion exchanger as needed. When the liquid resin composition contains an ion exchanger, the migration resistance, moisture resistance, high-temperature storage characteristics, etc. of semiconductor elements such as ICs tend to be improved. Examples of the ion exchanger include compounds represented by the following compositional formula (A) or (B). Mg 1-X Al X (OH)2(CO3) X / 2 ·mH2O ···(A) (0 < X ≦ 0.5, m is a positive number) BiO x (OH) y (NO3) z ···(B) (0.9 ≦ x ≦ 1.1, 0.6 ≦ y ≦ 0.8, 0.2 ≦ z ≦ 0.4)

[0090] The content of the ion exchanger is not particularly limited, but is preferably 0.1 to 3.0% by mass, more preferably 0.3 to 1.5% by mass, of the total liquid resin composition. The volume average particle size of the ion exchanger is preferably 0.1 to 3.0 μm. The volume average particle size of the ion exchanger can be measured as the particle size (D50) at which the cumulative total from the small diameter side reaches 50% in the volume-based particle size distribution measured using a laser diffraction / scattering particle size distribution analyzer. The maximum particle size of the ion exchanger is preferably 10 μm.

[0091] An example of the compound represented by the composition formula (A) is the commercially available product DHT-4A (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.). An example of the compound represented by the composition formula (B) is the commercially available product IXE500 (trade name, manufactured by Toagosei Co., Ltd.). If necessary, other anion exchangers may be added. The type of anion exchanger is not particularly limited, and conventionally known anion exchangers can be used. Examples include hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, etc. One type of ion exchanger may be used alone, or two or more types may be used in combination.

[0092] (Other additives) The liquid resin composition may contain other additives, such as dyes, colorants such as carbon black, diluents, leveling agents, antifoaming agents, and antioxidants, as needed.

[0093] [Method for preparing liquid resin composition] The liquid resin composition may be prepared by any method that can uniformly disperse and mix the various components, for example, by weighing the components, mixing and kneading them using a three-roll mill, a mixing machine, a mixing roll, a planetary mixer, or the like, and degassing as necessary.

[0094] [Physical Properties of Liquid Resin Composition] (viscosity) The viscosity of the liquid resin composition is not particularly limited. From the viewpoint of fluidity, the viscosity of the liquid resin composition is preferably 1 Pa·s to 50 Pa·s at 25°C, more preferably 3 Pa·s to 30 Pa·s, and even more preferably 3 Pa·s to 20 Pa·s. The viscosity of the liquid resin composition at 25°C is measured using an EHD rotational viscometer. Specifically, it can be measured by the method described in the examples.

[0095] Furthermore, from the viewpoint of filling properties when filling a narrow gap with a liquid resin composition at around 100°C to 120°C for applications such as underfill material, the viscosity of the liquid resin composition at 110°C is, for example, preferably 0.3 Pa·s or less, and more preferably 0.2 Pa·s or less. The viscosity of the liquid resin composition at 110°C may be 0.05 Pa·s or more. The viscosity of the liquid resin composition at 110° C. is measured using a rheometer. Specifically, it can be measured by the method described in the examples.

[0096] [Physical Properties of Cured Liquid Resin Composition] In the measurements of the thermal expansion coefficient, modulus of elasticity, and glass transition temperature of the cured product of the liquid resin composition described below, the cured product is obtained by heating the liquid resin composition at 150°C for 2 hours.

[0097] (coefficient of linear expansion) The linear expansion coefficient of the liquid resin composition when cured is not particularly limited. For example, when the temperature is increased from 0°C to 300°C at a rate of 5°C / min by a compression method, the linear expansion coefficient (CTE1) is calculated as the slope of the tangent from 10°C to 30°C. The linear expansion coefficient (CTE1) is preferably 35 ppm / °C or less, more preferably 32 ppm / °C or less, even more preferably 30 ppm / °C or less, and particularly preferably 28 ppm / °C or less. When the linear expansion coefficient at or below the glass transition temperature is 35 ppm / °C or less, the occurrence of bump cracks during reflow tends to be suppressed and the temperature cycle resistance tends to be improved. The thermal expansion coefficient at or below the glass transition temperature may be 15 ppm / °C or more. The thermal expansion coefficient at or below the glass transition temperature can be measured by TMA (thermomechanical analysis). Specifically, it can be measured by the method described in the Examples.

[0098] Generally, when the elastic modulus of a liquid resin composition decreases, the linear expansion coefficient tends to increase. Therefore, it is generally difficult to suppress the linear expansion coefficient while decreasing the elastic modulus. However, the liquid resin composition of the present disclosure tends to be able to suppress the linear expansion coefficient while decreasing the elastic modulus. Therefore, it is believed that the liquid resin composition of the present disclosure can effectively improve temperature cycle resistance.

[0099] (elastic modulus) The elastic modulus of the liquid resin composition when cured is not particularly limited. For example, from the viewpoint of further improving temperature cycle resistance, the elastic modulus of the liquid resin composition when cured at room temperature (25°C) is preferably 7.0 GPa or less, more preferably 6.8 GPa or less, and even more preferably 6.5 GPa or less. Furthermore, for example, from the viewpoint of reflow resistance, the elastic modulus at 200°C when the liquid resin composition of the present disclosure is cured is preferably 0.15 GPa or less, more preferably 0.10 GPa or less, and even more preferably 0.08 GPa or less. The elastic modulus of the liquid resin composition when cured can be measured by DMA (dynamic viscoelasticity measurement), specifically by the method described in the examples.

[0100] (glass transition temperature) The glass transition temperature (Tg) of the liquid resin composition when cured is not particularly limited, but is preferably 60°C to 150°C, more preferably 70 to 150°C, and even more preferably 80 to 150°C. A glass transition temperature of 60°C or higher tends to provide high bump protection at high temperatures and reduce the risk of breakage. A glass transition temperature of 150°C or lower tends to reduce the risk of significant warping at room temperature (25°C). The glass transition temperature of the cured product can be measured using a thermomechanical analyzer (TMA). Specifically, it can be measured by the method described in the examples.

[0101] [Uses of liquid resin composition] The liquid resin composition of the present disclosure can be used to seal the connection portion of an electronic component device including an electronic component and a support member electrically connected to the electronic component via the connection portion. The configuration of the electronic component device and the sealing method are described in detail below.

[0102] <Electronic component device and method for manufacturing electronic component device> The electronic component device of the present disclosure includes an electronic component, a support member electrically connected to the electronic component via a connection portion, and a cured product of the liquid underfill resin composition of the present disclosure that seals the connection portion. The manufacturing method of the electronic component device of the present disclosure includes a step of sealing the connection between the electronic component and the support member electrically connected to the electronic component via the connection with the underfill liquid resin composition of the present disclosure.

[0103] Examples of electronic components include active elements such as semiconductor elements, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, resistor arrays, coils, and switches. The size of the electronic component is not particularly limited, and an example is a semiconductor element measuring 20 mm in length and 20 mm in width. Furthermore, the liquid resin composition of the present disclosure exhibits excellent reliability as an underfill material even for larger semiconductor elements.

[0104] Examples of the support member include a lead frame, a pre-wired tape carrier, a wiring board (rigid or flexible), glass, a silicon wafer, and the like.

[0105] In the electronic component device of the present disclosure, the electronic component and the support member are electrically connected via a connecting portion. Examples of the connecting portion include bumps. The bumps may be, for example, bumps using copper pillars. Packages with bumps using copper pillars have become increasingly popular for thinner or denser packages, but generally tend to suffer from defects such as peeling after temperature cycling, cracking, and peeling after moisture absorption and heat resistance testing. However, the electronic component device of the present disclosure uses the liquid resin composition of the present disclosure, and therefore has excellent temperature cycle resistance even for packages using copper pillars.

[0106] Examples of electronic component devices include flip-chip semiconductor devices obtained by flip-chip bonding electronic components onto a support member using bump connections. Examples of flip-chip semiconductor devices include BGA (Ball Grid Array), LGA (Land Grid Array), and COF (Chip On Film).

[0107] The electronic component device may be a high-density or large-sized electronic component device. Generally, as the density or size of electronic component devices increases, the size of electronic components increases, and the number of pins increases, resulting in smaller bump diameters, narrower pitches, and narrower gaps. This tends to result in defects such as peeling and cracks after temperature cycling. However, because the electronic component device of the present disclosure uses the liquid resin composition of the present disclosure, even high-density or large-sized electronic component devices have excellent temperature cycle resistance.

[0108] In the electronic component device of the present disclosure, the connection portions are sealed with a cured product of the liquid resin composition of the present disclosure. The method of applying the liquid resin composition to the connection portions is not particularly limited, and examples thereof include a dispensing method, a casting method, and a printing method. [Example]

[0109] The present disclosure will be specifically described below using examples, but the present invention is not limited to these examples.

[0110] The components used in the liquid resin compositions of the Examples and Comparative Examples are shown below. Epoxy resin 1: Bisphenol F liquid epoxy resin with an epoxy equivalent of 160 g / eq (Nippon Steel Chemical & Material Co., Ltd., product name: YDF8170C) Epoxy resin 2: A trifunctional liquid epoxy resin with an epoxy equivalent of 95 g / eq (manufactured by Mitsubishi Chemical Corporation, product name: jER630) Flexible agent: Core-shell rubber particles in which the core contains cross-linked polydimethylsiloxane and the shell contains polymethyl methacrylate and glycidyl methacrylate as structural units (content of cross-linked polymethylsiloxane: 68% by mass based on the total mass of the core and shell, volume average particle size (primary particles): 131 nm) Specific silicone compound: Polycaprolactone-modified dimethyl silicone, amorphous polymer, Tg 55°C (Gelest, product name "DBL-C32" (compound represented by general formula (F))) Curing agent 1: Liquid amine resin with an active hydrogen equivalent of 45 g / eq (manufactured by Mitsubishi Chemical Corporation, product name: jER Cure W) Curing agent 2: Liquid amine resin with an active hydrogen equivalent of 63 g / eq (manufactured by Nippon Kayaku Co., Ltd., product name: Kayahard AA) Colorant: Carbon black, Mitsubishi Chemical product name "MA-100" Antioxidant: Tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid)pentaerythritol Ion exchanger: a compound represented by formula (B) (IXE500 (product name, Toagosei Co., Ltd.)) Inorganic filler: Spherical fused silica with an average particle size of 0.6 μm and a maximum particle size of 25 μm, the surface of which has been treated with an epoxy silane coupling agent (manufactured by Admatechs Co., Ltd., product name "SE2200-SEJ")

[0111] The components were mixed in the compositions shown in Table 1 and kneaded and dispersed using a three-roll mill and a vacuum kneading mill to prepare liquid resin compositions for the Examples and Comparative Examples.

[0112] <Evaluation of flow characteristics> (Viscosity at 25°C) The prepared liquid resin composition was rotated at a predetermined rotation speed (10 rotations / min, 5 rotations / min, 2.5 rotations / min, 1 rotation / min) for 1 minute at 25°C in an EHD rotational viscometer, and the measured value was multiplied by a predetermined conversion factor to obtain the viscosity at 25°C. The measured value was obtained for the composition kept at 25±1°C using an EHD rotational viscometer equipped with a cone rotor with a cone angle of 3° and a cone radius of 14 mm. The rotation speed and conversion factor were determined based on a rough estimate of the viscosity of the composition to be measured. When the estimated viscosity of the composition to be measured was 0 Pa·s or more and less than 50 Pa·s, the rotation speed was 10 rpm and the conversion factor was 0.5; when the estimated viscosity was 50 Pa·s or more and less than 100 Pa·s, the rotation speed was 5 rpm and the conversion factor was 1; when the estimated viscosity was 100 Pa·s or more and less than 200 Pa·s, the rotation speed was 2.5 rpm and the conversion factor was 2; and when the estimated viscosity was 200 Pa·s or more and less than 500 Pa·s, the rotation speed was 1 rpm and the conversion factor was 5.

[0113] (Viscosity at 110°C) The viscosity of the prepared liquid resin composition at 110°C was measured using AR2000 (trade name, manufactured by TA Instruments) under conditions of 40 mm parallel plates and a shear rate of 32.5 (1 / s), and the viscosity at 110°C was measured.

[0114] (Evaluation of coefficient of thermal expansion (CTE1)) The liquid resin composition was cured at 150°C for 2 hours to prepare a test piece. The cured liquid resin composition was cut into a piece measuring φ8 mm x 20 mm, and the temperature was measured by the compression method using a thermomechanical analyzer (trade name: TMA2940, manufactured by TA Instruments) by increasing the temperature from 0°C to 300°C at a rate of 5°C / min, and the slope of the tangent from 10°C to 30°C was defined as CTE1.

[0115] (glass transition temperature) A test piece was prepared by curing the liquid resin composition at 150°C for 2 hours. Measurement was carried out using the same equipment and conditions as in the evaluation of the thermal expansion coefficient, and the temperature corresponding to the intersection of the tangent lines at 50°C and 150°C was taken as the glass transition temperature (°C).

[0116] (Evaluation of elastic modulus) The liquid resin composition was cured at 150°C for 2 hours to prepare a test piece. The cured liquid resin composition was cut into a piece measuring 50 mm x 10 mm x 3 mm, and the temperature was raised from 20°C to 300°C at a rate of 5°C / min using a viscoelasticity measuring device (trade name: RSAIII, manufactured by TA Instruments) under conditions of a span distance of 40 mm and a frequency of 1 Hz using a three-point bending method. The storage modulus value at 25°C was taken as the room-temperature modulus. The storage modulus value at 200°C was taken as the high-temperature modulus.

[0117] (Measurement of fracture toughness value) The liquid resin composition was poured into a mold and cured at 150°C for 2 hours to prepare test pieces measuring 12.75 mm x 60 mm x 4 mm. The fracture toughness value (MPa m 1 / 2 The fracture toughness of the test piece was calculated by three-point bending measurement based on ASTM D5045. The evaluation device used was an Instron 5948 (Instron Corporation). The obtained measurement value is shown in Table 1 as fracture toughness 1. The test pieces were further heat-treated at 150°C for 100 hours, and the fracture toughness values ​​of the heat-treated test pieces were measured in the same manner. The measured values ​​are shown in Table 1 as fracture toughness 2.

[0118] [Table 1]

[0119] The amount of curing agent in Table 1 is shown as a mass ratio when the total mass of the curing agent is taken as 100. The amount of inorganic filler is shown as a content (mass %) relative to the total mass of the liquid resin composition for underfill. The amounts of flexibilizer, specific silicone compound, colorant, antioxidant, and ion exchanger are shown in parts by mass of each component relative to a total of 100 parts by mass of epoxy resin. In the above liquid underfill resin composition, the ratio of the number of active hydrogens in the curing agent to the number of epoxy groups in the epoxy resin (number of active hydrogens in the curing agent / number of epoxy groups in the epoxy resin) is 1.0.

[0120] As is clear from the evaluation results shown in Table 1, the viscosity at 110°C of Examples 1-3 containing the specific silicone compound is equivalent to the viscosity at 110°C of Comparative Example 1 not containing the specific silicone compound, and it is clear that the liquid resin compositions of Examples 1-3 have excellent fluidity. Furthermore, when the composition other than the flexibilizer or specific silicone compound was the same, the cured product of the liquid resin composition of Example 1-3 was found to have superior fracture toughness compared to the cured product of the liquid resin composition of Comparative Example 2-3. These results demonstrate that the liquid resin composition of Example 1-3 has superior fracture toughness when cured.

Claims

1. Epoxy resin, A hardener; an inorganic filler; a silicone compound including a structural unit (A) represented by the following formula (A), a structural unit (B) represented by the following formula (B), and a structural unit (C) represented by the following formula (C); Contains the content of the silicone compound is 1 part by mass to 50 parts by mass relative to 100 parts by mass of the epoxy resin, the curing agent comprises an amine curing agent; A liquid resin composition for underfill. 【Chemistry 1】 (In formula (A), R １ represents an alkylene group having 1 to 10 carbon atoms. 【Chemistry 2】 (In formula (B), R ２ and R ３ each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a monovalent organic group having 1 to 10 carbon atoms and an epoxy group, a monovalent organic group having 1 to 10 carbon atoms and a carboxy group, or a polyalkylene ether group having 3 to 500 carbon atoms. 【Transformation 3】 (In formula (C), R ４Ａ and R ４Ｂ each independently represents an alkylene group having 1 to 10 carbon atoms.

2. 2. The silicone compound according to claim 1, wherein the number average molecular weight Mn of the silicone compound is 2,000 to 20,000. The liquid resin composition for underfill described above.

3. 3. The liquid resin composition for underfill according to claim 1, wherein a mass ratio of the structural unit (A) to the structural unit (B) contained in the silicone compound (structural unit (A) / structural unit (B)) is 3 / 7 to 7 / 3.

4. 4. The liquid resin composition for underfill according to claim 1, wherein the silicone compound comprises a triblock copolymer having a polymer block (A1) containing the structural unit (A), a polymer block (B) containing the structural unit (B), and a polymer block (A2) containing the structural unit (A).

5. 5. The liquid resin composition for underfill according to claim 4, wherein in the triblock copolymer, the polymer block (A1) and the polymer block (B) are bonded via the structural unit (C), and the polymer block (A2) and the polymer block (B) are bonded via the structural unit (C).

6. 6. The liquid resin composition for underfill according to claim 1, wherein the silicone compound comprises a compound represented by the following general formula (F): 【Chemistry 4】 (In general formula (F), l represents an integer of 1 to 200, m １ +m ２ represents an integer of 2 to 400. １ R each independently represents an alkylene group having 1 to 10 carbon atoms. ２ and R ３ R each independently represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a monovalent organic group having 1 to 10 carbon atoms and an epoxy group, a monovalent organic group having 1 to 10 carbon atoms and a carboxy group, or a polyalkylene ether group having 3 to 500 carbon atoms. ４Ａ and R ４Ｂ R each independently represents an alkylene group having 1 to 10 carbon atoms. ５ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

7. 7. The liquid underfill resin composition according to claim 1, wherein the cured product has an elastic modulus at 25° C. of 7.0 GPa or less.

8. The liquid resin composition for underfill according to any one of claims 1 to 7, wherein the cured product has a coefficient of linear expansion (CTE1) of 35 ppm / °C or less, which is measured by a compression method with the temperature raised from 0°C to 300°C at a rate of 5°C / min and is calculated as the slope of the tangent line from 10°C to 30°C.

9. 9. The liquid resin composition for underfilling according to claim 1, wherein the content of the inorganic filler is 50% by mass to 75% by mass.

10. 10. The liquid resin composition for underfill according to claim 1, wherein the epoxy resin contains an epoxy resin having an epoxy equivalent of 300 g / eq to 600 g / eq.

11. 11. The liquid resin composition for underfilling according to claim 10, wherein the epoxy resin having an epoxy equivalent of 300 g / eq to 600 g / eq has a polyether skeleton.

12. The underfill liquid resin composition according to any one of claims 1 to 11, which is used to seal a connection portion of an electronic component device including an electronic component and a support member electrically connected to the electronic component via a connection portion.

13. Electronic components and a support member electrically connected to the electronic component via a connection portion; a cured product of the liquid underfill resin composition according to any one of claims 1 to 12, which seals the connection portion; and An electronic component device comprising:

14. A method for manufacturing an electronic component device, comprising a step of sealing a connection between an electronic component and a support member electrically connected to the electronic component via a connection portion with the underfill liquid resin composition according to any one of claims 1 to 12.

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