Resin composition, electronic component device, and method for manufacturing electronic component device

Abstract

Provided is a resin composition containing a compound having an oxazoline group, a phenolic curing agent, and an inorganic filler.

Description

Technical Field

[0001] The present invention relates to a resin composition, an electronic component device, and a method for producing an electronic component device. Background Art

[0002] The amount of transmission loss caused by the heat conversion of radio waves sent for communication in the dielectric can be expressed as the product of the frequency and the square root of the relative dielectric constant and the dielectric loss tangent. In other words, the transmission signal is easily converted into heat in proportion to the frequency, so in order to suppress the transmission loss, the higher the frequency band, the lower the dielectric properties required for the materials of the communication components.

[0003] A sealing resin composition containing an epoxy resin and a phenolic curing agent is widely used for electronic components. In recent years, a cured product of the sealing resin composition is required to have a low relative dielectric constant and a low dielectric loss tangent.

[0004] For example, Patent Document 1 studies a sealing resin composition having a low relative dielectric constant of a cured product, and discloses a sealing resin composition containing an epoxy resin and a phenol resin.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2001-40182 Summary of the invention

[0008] Problems to be solved by the invention

[0009] The present inventors have found that the dielectric loss tangent of the cured product of the sealing resin composition disclosed in Patent Document 1 has room for further improvement.

[0010] An object of one embodiment of the present invention is to provide a resin composition having a low dielectric loss tangent of a cured product, an electronic component device sealed using the resin composition, and a method for producing an electronic component device including an operation of sealing using the resin composition.

[0011] Means for solving problems

[0012] <1> A resin composition comprises a compound having an oxazoline group, a phenolic curing agent and an inorganic filling material.

[0013] <2> According to the above <1> The resin composition described in , wherein the compound having an oxazoline group comprises an aromatic oxazoline compound.

[0014] <3> According to the above <1> or <2> The resin composition described in , wherein the molecular weight of the compound having an oxazoline group is 100 to 1000.

[0015] <4> According to the above <1> ~ <3> The resin composition according to any one of the above, wherein an equivalent ratio of the phenolic hydroxyl group of the phenolic curing agent to the oxazoline group of the compound having an oxazoline group is 0.75 to 1.25.

[0016] <5> According to the above <1> ~ <4> The resin composition according to any one of the above, further comprising at least one of a sulfonic acid-based curing accelerator and a phosphoric acid-based curing accelerator.

[0017] <6> According to the above <1> ~ <5> The resin composition according to any one of the above, which is solid at 25°C.

[0018] <7> According to the above <1> ~ <6> The resin composition according to any one of claims , wherein the curing start temperature is 175° C. or lower.

[0019] <8> According to the above <1> ~ <7> The resin composition according to any one of the above, which is a resin composition for a sealing material.

[0020] <9> An electronic component device comprising:

[0021] Supporting member,

[0022] An element disposed on the supporting member, and

[0023] The above-mentioned components are sealed <1> ~ <8> A cured product of the resin composition according to any one of the above.

[0024] <10> A method for manufacturing an electronic component device, the method comprising:

[0025] a step of placing the element on the support member, and

[0026] The above components are used <1> ~ <8> The step of sealing with the resin composition according to any one of claims .

[0027] Effects of the Invention

[0028] According to the present invention, there can be provided a resin composition having a low dielectric loss tangent of a cured product, an electronic component device sealed using the resin composition, and a method for producing an electronic component device including an operation of sealing using the resin composition. DETAILED DESCRIPTION

[0029] Hereinafter, the mode for implementing the present invention is described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, its constituent elements (including element steps, etc.) are not necessary except for the particularly explicit situations. For numerical values ​​and their ranges, the present invention is not limited.

[0030] In the present invention, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes as long as the purpose of the process can be achieved. In the numerical range expressed by "to" in the present invention, the numerical values ​​recorded before and after "to" are respectively included as the minimum value and the maximum value.

[0031] In the numerical ranges described in stages in the present invention, the upper limit or lower limit described in one numerical range may be replaced by the upper limit or lower limit of another numerical range described in stages.

[0032] In addition, in the numerical range described in the present invention, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the Examples.

[0033] In the present invention, each component may include a plurality of corresponding substances. When a plurality of corresponding substances are present in the composition, the content rate or content of each component means the total content rate or content of the plurality of substances present in the composition unless otherwise specified.

[0034] The present invention may contain a plurality of particles corresponding to each component. When a plurality of particles corresponding to each component are present in the composition, the particle size of each component refers to a value for a mixture of the plurality of particles present in the composition unless otherwise specified.

[0035] [Resin composition]

[0036] The resin composition of the present invention (hereinafter also referred to as a specific resin composition) contains a compound having an oxazoline group (hereinafter also referred to as an oxazoline compound), a phenolic curing agent, and an inorganic filler.

[0037] The dielectric loss tangent of the cured product of the specific resin composition is low, and the specific resin composition can be suitably used as a resin composition for a sealing material. The reason why the above effect is exerted is not clear, but it is presumed as follows.

[0038] When using a sealing material resin composition comprising an epoxy resin and a phenolic curing agent to manufacture a cured product, the reactant of the epoxy resin and the phenolic curing agent has a secondary hydroxyl group with a large polarity, thereby having a trend of increasing the dielectric loss tangent. It can be inferred that the specific resin composition replaces the epoxy resin and contains an oxazoline compound, and the reactant of the oxazoline compound and the phenolic curing agent does not have a secondary hydroxyl group, and the dielectric loss tangent of the cured product is reduced.

[0039] The glass transition temperature of the specific resin composition is preferably 85°C to 150°C, more preferably 90°C to 145°C, and even more preferably 100°C to 135°C from the viewpoint of improving the heat resistance of the cured product.

[0040] In the present invention, the glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), more specifically, according to the "extrapolated glass transition start temperature" described in the method for determining the glass transition temperature of JIS K 7121 (1987) "Methods for determining transition temperatures of plastics".

[0041] The specific resin composition is preferably solid at 25° C. When the specific resin composition is solid at 25° C., its shape is not particularly limited, and examples thereof include powder, granules, and tablets. Regarding the size and mass of the specific resin composition in the form of a tablet, from the viewpoint of operability, the size and mass are preferably those that match the molding conditions of the package.

[0042] The curing start temperature of the specific resin composition is preferably 200° C. or less, more preferably 190° C. or less, and further preferably 175° C. or less. By setting the curing start temperature of the specific resin composition to 200° C. or less, the conditions required for the device used for curing can be reduced, and a cured product can be easily produced. The lower limit of the curing start temperature is not particularly limited, and can be set to 100° C. or more.

[0043] In the present invention, the curing start temperature is measured by differential scanning calorimetry (DSC). In the measurement of the curing start temperature, a Discovery DSC 250 manufactured by TA instruments or an apparatus of the same degree can be used. It should be noted that the curing start temperature is measured at a heating rate of 10°C / min in the range of 40°C to 300°C, and the onset temperature of the peak (the rising temperature of the peak) is set as the reaction start temperature.

[0044] From the viewpoint of adhesion to electronic component devices such as lead frames, the linear expansion coefficient of the cured product of the specific resin composition at 80°C to 120°C is preferably 0.90 ppm / °C to 2.00 ppm / °C, more preferably 0.95 ppm / °C to 1.70 ppm / °C, and even more preferably 1.00 ppm / °C to 1.50 ppm / °C.

[0045] In the present invention, the linear expansion coefficient of the cured product is measured as follows.

[0046] The specific resin composition was molded using a transfer molding machine under the conditions of a molding temperature of 175° C., a molding pressure of 6.9 MPa, and a curing time of 120 seconds to obtain a plate-shaped molded product (127 mm in length, 12.7 mm in width, and 6.4 mm in thickness).

[0047] Then, the slope of the tangent line when the strain of the molded product is plotted against the temperature in the range of 80°C to 120°C and the range of 200°C to 240°C was determined by thermomechanical analysis in accordance with JIS K 7197:2012 and was defined as the linear expansion coefficient.

[0048] In addition, the measurement was performed with a test load of 5 g and a temperature increase rate of 5° C. / min.

[0049] In addition, for the measurement of the linear expansion coefficient, a TMA high-precision two-sample thermal analyzer (device name: SS6100) manufactured by Seiko Instruments Co., Ltd. or an apparatus equivalent thereto can be used.

[0050] The cured product of the specific resin composition has a low dielectric loss tangent and can be particularly suitably used as a resin composition for a sealing material.

[0051] <Oxazoline compounds>

[0052] The type of the oxazoline compound is not particularly limited as long as it has an oxazoline group in the molecule. The oxazoline compound preferably has two or more oxazoline groups. The specific resin composition may contain two or more oxazoline compounds.

[0053] From the viewpoint of reducing the dielectric loss tangent of the cured product, the oxazoline compound preferably contains an aromatic oxazoline compound.

[0054] The content of the aromatic oxazoline compound relative to the total mass of the oxazoline compound is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and may be 100% by mass.

[0055] From the viewpoint of reducing the dielectric loss tangent of the cured product, the oxazoline compound preferably includes an oxazoline compound represented by the following formula (1) (hereinafter also referred to as a specific oxazoline compound).

[0056] The content of the specific oxazoline compound relative to the total mass of the oxazoline compound is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, and may be 100% by mass.

[0057] [Chemistry 1]

[0058]

[0059] In formula (1), R 1 ~R 4 Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom.

[0060] In formula (1), X is an n-valent hydrocarbon group having 1 to 10 carbon atoms, preferably an n-valent linear or branched hydrocarbon group having 1 to 10 carbon atoms, an n-valent alicyclic hydrocarbon group having 1 to 10 carbon atoms, or an n-valent aromatic hydrocarbon group.

[0061] When n is 2, X is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 1 to 10 carbon atoms, or a phenylene group, and is preferably a phenylene group.

[0062] In the formula (1), n ​​represents an integer of 2 to 6.

[0063] When X in formula (1) is a phenylene group and n is 2, the two oxazoline groups are preferably bonded to the phenylene group in a meta-position or a para-position from the viewpoint of reducing the dielectric loss tangent of the cured product.

[0064] Specific examples of the oxazoline compound include 2,2′-(1,3-phenylene)bis(2-oxazoline), 1,2-bis(2-oxazolinyl-2)ethane, 1,4-bis(2-oxazolinyl-2)butane, 1,8-bis(2-oxazolinyl-2)octane, and 1,4-bis(2-oxazolinyl-2)cyclohexane.

[0065] From the viewpoint of reducing the dielectric loss tangent of the cured product, the molecular weight of the oxazoline compound is preferably 100 to 1,000, more preferably 150 to 750, and even more preferably 180 to 500.

[0066] The oxazoline compound may be solid or liquid at 25° C. When the oxazoline compound is solid at 25° C., the softening point or melting point of the oxazoline compound is not particularly limited.

[0067] From the viewpoint of the balance between moldability and heat resistance, the softening point or melting point of the oxazoline compound is preferably 40° C. to 180° C. From the viewpoint of handleability, the softening point or melting point of the oxazoline compound is preferably 50° C. to 130° C.

[0068] In the present invention, the softening point refers to a value measured by the ring and ball method of JIS K 7234:1986.

[0069] In the present invention, the melting point refers to a value measured by a visual method in accordance with JIS K 0064:1992.

[0070] The content of the oxazoline compound relative to the total mass of the specific resin composition is preferably 3 to 25 mass %, more preferably 5 to 20 mass %, from the viewpoint of dielectric loss tangent, strength, fluidity, heat resistance, moldability, etc. of the cured product.

[0071] <Phenol-based curing agent>

[0072] The specific resin composition contains a phenolic curing agent. The type of the phenolic curing agent is not particularly limited. The phenolic curing agent may be used alone or in combination of two or more.

[0073] Examples of the phenolic curing agent include phenol resins and polyphenol compounds having two or more phenolic hydroxyl groups in one molecule.

[0074] Specific examples of the phenolic curing agent are described below, but the invention is not limited to these.

[0075] As the phenolic curing agent, there can be mentioned polyphenolic compounds such as resorcinol, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenols; phenolic compounds selected from phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, etc. and α Novolac-type phenolic resins obtained by condensing or co-condensing at least one phenolic compound selected from naphthol compounds such as α-naphthol, β-naphthol, dihydroxynaphthol, and aldehyde compounds such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst; aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins synthesized from the above phenolic compounds and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, etc.; p-xylene and / or m-xylene modified phenolic resins; melamine modified phenolic resins; terpene modified phenolic resins; dicyclopentadiene synthesized by copolymerization of the above phenolic compounds and dicyclopentadiene Polycyclopentadiene type phenolic resin and dicyclopentadiene type naphthol resin; cyclopentadiene modified phenolic resin; polycyclic aromatic ring modified phenolic resin; biphenyl type phenolic resin; triphenylmethane type phenolic resin obtained by condensing or co-condensing the above phenolic compounds, aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; triazine type phenolic resins such as 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; phenolic resins obtained by copolymerizing two or more of them, etc.

[0076] From the viewpoint of reducing the dielectric loss tangent of the cured product, the phenolic curing agent preferably contains one or more phenolic curing agents selected from aralkyl phenolic resins and novolac phenolic resins. The phenolic curing agent is described in more detail below, but is not limited thereto.

[0077] The aralkyl type phenol resin is not particularly limited, and examples thereof include phenol resins synthesized from at least one selected from phenol compounds and naphthol compounds, and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, or derivatives thereof.

[0078] Specific examples of the aralkyl-type phenol resin include phenol resins represented by the following general formulae (XII) to (XIV).

[0079] In formulas (XII) to (XIV), R 23 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. 22 , R 24 , R 25 and R 28 represents a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. 26 and R 27 represents a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i is each independently an integer of 0 to 3, j is each independently an integer of 0 to 2, k is each independently an integer of 0 to 4, and p is each independently an integer of 0 to 4. n is an average value and is each independently an integer of 0 to 10.

[0080] For R in the above general formula 22 The phrase "each may be the same or different" as used herein means, for example, that all i R 22 They may be the same or different from each other. 22 ~R 36 Each can be the same or different. For example, for R 22 and R 23 All of can be the same or different.

[0081] [Chemistry 2]

[0082]

[0083] The aralkyl phenolic resin may also be a copolymerized phenolic resin with other phenolic resins. Examples of the copolymerized phenolic resin include a copolymerized phenolic resin of a triphenylmethane phenolic resin and an aralkyl phenolic resin, a copolymerized phenolic resin of a salicylaldehyde phenolic resin and an aralkyl phenolic resin, and a copolymerized phenolic resin of a novolac phenolic resin and an aralkyl phenolic resin.

[0084] The dicyclopentadiene-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained from a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenolic resin represented by the following general formula (XV) is preferred.

[0085] [Chemistry 3]

[0086]

[0087] In formula (XV), R 29 The monovalent organic groups having 1 to 18 carbon atoms may be all the same or different. i each independently represents an integer of 0 to 3. n is an average value and represents an integer of 0 to 10.

[0088] The triphenylmethane-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained from an aromatic aldehyde compound as a raw material. For example, a phenolic resin represented by the following general formula (XVI) is preferred.

[0089] [Chemistry 4]

[0090]

[0091] In formula (XVI), R 30 and R 31 The monovalent organic groups having 1 to 18 carbon atoms may be all the same or different. i is an integer of 0 to 3, and k is an integer of 0 to 4. n is an average value and an integer of 0 to 10.

[0092] The copolymerized phenolic resin of triphenylmethane phenolic resin and aralkyl phenolic resin is not particularly limited as long as it is a copolymerized phenolic resin of a phenolic resin and an aralkyl phenolic resin obtained from a compound having a benzaldehyde skeleton as a raw material. For example, a phenolic resin represented by the following general formula (XVII) is preferred.

[0093] [Chemistry 5]

[0094]

[0095] In formula (XVII), R 32 ~R 34 Represents a monovalent organic group having 1 to 18 carbon atoms, which may be all the same or different. i is each independently an integer of 0 to 3, k is each independently an integer of 0 to 4, and q is each independently an integer of 0 to 5. l and m are each an average value and are each independently an integer of 0 to 11. The total of l and m is an integer of 1 to 11.

[0096] The novolac phenolic resin is not particularly limited as long as it is a phenolic resin obtained by condensing or co-condensing at least one phenolic compound selected from phenol compounds and naphthol compounds with an aldehyde compound under an acidic catalyst. For example, a phenolic resin represented by the following general formula (XVIII) is preferred.

[0097] [Chemistry 6]

[0098]

[0099] In formula (XVIII), R 35 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. 36 The monovalent organic groups having 1 to 18 carbon atoms may be all the same or different. i each independently represents an integer of 0 to 3. n is an average value and represents an integer of 0 to 10.

[0100] Regarding R in the above general formulae (XII) to (XVIII), 22 ~R 36 The phrase "each may be the same or different" means, for example, that all i R in formula (XII) are 22 They may be the same or different from each other. 23 ~R 36 , which also means that the total number of each contained in the pair of formulas can be the same or different. 22 ~R 36 Each can be the same or different. For example, for R 22 and R 23 All of can be the same or different. For R 30 and R 31 All of can be the same or different.

[0101] In the above general formulae (XII) to (XVIII), n is preferably an integer of 0 to 10. If it is 10 or less, the melt viscosity of the resin component will not be too high, and the viscosity of the resin composition during melt molding will also be low, which will not easily cause poor filling, deformation of the bonding wire (gold wire connecting the element to the lead), etc. The average n in one molecule is preferably set in the range of 0 to 4.

[0102] The hydroxyl equivalent of the phenolic curing agent is not particularly limited, but is preferably 10 g / eq to 1000 g / eq, more preferably 30 g / eq to 500 g / eq, from the viewpoint of balancing various properties of the cured product such as dielectric loss tangent, moldability, and electrical reliability.

[0103] The hydroxyl equivalent is a value calculated based on the hydroxyl value measured in accordance with JIS K 0070:1992.

[0104] From the viewpoint of reducing the dielectric loss tangent of the cured product, the equivalent ratio of the phenolic hydroxyl group of the phenolic curing agent to the oxazoline group of the oxazoline compound is preferably 0.50 to 1.50, more preferably 0.75 to 1.25, and even more preferably 0.90 to 1.10.

[0105] When the phenolic curing agent is solid at 25° C., the softening point or melting point thereof is not particularly limited. From the viewpoint of moldability and heat resistance, the softening point or melting point of the phenolic curing agent is preferably 40° C. to 180° C. From the viewpoint of operability, the softening point or melting point of the phenolic curing agent is preferably 50° C. to 130° C.

[0106] From the viewpoint of reducing the dielectric loss tangent of the cured product, the content of the phenolic curing agent relative to the total mass of the specific resin composition is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass, and even more preferably 2 to 20% by mass.

[0107] <Inorganic filler>

[0108] The specific resin composition contains an inorganic filler.

[0109] As inorganic fillers, inorganic materials such as silica fillers (such as fused silica, crystalline silica), glass, aluminum oxide, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zirconium dioxide, zircon, forsterite, steatite, spinel, mullite, titanium dioxide, talc, clay, mica can be cited. Inorganic fillers with flame retardant effects can also be used. As inorganic fillers with flame retardant effects, composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, composite hydroxides of magnesium and zinc, zinc borate, etc. can be cited.

[0110] Among the above, the inorganic filler is preferably a silica filler from the viewpoint of reducing the dielectric loss tangent of the cured product.

[0111] The shape of the inorganic filler is not particularly limited, and may be in a particle form or in a non-particle form such as a fiber form.

[0112] The specific resin composition may contain two or more inorganic fillers.

[0113] When the inorganic filler is in the form of particles, the average particle size is preferably 0.1 μm to 100 μm, more preferably 0.3 μm to 50 μm, and further preferably 0.5 μm to 10 μm. If the average particle size is 0.1 μm or more, there is a tendency to suppress the increase in the viscosity of the specific resin composition. If the average particle size is 100 μm or less, there is a tendency to improve the filling property.

[0114] The average particle size of the inorganic filler is determined as a volume average particle size (D50) using a laser scattering diffraction particle size distribution measuring apparatus.

[0115] From the viewpoint of fluidity, the specific surface area of ​​the inorganic filler is preferably 1.3 m 2 / g~10.0m2 / g, more preferably 2.0m 2 / g~8.0m 2 / g, more preferably 2.5m 2 / g~7.5m 2 / g.

[0116] From the viewpoint of achieving both improved moldability of the specific resin composition and reduced dielectric loss tangent of the cured product, the content of the inorganic filler relative to the total mass of the specific resin composition is preferably 60 to 80 mass %, more preferably 60 to 75 mass %.

[0117] From the viewpoint of the fluidity of the specific resin composition and the relative dielectric constant and dielectric loss tangent of the cured product, the volume ratio of the inorganic filler to the entire specific resin composition is preferably 60% to 80% by volume, more preferably 63% to 78% by volume, and further preferably 65% ​​to 75% by volume.

[0118] <Curing Accelerator>

[0119] The specific resin composition of the present invention may contain a curing accelerator. The type of the curing accelerator is not particularly limited, and can be selected based on the type of the oxazoline compound or phenolic curing agent, the desired properties of the specific resin composition, and the like.

[0120] From the viewpoint of reducing the dielectric loss tangent of the cured product, the curing accelerator is preferably an acid catalyst, more preferably at least one of a sulfonic acid curing accelerator and a phosphoric acid curing accelerator, and still more preferably a sulfonic acid curing accelerator.

[0121] Examples of the sulfonic acid curing accelerator include methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, and methoxyethyl p-toluenesulfonate.

[0122] Examples of the phosphoric acid-based curing accelerator include phosphorous acid and the like.

[0123] Among the above, from the viewpoint of reducing the dielectric loss tangent of the cured product, the curing accelerator is preferably at least one selected from methyl p-toluenesulfonate, ethyl p-toluenesulfonate, and propyl p-toluenesulfonate.

[0124] In the case where a specific resin composition includes a curing accelerator, its amount is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the resin component (the total amount of the oxazoline compound and the phenolic curing agent), and more preferably 1 to 15 parts by mass. If the amount of the curing accelerator is more than 0.1 parts by mass relative to 100 parts by mass of the resin component, there is a trend of curing well in a short time. If the amount of the curing accelerator is less than 30 parts by mass relative to 100 parts by mass of the resin component, the curing speed will not be too fast, and there is a trend of obtaining a good molded product.

[0125] <Compounds other than oxazoline compounds>

[0126] The specific resin composition may contain a compound other than the oxazoline compound, and specific examples thereof include fluororesins and epoxy resins.

[0127] From the viewpoint of reducing the dielectric loss tangent of the cured product, the content of compounds other than the oxazoline compound relative to the total mass of the specific resin composition is preferably 5 mass % or less, more preferably 3 mass % or less, further preferably 1 mass % or less, and particularly preferably not contained.

[0128] <Curing Agents Other Than Phenolic Curing Agents>

[0129] The specific resin composition may contain a curing agent other than the phenolic curing agent, and specifically, an amine curing agent, a polythiol curing agent, a polyaminoamide curing agent, an isocyanate curing agent, a blocked isocyanate curing agent, and the like are mentioned.

[0130] From the viewpoint of reducing the dielectric loss tangent of the cured product, the content of the curing agent other than the phenolic curing agent relative to the total mass of the specific resin composition is preferably 5 mass % or less, more preferably 3 mass % or less, further preferably 1 mass % or less, and particularly preferably not contained.

[0131] <Various additives>

[0132] The specific resin composition may contain various additives such as coupling agents, ion exchangers, release agents, flame retardants, colorants, plasticizers, etc. in addition to the above components. The specific resin composition may contain various additives known in the art as needed in addition to the additives exemplified below.

[0133] <Coupling agent>

[0134] The specific resin composition may include a coupling agent. From the viewpoint of improving the adhesion between the resin component and the inorganic filler, the specific resin composition preferably includes a coupling agent. As the coupling agent, known coupling agents such as epoxy silane, mercapto silane, amino silane, alkyl silane, urea silane, vinyl silane, disilazane and the like, titanium compounds, aluminum chelate compounds, aluminum / zirconium compounds and the like can be cited.

[0135] When the specific resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2.5 parts by mass, relative to 100 parts by mass of the inorganic filler. If the amount of the coupling agent is 0.05 parts by mass or more relative to 100 parts by mass of the inorganic filler, there is a tendency to further improve the adhesion to electronic component devices such as lead frames. If the amount of the coupling agent is 5 parts by mass or less relative to 100 parts by mass of the inorganic filler, there is a tendency to further improve the formability of the package.

[0136] <Ion Exchanger>

[0137] The specific resin composition may contain an ion exchanger. When the specific resin composition is used as the specific resin composition, from the viewpoint of improving the moisture resistance and high temperature placement characteristics of the electronic component device having the sealed element, the specific resin composition preferably contains an ion exchanger. There is no particular limitation on the ion exchanger, and conventionally known ion exchangers can be used. Specifically, hydrotalcite compounds and hydrous oxides of at least one element selected from magnesium, aluminum, titanium, zirconium and bismuth can be cited. The ion exchanger can be used alone or in combination of two or more. Among them, the hydrotalcite represented by the following general formula (A) is preferred.

[0138] Mg (1-X) Al X (OH) 2 (CO 3 ) X / 2 ·mH 2 O…(A)

[0139] (0<X≤0.5, m is a positive number)

[0140] When the specific resin composition includes an ion exchanger, the content thereof is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions. For example, the content is preferably 0.1 to 30 parts by mass, and more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the resin component (the total amount of the oxazoline compound and the phenolic curing agent).

[0141] <Release Agent>

[0142] From the viewpoint of obtaining good demoulding properties with the mold during molding, the specific resin composition may include a release agent. The release agent is not particularly limited, and a previously known release agent can be used. Specifically, ester waxes such as carnauba wax, montanic acid, stearic acid, higher fatty acids, higher fatty acid metal salts, montanic acid esters, oxidized polyethylene, non-oxidized polyethylene, and other polyolefin waxes can be cited. The release agent can be used alone or in combination of two or more.

[0143] When the specific resin composition includes a release agent, the amount thereof is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the resin component (the total amount of the oxazoline compound and the phenolic curing agent), and more preferably 0.1 to 5 parts by mass. If the amount of the release agent is 0.01 parts by mass or more relative to 100 parts by mass of the resin component, there is a tendency to fully obtain demoulding properties. If it is 10 parts by mass or less, there is a tendency to obtain better adhesion.

[0144] <Flame retardant>

[0145] The specific resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known flame retardants may be used. Specifically, organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, metal hydroxides, etc. may be cited. The flame retardant may be used alone or in combination of two or more.

[0146] When a specific resin composition includes a flame retardant, the amount thereof is not particularly limited as long as it is an amount sufficient to obtain the desired flame retardant effect. For example, it is preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, relative to 100 parts by mass of the resin component (the total amount of the oxazoline compound and the phenolic curing agent).

[0147] <Colorant>

[0148] The specific resin composition may contain a colorant. As the colorant, known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and iron oxide may be cited. The content of the colorant may be appropriately selected according to the purpose, etc. The colorant may be used alone or in combination of two or more.

[0149] [Method for preparing specific resin composition]

[0150] The preparation method of the specific resin composition is not particularly limited. As a general method, a method in which the components of the specified amount are fully mixed by a mixer, etc., and then melt-kneaded, cooled, and crushed by a mixing roll, an extruder, etc. is mentioned. More specifically, for example, the following method can be mentioned, that is, the specified amount of the above-mentioned components is uniformly stirred and mixed, and kneaded, cooled, and crushed by a kneader, a roll, an extruder, etc. preheated to 70°C to 140°C.

[0151] [Electronic component devices]

[0152] The electronic component device of the present invention comprises a supporting member, an element arranged on the supporting member, and a cured product of a specific resin composition that seals the element.

[0153] Examples of electronic component devices include devices (e.g., high-frequency devices) in which a component portion is mounted on a supporting member such as a lead frame, a wired tape carrier, a wiring board, glass, a silicon wafer, an organic group board, etc., and components (active components such as semiconductor chips, transistors, diodes, thyristors, etc., passive components such as capacitors, resistors, coils, etc.) and sealed with a specific resin composition.

[0154] More specifically, there can be mentioned conventional resin-sealed ICs such as DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package), which have a structure in which a component is fixed to a lead frame, a terminal portion of the component such as a pad and a lead portion are connected by wire bonding, bumps, etc., and then sealed using a specific resin composition by transfer molding or the like; TCP (Tape Carrier Package), which has a structure in which a component connected to a tape carrier by bumps is sealed using a specific resin composition; COB (Chip On Board) Board: chip on board package) module, hybrid IC, multi-chip module, etc., which have the following structure, that is, the element connected to the wiring formed on the supporting member by wire bonding, flip chip bonding, solder, etc. is sealed with a specific resin composition; BGA (Ball Grid Array: ball grid array package), CSP (Chip Size Package: chip size package), MCP (Multi Chip Package: multi-chip package), etc., which have the following structure, that is, the surface of the supporting member with a terminal for wiring board connection formed on the back is equipped with a component, and the element is connected to the wiring formed on the supporting member by bumps or wire bonding, and then the element is sealed with a specific resin composition. In addition, the specific resin composition can also be appropriately used in printed wiring boards.

[0155] The type of the supporting member is not particularly limited, and any supporting member commonly used in the production of electronic component devices can be used.

[0156] The electronic component may include an antenna, or may include an antenna and an element other than an antenna. The antenna is not limited as long as it functions as an antenna, and may be an antenna element or wiring.

[0157] In addition, in the electronic component device of this embodiment, other electronic components can be arranged on the surface of the support member opposite to the surface on which the above-mentioned electronic components are arranged, as required. Other electronic components can be sealed by the aforementioned molding resin composition, can be sealed by other resin compositions, or can be not sealed.

[0158] [Method for manufacturing electronic component device]

[0159] The method for producing an electronic component device of the present invention includes a step of placing an element on a supporting member and a step of sealing the element with a specific resin composition.

[0160] There is no particular limitation on the method of implementing each of the above steps, and a common method can be used. In addition, there is no particular limitation on the type of support members and elements used in the manufacture of electronic component devices, and support members and elements commonly used in the manufacture of electronic component devices can be used.

[0161] Examples of a method for sealing a device using a specific resin composition include low-pressure transfer molding, injection molding, compression molding, etc. Among them, low-pressure transfer molding is a common method.

[0162] Example

[0163] Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited to these examples. In addition, the numerical values ​​in the tables are "parts by mass" unless otherwise specified.

[0164] (Examples 1 to 2 and Comparative Examples 1 to 2)

[0165] The resin compositions of Examples and Comparative Examples were prepared by mixing the following components at the blending ratios (parts by mass) shown in Table 1. The specific resin composition is solid at normal temperature and pressure.

[0166] The volume ratio of the inorganic filler in Example 1 and Comparative Example 1 to the entire resin composition was 65 volume %, and the volume ratio of the inorganic filler in Example 2 and Comparative Example 2 to the entire resin composition was 72 volume %.

[0167] In addition, Table 1 summarizes the equivalent ratios of the phenolic hydroxyl group of the phenolic curing agent to the oxazoline group of the oxazoline compound.

[0168] ■Oxazoline compound: 2,2'-(1,3-phenylene)bis(2-oxazoline), molecular weight 216

[0169] ■Epoxy resin A: Biphenyl aralkyl type epoxy resin

[0170] ■Epoxy resin B: Biphenyl type epoxy resin

[0171] ■Phenol curing agent: Biphenyl aralkyl type phenol curing agent

[0172] ■Curing accelerator A: methyl p-toluenesulfonate

[0173] ■Curing accelerator B: adduct of tributylphosphine and 1,4-benzoquinone

[0174] ■ Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane

[0175] ■Inorganic filler A: silica filler, average particle size 6.0μm, specific surface area 2.8m 2 / g

[0176] ■Inorganic filler B: silica filler, average particle size 0.5μm, specific surface area 6.6m 2 / g

[0177] ■Colorant: Carbon black

[0178] 《Determination of curing start temperature》

[0179] The curing start temperature of the resin composition obtained in the examples and comparative examples was measured by differential scanning calorimetry using Discovery DSC 250 manufactured by TA Instruments. It should be noted that the curing start temperature was measured at a temperature increase rate of 10°C / min in the range of 40°C to 300°C, and the onset temperature of the peak (peak rise temperature) was set as the reaction start temperature. The results are summarized in Table 1.

[0180] 《Determination of relative dielectric constant Dk and dielectric loss tangent Df》

[0181] The resin composition obtained in the embodiment and the comparative example was placed in a vacuum hand press and molded under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 600 seconds. After curing at 180°C for 6 hours, a plate-shaped cured product (12.5 mm long, 25 mm wide, and 0.2 mm thick) was obtained.

[0182] The plate-shaped cured product was used as a test piece, and the relative dielectric constant Dk and dielectric loss tangent Df at about 5 GHz were measured at a temperature of 25±3°C using a dielectric constant measuring device (Agilent Technology, product name "Network Analyzer N5227A"), and the respective values ​​were evaluated based on the following evaluation criteria. The results are summarized in Table 1. It should be noted that the measured values ​​are also summarized in Table 1.

[0183] (Evaluation Criteria)

[0184] A: The relative dielectric constant Dk is less than 3.60.

[0185] B: The relative dielectric constant Dk is 3.60 or more.

[0186] (Evaluation Criteria)

[0187] A: Dielectric loss tangent Df is less than 0.0075.

[0188] B: Dielectric loss tangent Dk is 0.0075 or more.

[0189] <Measurement of Glass Transition Temperature (Tg) of Resin Composition>

[0190] The glass transition temperature of the specific resin composition was measured using the "Extrapolated glass transition start temperature" described in the method for determining the glass transition temperature in "Methods for Determining Transition Temperatures of Plastics" in JIS K 7121 (1987).

[0191] <Determination of Linear Expansion Coefficient>

[0192] The resin compositions obtained in Examples and Comparative Examples were molded using a transfer molding machine at a molding temperature of 175° C., a molding pressure of 6.9 MPa, and a curing time of 120 seconds to obtain a plate-shaped molded product (127 mm in length, 12.7 mm in width, and 6.4 mm in thickness).

[0193] Then, the slope of the tangent line when the strain of the molded product is plotted against the temperature was obtained by thermomechanical analysis in the range of 80°C to 120°C and the range of 200°C to 240°C in accordance with JIS K 7197: 2012. The slope of the tangent line in the range of 80°C to 120°C is referred to as CTE1 (ppm / °C), and the slope of the tangent line in the range of 200°C to 240°C is referred to as CTE2 (ppm / °C) and are shown in Table 1.

[0194] In addition, the measurement was performed with a test load of 5 g and a temperature increase rate of 5° C. / min.

[0195] In addition, the linear expansion coefficient was measured using a TMA high-precision two-sample thermal analyzer (device name: SS6100) manufactured by Seiko Instruments.

[0196] 《Determination of molding shrinkage》

[0197] The resin composition was molded using a transfer molding machine at a molding temperature of 175° C., a molding pressure of 6.9 MPa, and a curing time of 120 seconds to obtain a plate-shaped molded product (127 mm in length, 12.7 mm in width, and 6.4 mm in thickness).

[0198] The molding shrinkage A (%) was calculated from the previously measured length D of the mold cavity at 25°C and the length d of the molded product at room temperature (25°C) using the following formula.

[0199] Molding shrinkage A (%) = ((Dd) / D) × 100

[0200] The resin composition was molded using a transfer molding machine at a molding temperature of 175° C., a molding pressure of 6.9 MPa, and a curing time of 120 seconds to obtain a plate-shaped molded product (127 mm in length, 12.7 mm in width, and 6.4 mm in thickness). The molded product was post-cured at 175° C. for 5 hours to obtain a plate-shaped cured product.

[0201] The molding shrinkage B (%) was calculated from the previously measured length D of the cavity of the mold at 25° C. and the length d of the cured product at room temperature (25° C.) using the following formula. The results are summarized in Table 1.

[0202] Molding shrinkage B (%) = ((Dd) / D) × 100

[0203] [Table 1]

[0204]

[0205] As can be seen from Table 1, when comparing the resin composition of Example 1 in which the volume ratio of the inorganic filler is 65 volume % with the resin composition of Comparative Example 1, the cured product obtained using the resin composition of Example 1 has a lower dielectric loss tangent.

[0206] As can be seen from Table 1, when comparing the resin composition of Example 2 in which the volume ratio of the inorganic filler is 72 volume % with the resin composition of Comparative Example 2, the cured product obtained using the resin composition of Example 2 has a lower dielectric loss tangent.

[0207] Furthermore, it was found that the linear expansion coefficient and the molding shrinkage ratio of the resin composition of the example were similar to those of the resin composition of the comparative example.

Claims

1. A resin composition comprising a compound having an oxazoline group, a phenolic curing agent and an inorganic filler.

2. The resin composition according to claim 1, wherein The compound having an oxazoline group includes an aromatic oxazoline compound.

3. The resin composition according to claim 1, wherein The molecular weight of the compound having an oxazoline group is 100-1000.

4. The resin composition according to claim 1, wherein The equivalent ratio of the phenolic hydroxyl group of the phenolic curing agent to the oxazoline group of the compound having an oxazoline group is 0.75 to 1.

25. The resin composition according to claim 1 , further comprising at least one of a sulfonic acid-based curing accelerator and a phosphoric acid-based curing accelerator. The resin composition according to claim 1 , which is solid at 25° C. . The resin composition according to claim 1 , which has a curing start temperature of 175° C. or lower. The resin composition according to claim 1 , which is a resin composition for a sealing material.

9. An electronic component device comprising: Supporting member, an element disposed on the support member, and A cured product of the resin composition according to any one of claims 1 to 8, which seals the element.

10. A method for manufacturing an electronic component device, the method comprising: The step of placing the element on the support member; as well as A step of sealing the element with the resin composition according to any one of claims 1 to 8.

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