Resin composition and structure

Abstract

To provide a resin composition that can improve flame retardancy.SOLUTION: A resin composition contains epoxy resin, a curing agent, and a latent crosslinker. The curing agent contains a phenolic resin and / or an acid anhydride. The latent crosslinker contains an aminophenyl phosphine compound in which a trivalent P element has an N-P bond and a phenyl group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition and a structure. [Background technology]

[0002] Various developments have been made so far regarding epoxy resin compositions. For example, the technology described in Patent Document 1 is known as an example of this type of technology. Patent Document 1 describes the use of an imidazole-type latent curing agent such as 2-ethyl-4-methylimidazole in an epoxy resin composition (e.g., claims 1 and 5, paragraph 0043 of Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-256483 Summary of the Invention [Problem to be solved by the invention]

[0004] However, as a result of investigations by the present inventors, it has been found that the epoxy resin composition described in Patent Document 1 has room for improvement in terms of flame retardancy. [Means for solving the problem]

[0005] As a result of intensive research conducted by the present inventors in light of the above circumstances, they have found that the flame retardancy of a resin composition containing an epoxy resin and a phenolic resin and / or an acid anhydride can be improved by using, as a latent crosslinking agent, an aminophenylphosphine compound in which a trivalent P element has an N-P bond and a phenyl group, and have thus completed the present invention.

[0006] According to the present invention, Epoxy resin, A hardener; a latent crosslinking agent; the curing agent comprises a phenolic resin and / or an acid anhydride; the latent crosslinking agent contains an aminophenylphosphine compound in which a trivalent P element has an N-P bond and a phenyl group; A resin composition is provided.

[0007] Further, according to the present invention, A structure is provided that includes a cured product of the above resin composition. [Effects of the Invention]

[0008] According to the present invention, there are provided a resin composition capable of improving flame retardancy, and a structure using the same. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a cross-sectional view showing an example of a configuration of an electronic device according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all drawings, similar components are designated by similar reference numerals, and descriptions thereof will be omitted where appropriate. Furthermore, the drawings are schematic diagrams and do not correspond to actual dimensional proportions.

[0011] The resin composition of this embodiment will be outlined below.

[0012] The resin composition of the present embodiment includes an epoxy resin, a curing agent, and a latent crosslinking agent, wherein the curing agent includes a phenolic resin and / or an acid anhydride, and the latent crosslinking agent includes an aminophenylphosphine compound in which a trivalent P element has an N-P bond and a phenyl group.

[0013] According to the findings of the present inventors, it has been found that an aminophenylphosphine compound in which a trivalent P element has an N-P bond and a phenyl group (hereinafter, sometimes simply referred to as an "aminophenylphosphine compound") not only functions as a latent crosslinking agent in the polymerization reaction of an epoxy resin, but also can improve the flame retardancy of a first resin composition containing an epoxy resin and a phenolic resin, or a second resin composition containing an epoxy resin and an acid anhydride.

[0014] Although the detailed mechanism is unclear, it is thought that in the epoxy / phenol-based first resin composition, the aminophenylphosphine compound promotes the ring-opening of the epoxy group and the crosslinking of the phenol resin, thereby promoting the curing reaction. Furthermore, in the first resin composition, the aminophenylphosphine compound reacts with the resin to form part of the crosslinked structure and is uniformly dispersed, which is thought to improve the flame retardancy of the resin itself after curing and enable the flame retardancy to be stably expressed.

[0015] Although the detailed mechanism is unclear, it is thought that in the epoxy / acid anhydride-based second resin composition, the aminophenylphosphine compound promotes the ring-opening of the acid anhydride or epoxy group, and the ring-opening compound promotes the propagation reaction, thereby promoting the curing reaction. Furthermore, in the second resin composition, the aminophenylphosphine compound reacts with the resin to form part of the crosslinked structure and is uniformly dispersed, which is thought to improve the flame retardancy of the resin itself after curing and enable the flame retardancy to be stably expressed.

[0016] According to this embodiment, by using an aminophenylphosphine compound as a latent crosslinking agent, the flame retardancy and curing acceleration properties of the resin composition can be improved.

[0017] The resin composition of the present embodiment may be configured so that the 5% weight loss temperature Td5 of the cured product of the resin composition is, for example, 300° C. or higher, thereby improving the heat resistance of the resin composition. The lower limit of Td5 is, for example, 300°C or higher, preferably 320°C or higher, and more preferably 340°C or higher. On the other hand, the upper limit of Td5 is not particularly limited, but may be, for example, 500°C or lower.

[0018] The resin composition can be used, for example, as a heat dissipation material, an insulating material, or a semiconductor encapsulation material in electric and electronic devices. The electric / electronic device may be, for example, a conventional semiconductor device (an electronic device having semiconductor elements as electronic components), a power module (an electronic device having power semiconductor elements as electronic components), etc. Specific examples of power semiconductor elements include a rectifier diode, a power transistor, a power MOSFET, an insulated gate bipolar transistor (IGBT), a thyristor, a gate turn-off thyristor (GTO), a triac, etc.

[0019] The resin composition can also be used in a variety of applications, such as an encapsulating material for encapsulating components such as electronic components such as semiconductor chips; a molding material for forming components for constituting electronic devices, vehicles such as automobiles, aircraft, power generation facilities, medical instruments, daily necessities, etc.; and other materials in which epoxy resins are used. The resin composition may be used alone, or may be used as a composite material in which it is combined with other materials.

[0020] The resin composition of this embodiment will be described in detail below.

[0021] (epoxy resin) The resin composition is a thermosetting epoxy resin composition containing an epoxy resin. The epoxy resin is a compound having two or more epoxy groups in one molecule, and can be a monomer, oligomer, or polymer in general, with no particular limitation on its molecular weight or molecular structure. These may be used alone or in combination of two or more.

[0022] Examples of epoxy resins include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4'-(1,3-phenylenediisopridiene)bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene)bisphenol type epoxy resin), and bisphenol Z type epoxy resin (4,4'-cyclohexidienebisphenol type epoxy resin); phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type novolac type epoxy resin, tetraphenol group ethoxylated epoxy resin, and the like. Examples of epoxy resins include novolac-type epoxy resins such as benzophenone-type novolac-type epoxy resins and novolac-type epoxy resins having a condensed ring aromatic hydrocarbon structure; biphenyl-type epoxy resins; aryl alkylene-type epoxy resins such as xylylene-type epoxy resins and biphenyl aralkyl-type epoxy resins; naphthalene-type epoxy resins such as naphthylene ether-type epoxy resins, naphthol-type epoxy resins, naphthalene diol-type epoxy resins, bifunctional to tetrafunctional epoxy-type naphthalene resins, binaphthyl-type epoxy resins, and naphthalene aralkyl-type epoxy resins; anthracene-type epoxy resins; phenoxy-type epoxy resins; dicyclopentadiene-type epoxy resins; norbornene-type epoxy resins; adamantane-type epoxy resins; and fluorene-type epoxy resins. These may be used alone or in combination of two or more. Among these, the epoxy resin may contain one or more selected from the group consisting of bisphenol A type epoxy resins, novolac type epoxy resins, and biphenyl aralkyl type epoxy resins, and preferably contains either a novolac type epoxy resin or a biphenyl aralkyl type epoxy resin.

[0023] The content of the epoxy resin can be appropriately selected depending on the application.

[0024] The resin composition may contain other thermosetting resins in addition to the epoxy resin, but does not necessarily have to contain other thermosetting resins. Other thermosetting resins include, for example, polyimide resins, benzoxazine resins, unsaturated polyester resins, phenolic resins, melamine resins, silicone resins, bismaleimide resins, acrylic resins, and phenol derivatives and their derivatives. These thermosetting resins can be any monomer, oligomer, or polymer having two or more reactive functional groups per molecule, and their molecular weights and molecular structures are not particularly limited. These resins may be used alone or in combination of two or more.

[0025] (hardening agent) The resin composition includes a curing agent for the epoxy resin. Such curing agents include polyaddition type curing agents of at least one of phenolic resins and acid anhydrides.

[0026] Examples of phenolic resin-based curing agents include novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, naphthol novolac resin, aminotriazine novolac resin, novolac resin, and trisphenylmethane-type phenol novolac resin; modified phenolic resins such as terpene-modified phenolic resin and dicyclopentadiene-modified phenolic resin; aralkyl-type resins such as phenol aralkyl resins having a phenylene skeleton and / or biphenylene skeleton and naphthol aralkyl resins having a phenylene skeleton and / or biphenylene skeleton; bisphenol compounds such as bisphenol A and bisphenol F; and resol-type phenolic resins. These may be used alone or in combination of two or more.

[0027] Examples of acid anhydride curing agents include alicyclic acid anhydrides such as phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, hexahydro-3-methylphthalic anhydride, hexahydro-4-methylphthalic anhydride, and methyltetrahydrophthalic anhydride, and aromatic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic acid, etc. These may be used alone or in combination of two or more.

[0028] The curing agent may contain other curing agents in addition to the phenolic resin and the acid anhydride, as necessary, and known curing agents such as polyaddition type curing agents, catalyst type curing agents, and condensation type curing agents may be used as the other curing agents.

[0029] The content of the curing agent can be appropriately set depending on the content of the epoxy resin.

[0030] (latent crosslinking agent) Latent crosslinkers include aminophenylphosphine compounds.

[0031] The aminophenylphosphine compound has, in its molecule, a trivalent P element, an N-P bond in which the N atom of the N-atom-containing group directly bonds to the trivalent P element, and a phenyl group. The trivalent P element may be bonded to the phenyl group directly or via a linking group. The N atom-containing group may be any reactive functional group that is reactive with the epoxy resin or the curing agent.

[0032] The aminophenylphosphine compound may include a compound having a structure of the following general formula (I): These may be used alone or in combination of two or more.

[0033] (R a ) m -P-(NR b R c ) n ·General formula (I)

[0034] In the above general formula (I), R a is either an aromatic group containing a substituted or unsubstituted phenyl group or a group containing a substituted or unsubstituted heterocycle, and R b , and R c may be the same or different and are independently any of a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, and a group containing a substituted or unsubstituted heterocycle; R b , and R cTwo or more of any of the above groups may be bonded to each other to form a ring, n is an integer of 1 to 3, each m is independently an integer of 0 to 2, and the sum of m and n is 3.

[0035] Examples of the aliphatic group include linear, branched, or cyclic, saturated or unsaturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms. The aliphatic hydrocarbon group may contain a heteroatom such as a nitrogen atom or an oxygen atom within the group.

[0036] Examples of aromatic groups (aryl groups) include phenyl groups and naphthyl groups.

[0037] The substitution may be such that one or more of substituents such as an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, or an aryl group are bonded to any atom in the group, or one or more of the atoms in the group may be replaced with a heteroatom such as a nitrogen atom or an oxygen atom.

[0038] R b and R c may each contain at least one of a ring, an unsaturated bond, a nitrogen atom, and an oxygen atom in the group, and may be bonded to each other to form a ring.

[0039] The ring may include one or more of an alicyclic ring, an aromatic ring, and a heterocyclic ring. When two or more rings are included, they may be bonded via a single bond or an alkyl group, or may be fused together to form a fused ring. The ring may be unsubstituted or substituted. Examples of the alicyclic ring include monocyclic rings such as cycloalkanes, and bicyclic rings such as decahydronaphthalene. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. The heterocyclic ring may be saturated or unsaturated, and includes three-, four-, five-, and six-membered rings containing one or more heteroatoms such as nitrogen or oxygen atoms.

[0040] The aminophenylphosphine compound may contain one or more compounds of the general formula (I) where n is any one of 1 to 3, and preferably contains a compound where n is 2. By setting n to 2 or more, curability can be improved. By setting n to 2 or less, flame retardancy and stability can be improved.

[0041] The aminophenylphosphine compound is a compound represented by the general formula (I) in which m is 1 and R a may contain a compound in which is a phenyl group, whereby the flame retardancy of the latent crosslinking agent in the resin composition can be enhanced. At this time, R b and R c The rings formed by bonding these two groups may be the same or different. From the viewpoint of curability, the ring preferably has two or more nitrogen atoms therein.

[0042] The aminophenylphosphine compound may include a compound having a structure of the following general formula (II): These may be used alone or in combination of two or more.

[0043] [ka]

[0044] In the general formula (II), R1, R2, R3, and R4 may be the same or different and each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, or a group containing a substituted or unsubstituted heterocycle. Either R1 and R2, or R3 and R4, may be bonded to each other to form a ring. Examples of the aliphatic group, aromatic group, and ring in general formula (II) may be the same as those in general formula (I).

[0045] In addition, -NR1R2 and -NR3R4 in the general formula (II) may each be composed of the same or different functional groups, or may each constitute one functional group.

[0046] At least one of the functional groups R1, R2, R3, and R4 may or may not have a ring within the group. When a ring is present, at least one of R2 and R4 may have a group with the same structure as R1 and R3, or may have a different group, which may be a hydrogen atom or an alkyl group such as a methyl group. The ring contained in the group of R1, R2, R3, and R4 may be configured to include an N atom in the above general formula (II), or may be configured to bond to the N atom via an alkyl group such as a methyl group or an ethyl group.

[0047] The functional group may also have a ring formed by bonding two groups, R1 and R2, and two groups, R3 and R4, to each other.

[0048] Examples of functional groups are shown below. In the examples, the bond of the N element in -NR1R2 and -NR3R4 is indicated by a wavy line.

[0049] [ka]

[0050] An example of the resin composition of the present embodiment includes an epoxy resin, a curing agent, and a latent crosslinking agent, wherein the curing agent includes a phenolic resin and / or an acid anhydride, and the latent crosslinking agent includes an aminophenylphosphine compound in which a trivalent P element has an N-P bond and a phenyl group, and the content of the aminophenylphosphine compound may be 0.3 mol % or more relative to 100 mol % of the total content of the phenolic resin and the anhydride.

[0051] The lower limit of the content of the aminophenylphosphine compound in the resin composition is, for example, 0.3 mol % or more, preferably 0.5 mol % or more, and more preferably 1.0 mol % or more, relative to 100 mol % of the total content of the phenolic resin and the acid anhydride, thereby improving the flame retardancy of the resin composition. On the other hand, the lower limit of the content of the aminophenylphosphine compound in the resin composition is, for example, 12 mol % or less, preferably 10 mol % or less, relative to 100 mol % of the total content of the phenolic resin and the acid anhydride, thereby preventing a decrease in the heat resistance of the resin composition.

[0052] The resin composition may contain an organic base in addition to the aminophenylphosphine compound, if necessary. As the organic base, an amine-based curing accelerator or a phosphorus-based curing accelerator may be used. Examples of organic bases that can be used include compounds having a heterocyclic structure containing a heteroatom such as a nitrogen atom or a phosphorus atom, compounds having a structure in which an aromatic group is bonded to a heteroatom, etc. These may be used alone or in combination of two or more.

[0053] Examples of organic bases include organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds. Examples of organic phosphines include primary phosphines such as ethylphosphine and phenylphosphine; secondary phosphines such as dimethylphosphine and diphenylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, tributylphosphine and triphenylphosphine.

[0054] Examples of organic bases include imidazoles, heterocyclic amines such as pyridine, dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), and N,N-dimethyl-4-aminopyridine (DMAP); and other primary, secondary, and tertiary amines. Examples of imidazoles include 2-phenylimidazole, 2-methylimidazole, 2-phenyl-4-methylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole.

[0055] Examples of organic bases include phosphorus / nitrogen-containing phosphazene derivatives.

[0056] The resin composition may contain a filler. As the filler, an inorganic filler or an organic filler is used. Examples of inorganic fillers include silica such as fused crushed silica, fused spherical silica, crystalline silica, secondary agglomerated silica, and finely divided silica; metal compounds such as alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, silicon carbide, aluminum hydroxide, magnesium hydroxide, and titanium white; talc; clay; mica; glass fiber; etc. These may be used alone or in combination of two or more.

[0057] (Other ingredients) The resin composition may contain, as needed, one or more of various additives such as a coupling agent, a fluidity imparting agent, a mold release agent, an ion scavenger, a curing accelerator other than an organic base, a stress reducing agent, a colorant, and a flame retardant.

[0058] Specific examples of coupling agents include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styryl silanes such as p-styryltrimethoxysilane; methacryl silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; acryl silanes such as 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-amino Examples of suitable coupling agents include aminosilanes such as N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and phenylaminopropyltrimethoxysilane; isocyanurate silanes; alkyl silanes; ureidosilanes such as 3-ureidopropyltrialkoxysilane; mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate silanes such as 3-isocyanatopropyltriethoxysilane; titanium compounds; aluminum chelates; and aluminum / zirconium compounds. The coupling agent may be one or more of the above specific examples.

[0059] The fluidity imparting agent can suppress the reaction of non-latent curing accelerators such as phosphorus atom-containing curing accelerators during melt-kneading of the resin composition, thereby improving the productivity of the resin composition. Specific examples of the fluidity imparting agent include compounds in which hydroxyl groups are bonded to two or more adjacent carbon atoms constituting an aromatic ring, such as catechol, pyrogallol, gallic acid, gallic acid esters, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and derivatives thereof.

[0060] Specific examples of the release agent include natural waxes such as carnauba wax, synthetic waxes such as Montan acid ester wax and oxidized polyethylene wax, higher fatty acids such as zinc stearate and metal salts thereof, paraffin, carboxylic acid amides such as erucic acid amide, etc. One or more of the above specific examples can be blended as the release agent.

[0061] Specific examples of the ion scavenger include hydrotalcites such as hydrotalcite and hydrotalcite-like substances, and hydrated oxides of elements selected from magnesium, aluminum, bismuth, titanium, and zirconium. One or more of the above specific examples can be blended as the ion scavenger.

[0062] As the curing accelerator, for example, other curing accelerators than the above organic bases may be used.

[0063] Specific examples of the low stress agent include silicone compounds such as silicone oil and silicone rubber, polybutadiene compounds, and acrylonitrile-butadiene copolymer compounds such as acrylonitrile-carboxyl group-terminated butadiene copolymer compounds. One or more of the above specific examples can be blended as the low stress agent.

[0064] Specific examples of the colorant include carbon black, red iron oxide, titanium oxide, etc. One or more of the above specific examples of the colorant may be blended.

[0065] Specific examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, phosphazene, carbon black, etc. One or more of the above specific examples can be blended as the flame retardant.

[0066] The resin composition of the present embodiment may be a liquid resin composition or a solid resin composition at 25°C. The solid resin composition may be in the form of, for example, granules, powder, tablets, sheets, etc. Furthermore, the solid resin composition for semiconductor encapsulation may be in the form of, for example, powder, granules, or tablets.

[0067] A method for producing the resin composition of this embodiment will be described. The method for producing the resin composition includes a mixing step of mixing the above-mentioned raw material components.

[0068] In the mixing step, the mixing method is not limited, and a known method can be used depending on the components used. For example, a mixer or the like can be used as a mixing method. If necessary, after mixing, the components can be melt-kneaded using a kneading machine such as a roll, kneader, or extruder.

[0069] A structure using the resin composition of this embodiment will be described.

[0070] The structure of this embodiment includes a cured product of the above-described resin composition. As an example of a structure, an electronic device will be given with reference to FIG. FIG. 1 is a cross-sectional view showing an electronic device 100. As shown in FIG. 1 includes a substrate 30, an electronic component 20 provided on the substrate 30, and an encapsulating resin layer 50 that encapsulates the electronic component 20. The encapsulating resin layer 50 is formed from a cured product of the above-described resin composition. The electronic component 20 may be electrically connected to the outside by a bonding wire 40 .

[0071] Specifically, the electronic component 20 is fixed onto the substrate 30 via the die attach material 10, and the electronic device 100 has outer leads 34 connected via bonding wires 40 to electrode pads (not shown) provided on the electronic component 20. The bonding wires 40 can be set taking into consideration the electronic component 20 to be used, and for example, Cu wires can be used.

[0072] The method for forming the encapsulating resin layer is not limited, and examples thereof include transfer molding, compression molding, injection molding, etc. By these methods, the encapsulating resin layer can be formed by molding and curing the resin composition.

[0073] The electronic component is preferably, but not limited to, a semiconductor element. Examples of semiconductor elements include, but are not limited to, integrated circuits, large scale integrated circuits, transistors, thyristors, diodes, and solid-state imaging elements. Among these, the semiconductor element for which the resin composition of the present embodiment is useful is a semiconductor element having an exposed metal portion. This can suppress corrosion of the metal portion. An example of such a semiconductor element having an exposed metal portion is a transistor. Among transistors, the resin composition of the present embodiment can be effectively used for encapsulating an MIS transistor having an exposed gate electrode.

[0074] The substrate is not limited to, but examples thereof include wiring substrates such as interposers, lead frames, and the like.

[0075] When electrical connection between an electronic component and a substrate is required, the connection may be made as appropriate. The electrical connection method is not limited, but examples thereof include wire bonding and flip-chip connection. Among these, the semiconductor element for which the resin composition of the present embodiment is useful is a semiconductor element in which a metal portion is exposed. This can suppress corrosion of the metal portion. An example of an electrical connection method for such an exposed metal portion is wire bonding.

[0076] An electronic device can be obtained by forming an encapsulating resin layer that encapsulates electronic components using the resin composition. The electronic device is not limited to, but is preferably a semiconductor device obtained by molding a semiconductor element. Specific types of semiconductor devices include MAP (Mold Array Package), QFP (Quad Flat Package), SOP (Small Outline Package), CSP (Chip Size Package), QFN (Quad Flat Non-leaded Package), SON (Small Outline Non-leaded Package), BGA (Ball Grid Array), LF-BGA (Lead Flame BGA), FCBGA (Flip Chip BGA), MAPBGA (Molded Array Process BGA), eWLB (Embedded Wafer-Level BGA), Fan-In type eWLB, and Fan-Out type eWLB.

[0077] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention. [Example]

[0078] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the descriptions of these examples.

[0079] The information on the raw material ingredients in Table 1 is shown below. (epoxy resin) Epoxy resin 1: Bisphenol A epoxy resin (liquid at 25°C) Epoxy resin 2: Biphenyl aralkyl epoxy resin (solid at 25°C) Epoxy resin 3: Novolac type epoxy resin (solid at 25°C) (hardening agent) Acid anhydride 1: Hexahydro-4-methylphthalic anhydride (liquid at 25°C) Phenolic resin 1: Novolac type phenolic resin (solid at 25°C)

[0080] (latent crosslinking agent)

[0081] Latent crosslinker 1: Aminophenylphosphine compound (solid at 25°C) represented by the following chemical formula

[0082] [ka]

[0083] Latent crosslinker 2: Aminophenylphosphine compound (solid at 25°C) represented by the following chemical formula

[0084] [ka]

[0085] Latent crosslinker 3: Aminophenylphosphine compound (liquid at 25°C) represented by the following chemical formula

[0086] [ka]

[0087] (organic base) Organic base 1: 2,4,6-tris(dimethylaminomethyl)phenol (TDAP) Organic base 2: 2-ethyl-4-methylimidazole (2E4MZ) Organic base 3: Triphenylphosphine (TPP) Organic base 4: 4-methylpiperidine

[0088] <Preparation of Resin Composition> (Examples 1 to 18, Comparative Examples 1 to 4) When either the epoxy resin or the curing agent contained a liquid component, the blended raw material components were measured according to the blending ratio (by weight) in Table 1 and mixed using a planetary centrifugal mixer to obtain a liquid resin composition. (Examples 19 to 24) When both the epoxy resin and the curing agent were solid components, the raw material components were weighed according to the compounding ratios (by weight) in Table 1, mixed in a mortar at room temperature, melt-mixed on a hot plate at 120°C for 1 minute, cooled, and then pulverized to obtain a solid resin composition.

[0089] [Table 1]

[0090] The resulting resin compositions were evaluated based on the following evaluation items.

[0091] (DSC) Using a differential scanning calorimeter (Seiko Instruments DSC-6100), a DSC curve was measured for 10 mg of the liquid or solid resin composition in a nitrogen stream at a temperature rise rate of 5°C / min over a temperature range of 0°C to 250°C. The exothermic onset temperature (Onset) was determined from the obtained DSC curve.

[0092] (flow time) A reference resin composition was prepared using the same raw material components and component ratios as those of the resin compositions of Examples 1, 4, and 5, except that it did not contain a latent crosslinking agent. The flow time (seconds) of the above resin composition and the reference resin composition at 120° C. was measured using a cone-plate viscometer (manufactured by Toa Kogyo Co., Ltd., serial number CV-1S). The resin compositions of Examples 1, 4, and 5 showed longer flow times than the corresponding reference resin compositions, confirming that the aminophenylphosphine compounds 1 to 3 function as latent crosslinking agents.

[0093] The resin compositions obtained in Examples 1, 3 to 6, 10 to 15 and Comparative Examples 1 to 4 were heat-treated in a mold at 120°C for 1 hour, then released from the mold and further heat-treated at 150°C for 1 hour to prepare evaluation samples. The resin compositions obtained in Examples 2 and 7 to 9 were heat-treated in a mold at 120° C. for 1 hour, then released from the mold and further heat-treated at 170° C. for 1 hour to prepare evaluation samples. The resin compositions obtained in Examples 16 to 24 were each heat-treated in a mold at 150°C for 10 minutes, then released from the mold and further heat-treated at 170°C for 1 hour to prepare evaluation samples. (Td5: 5% weight loss temperature) Using a thermogravimetric and differential thermal analyzer (Seiko Instruments, TG / DTA6200), the evaluation sample was heated from 30°C to 800°C at a heating rate of 10°C / min in a dry nitrogen stream, and the temperature (Td5) at which the sample loses 5% weight was calculated. The evaluation samples were dried at 100° C. for 1 hour immediately before the measurement.

[0094] (Char yield) The resulting evaluation sample was pulverized to obtain a hardened powder. The initial weight of the hardened powder was measured at room temperature (25°C). The sample was then heated from room temperature (25°C) to 800°C at a rate of 10°C / min. After holding at 800°C for 1 minute, the weight of the hardened powder remaining at 800°C was measured. The residual carbon percentage (%) was calculated based on the formula: (residual weight / initial weight)×100, which represents the ratio of the residual weight to the initial weight.

[0095] (Limiting Oxygen Index: LOI) The LOI (Limiting Oxygen Index, unit: %) was calculated using the Van Krevelen-Hoftyzer formula (LOI = 17.5 + 0.4CY). However, for CY (Char yield) in the formula, the value calculated from the residual carbon rate (%) was used. In Table 1, an LOI value of 26 or more is represented by ◎, an LOI value of 21 or more but less than 26 is represented by ○, and an LOI value of less than 21 is represented by ×.

[0096] The results of Comparative Example 4 show that the NP bond in the aminophenylphosphine compound has an effect on improving flame retardancy. The resin compositions of Examples 1 to 24 had higher LOI values than those of Comparative Examples 1 to 4 which did not contain a latent crosslinking agent, and therefore showed results that could improve flame retardancy. [Explanation of symbols]

[0097] 10 Die attach material 20 Electronic Elements 30 Base material 32 die pad 34 outer lead 40 Bonding Wire 50 Sealing resin layer 100 Electronic equipment

Claims

1. Epoxy resin, A hardener; a latent crosslinking agent; the curing agent comprises a phenolic resin and / or an acid anhydride; the latent crosslinking agent contains an aminophenylphosphine compound in which a trivalent P element has an N-P bond and a phenyl group; The resin composition, wherein the aminophenylphosphine compound comprises a compound having a structure of the following general formula (I): (R a ) m -P-(NR b R c ) n...General formula (I) (In the above general formula (I), R a is a phenyl group; R b and R c may be the same or different and each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, or a group containing a substituted or unsubstituted heterocycle; R b and R c may be bonded to each other to form a ring; R b and R c may contain a nitrogen element; n is 2; and m is 1.)

2. The resin composition according to claim 1, A resin composition configured so that the 5% weight loss temperature Td5 of the cured product of the resin composition is 300°C or higher.

3. A structure comprising a cured product of the resin composition according to claim 1 or 2.

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