JP7434972B2 - Latent crosslinkers, resin compositions, and structures - Google Patents

Description

The present invention relates to a latent crosslinking agent, a resin composition, and a structure.

Until now, various developments have been made regarding resin compositions. As this type of technology, for example, the technology described in Patent Document 1 is known. Patent Document 1 describes the use of an imidazole type latent curing agent in an epoxy resin composition (Claims 1 and 5 of Patent Document 1).

JP2009-256483A

However, as a result of studies conducted 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 reactivity in a low-temperature environment.

As a result of thorough studies on phosphorus-based compounds and nitrogen-based compounds, the present inventor discovered that aminophosphine compounds, in which a trivalent P element has an NP bond, have potential in the polymerization reaction of epoxy resins and phenolic resins. It functions as a crosslinking agent, and by adding it to a resin composition containing epoxy resin or phenol resin, the starting temperature of the polymerization reaction can be lowered, making it possible to realize a resin composition with excellent reactivity in a low-temperature environment. They discovered this and completed the present invention.

According to the invention,
A latent crosslinking agent used for polymerizing an epoxy resin or/and a phenolic resin, comprising:
A latent crosslinking agent is provided that includes an aminophosphine compound in which a trivalent P element has an NP bond.

Further, according to the present invention,
At least one of an epoxy resin and a phenolic resin;
A resin composition is provided that includes the latent crosslinking agent described above.

Further, according to the present invention, a structure including a cured product of the above resin composition is provided.

According to the present invention, a latent crosslinking agent with excellent reactivity in a low-temperature environment, a resin composition using the same, and a structure are provided.

1 is a cross-sectional view showing an example of the configuration of an electronic device according to an embodiment.

Embodiments of the present invention will be described below with reference to the drawings. Note that in all the drawings, similar components are denoted by the same reference numerals, and descriptions thereof will be omitted as appropriate. Furthermore, the figure is a schematic diagram and does not correspond to the actual dimensional ratio.

The latent crosslinking agent and resin composition of this embodiment will be summarized.

The latent crosslinking agent includes an aminophosphine compound in which a trivalent P element has an NP bond.
This latent crosslinking agent is used to polymerize epoxy resins or/and phenolic resins.

According to the findings of the present inventors, aminophosphine compounds in which a trivalent P element has an N-P bond (hereinafter sometimes simply referred to as aminophosphine compounds having an N-P bond) are epoxy resins and It functions as a latent crosslinking agent in the polymerization reaction of phenolic resins, and by adding it to resin compositions containing epoxy resins and phenolic resins, the starting temperature of the polymerization reaction can be lowered, reducing reactivity in low-temperature environments. It has been discovered that an excellent resin composition can be achieved.

Although the detailed mechanism is not clear, it is thought that the aminophosphine compound having an NP bond reacts in a low temperature environment and is included in the crosslinked structure of the polymer.

According to this embodiment, by using a latent crosslinking agent, it is possible to realize a resin composition that has excellent reactivity and low-temperature curability in a low-temperature environment.

The resin composition can be used, for example, as a heat dissipation material, an insulating material, or a semiconductor sealing material for electric/electronic equipment.
As the electric/electronic device, for example, a normal semiconductor device (an electronic device including a semiconductor element as an electronic component), a power module (an electronic device including a power semiconductor element as an electronic component), etc. can be used. Specific examples of power semiconductor devices include rectifier diodes, power transistors, power MOSFETs, insulated gate bipolar transistors (IGBT), thyristors, gate turn-off thyristors (GTO), triacs, and the like.

In addition, the resin composition is used as a sealing material for sealing members such as electronic components such as semiconductor chips, and as a molding material for forming members constituting electronic devices, vehicles such as automobiles, medical instruments, daily necessities, etc. In addition, it can be applied to various applications where epoxy resins and phenolic resins are used.

Hereinafter, the resin composition containing the latent crosslinking agent of this embodiment will be described in detail.

The resin composition includes at least one of an epoxy resin and a phenol resin, and a latent crosslinking agent.

(Epoxy resin)
Epoxy resin is a compound having two or more epoxy groups in one molecule, and monomers, oligomers, and polymers in general can be used, and the molecular weight and molecular structure thereof are not particularly limited. These may be used alone or in combination of two or more.

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, bisphenol S epoxy resin, and bisphenol M epoxy resin (4,4'-(1,3-phenylenediiso) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexy Bisphenol-type epoxy resins such as diene bisphenol-type epoxy resins; phenol novolac-type epoxy resins, cresol novolak-type epoxy resins, trisphenol-based methane-type novolak-type epoxy resins, tetraphenol-based ethane-type novolak-type epoxy resins, condensed ring aromatic carbonization Novolac type epoxy resins such as novolac type epoxy resins having a hydrogen structure; biphenyl type epoxy resins; aryl alkylene type epoxy resins such as xylylene type epoxy resins and biphenylaralkyl type epoxy resins; naphthylene ether type epoxy resins, naphthol type epoxy resins, Naphthalene type epoxy resins such as naphthalene diol type epoxy resins, difunctional to tetrafunctional epoxy type naphthalene resins, binaphthyl type epoxy resins, naphthalene aralkyl type epoxy resins; anthracene type epoxy resins; phenoxy type epoxy resins; dicyclopentadiene type epoxy resins; Norbornene type epoxy resin; adamantane type epoxy resin; fluorene type epoxy resin and the like. These may be used alone or in combination of two or more.

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

The resin composition may or may not contain other thermosetting resins in addition to the epoxy resin.
Other thermosetting resins include, for example, polyimide resins, benzoxazine resins, unsaturated polyester resins, phenol resins, melamine resins, silicone resins, bismaleimide resins, acrylic resins, phenol derivatives, and derivatives thereof. As these thermosetting resins, monomers, oligomers, and polymers in general having two or more reactive functional groups in one molecule can be used, and the molecular weight and molecular structure thereof are not particularly limited. These may be used alone or in combination of two or more.

(hardening agent)
The resin composition may contain an epoxy resin curing agent, if necessary.
The curing agent is selected depending on the type of thermosetting resin, and is not particularly limited as long as it reacts with the thermosetting resin. Specific examples of the curing agent include polyaddition type curing agents, catalyst type curing agents, and condensation type curing agents.

Specifically, the polyaddition type curing agents include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), metaxylylene diamine (MXDA); diaminodiphenylmethane (DDM), m-phenylene Aromatic polyamines such as diamine (MPDA) and diaminodiphenylsulfone (DDS); polyamine compounds such as dicyandiamide (DICY) and organic acid dihydralazide; alicyclic compounds such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA) Group acid anhydrides; acid anhydrides such as aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), and benzophenone tetracarboxylic acid (BTDA); novolac type phenolic resin, polyvinylphenol, aralkyl Examples include phenolic resin curing agents such as type phenolic resins; polymercaptan compounds such as polysulfides, thioesters, and thioethers; isocyanate compounds such as isocyanate prepolymers and blocked isocyanates; and organic acids such as carboxylic acid-containing polyester resins. As the polyaddition type curing agent, one or a combination of two or more of the above specific examples can be used.

Specifically, the above-mentioned catalytic curing agents include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole; Examples include imidazole compounds such as -ethyl-4-methylimidazole (EMI24); Lewis acids such as BF3 complex, and the like. As the catalytic curing agent, one or a combination of two or more of the above specific examples can be used.

Specific examples of the condensation type curing agent include resol type phenol resins; urea resins such as methylol group-containing urea resins; and melamine resins such as methylol group-containing melamine resins. As the condensation type curing agent, one or a combination of two or more of the above specific examples can be used.

Among the specific examples above, the curing agent may include a phenolic resin curing agent.
As the above-mentioned phenolic resin curing agent, a phenol resin can be used, and specifically, a phenol novolak resin, a cresol novolak resin, a naphthol novolak resin, an aminotriazine novolak resin, a novolak resin, a trisphenylmethane type phenol novolak resin Modified phenolic resins such as terpene-modified phenolic resins and dicyclopentadiene-modified phenolic resins; phenol aralkyl resins having a phenylene skeleton and/or biphenylene skeleton, naphthol aralkyl resins having a phenylene skeleton and/or biphenylene skeleton, etc. aralkyl type resins; bisphenol compounds such as bisphenol A and bisphenol F; and resol type phenol resins.
These may be used alone or in combination of two or more. Among these, novolac type phenolic resin can be used from the viewpoint of improving the glass transition temperature and reducing the coefficient of linear expansion.

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

(Latent crosslinking agent)
The latent crosslinking agent in the composition includes an aminophosphine compound in which the trivalent P element has an NP bond.

The aminophosphine compound may include a compound having the structure of general formula (I) below. These may be used alone or in combination of two or more.

(R ^a ) _m -P-(NR ^b R ^c ) _n ...General formula (I)

In the above general formula (I), R ^a , R ^b , and R ^c may each independently be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group. , and a group containing a substituted or unsubstituted heterocycle, and R ^b and R ^c may contain at least one of a ring, an unsaturated bond, a nitrogen element, and an oxygen atom in the group. Often, any two or more groups of R ^a , R ^b , and R ^c may be bonded to each other to form a ring, n is an integer from 1 to 3, and m is each independently 0. It is an integer of ~2, and the sum of m and n is 3.

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 in the group.

Examples of the aromatic group (aryl group) include phenyl group and naphthyl group.

Substitution means that one or more substituents such as an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, an aryl group, etc. may be bonded to any atom in the group. , one or more atoms in the group may be replaced with a heteroatom such as a nitrogen atom or an oxygen atom.

R ^b and R ^c may each have a ring in the group, or may be bonded to each other to form a ring.

The ring may include one or more of an alicyclic ring, an aromatic ring, and a heterocycle. When two or more rings are included, they may be bonded via a single bond or an alkyl group, or may be condensed with each other to form a condensed ring. Further, the ring may be unsubstituted or substituted.
Examples of the alicyclic ring include monocycles such as cycloalkane, bicycles such as decahydronaphthalene, and the like.
Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and the like.
Heterocycles may be saturated or unsaturated, and include three-, four-, five-, and six-membered rings containing one or more heteroatoms such as nitrogen atoms and oxygen atoms. It will be done.

The aminophosphine compound may include a compound where n is 2 in the above general formula (I). This makes it possible to improve the curability.

The aminophosphine compound may include a compound in the above general formula (I) where m is 1 and R ^a is a phenyl group. Thereby, the dispersibility of the latent crosslinking agent in the resin composition can be improved.
At this time, the rings formed by bonding the two groups R ^b and R ^c to each other may be the same or different. From the viewpoint of curability, the ring preferably has two or more nitrogen atoms inside.

The aminophosphine compound may include a compound having the structure of general formula (II) below. These may be used alone or in combination of two or more.

In the above general formula (II), R ₁ , R ₂ , R ₃ , and R ₄ may each independently be the same or different, and include a hydrogen atom, a substituted or unsubstituted aliphatic group, and a substituted or unsubstituted aliphatic group. An aromatic group, and a group containing a substituted or unsubstituted heterocycle.
Two groups of either R ₁ and R ₂ or R ₃ and R ₄ may be bonded to each other to form a ring. Regarding the examples of the aliphatic group, aromatic group, and ring in general formula (II), the same ones as in general formula (I) may be used.

Furthermore, -NR ₁ R ₂ and -NR ₃ R ₄ in the above general formula (II) may each be composed of the same or different functional groups, or may mutually constitute one functional group.

An example of the functional group is shown below.
In the examples, for the N element in -NR ₁ R ₂ and -NR ₃ R ₄ , a wavy line is drawn at the bond.

At least one of R ₁ , R ₂ , R ₃ , and R ₄ may have a ring in each functional group, but does not need to have one. When having a ring, at least one of R ₂ and R ₄ may have a group having the same structure as R ₁ and R ₃ , but may also have a different group, and the different groups include a hydrogen atom, a methyl It may be an alkyl group such as a group. The rings contained in the groups R ₁ , R ₂ , R ₃ , and R ₄ may be configured to include the N atom in the above general formula (II), and the N atom and the methyl group or ethyl group may be configured to be bonded via an alkyl group such as.

Further, the functional group may have a ring in which two groups R ₁ and R ₂ and two groups R ₃ and R ₄ are bonded to each other.

The aminophosphine compound reacts with the phenolic resin and can form part of the crosslinked structure of the phenolic resin polymer.

The aminophosphine compound may include at least one of a liquid at 25°C and a solid at 25°C. For example, the aminophosphine compound may include two or more types that are liquid at 25°C, may include two or more types that are solid at 25°C, or may include both liquid and solid.
The aminophosphine compound may include a compound having a lower limit of melting point, for example, 30°C or higher, preferably 35°C or higher, more preferably 40°C or higher, still more preferably 60°C or higher. This makes it possible to improve the handleability of the latent crosslinking agent, improve uniform dispersion in the composition, and improve reactivity. These may be used alone or in combination of two or more.
On the other hand, the aminophosphine compound may include a compound whose upper limit of melting point is, for example, 250° C. or lower. This makes it possible to provide a resin composition that exhibits excellent low-temperature curing.
Among these, the aminophosphine compound may include one or more solid compounds having a melting point of 35° C. or higher.

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

(Other ingredients)
The resin composition may contain 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, a low stress agent, a coloring agent, and a flame retardant, as necessary. Two or more types may be included as appropriate.

Specific examples of the coupling agent include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and - Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; 3-methacryloxypropyl Methacrylsilanes such as methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; Acrylicsilanes such as 3-acryloxypropyltrimethoxysilane; N -2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Aminosilanes such as triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and phenylaminopropyltrimethoxysilane; Isocyanurate silanes; Alkylsilanes; 3- ureidosilanes such as ureidopropyltrialkoxysilane; mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanatesilanes such as 3-isocyanatepropyltriethoxysilane; titanium-based compounds; aluminum chelates; Examples include aluminum/zirconium compounds. As the coupling agent, one or more of the above specific examples can be blended.

The fluidity imparting agent can suppress a curing accelerator that does not have latent properties, such as a phosphorus atom-containing curing accelerator, from reacting during melt-kneading of the resin composition. Thereby, productivity of the resin composition can be improved.
Specifically, the fluidity imparting agent includes two or more of aromatic rings such as catechol, pyrogallol, gallic acid, gallic acid ester, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and derivatives thereof. Examples include compounds in which a hydroxyl group is bonded to each adjacent carbon atom.

Specific examples of mold release agents include natural waxes such as carnauba wax; synthetic waxes such as montanic acid ester wax and oxidized polyethylene wax; higher fatty acids and their metal salts such as zinc stearate; paraffin; and erucic acid amide. Examples include carboxylic acid amide. As the mold release agent, one or more of the above specific examples can be blended.

Specific examples of the ion scavenger include hydrotalcites such as hydrotalcite and hydrotalcite-like substances; hydrous oxides of elements selected from magnesium, aluminum, bismuth, titanium, and zirconium. As the ion scavenger, one or more of the above specific examples can be blended.

The curing accelerator is, for example, a phosphorus atom-containing compound such as an organic phosphine, a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, an adduct of a phosphonium compound and a silane compound; [5.4.0] One type selected from nitrogen atom-containing compounds such as amidines, tertiary amines, and quaternary salts of the above-mentioned amidines and amines, exemplified by undecene-7, benzyldimethylamine, 2-methylimidazole, etc. Or it can contain two or more types. Among these, it is more preferable to include a phosphorus atom-containing compound from the viewpoint of improving curability. In addition, from the viewpoint of improving the balance between moldability and curability, it is desirable to have latent properties such as tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds. It is more preferable to include something.

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. As the low stress agent, one or more of the above specific examples can be blended.

Specific examples of the colorant include carbon black, red iron oxide, and titanium oxide. As the colorant, one or more of the above specific examples can be blended.

Specific examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, phosphazene, and carbon black. As the flame retardant, one or more of the above specific examples can be blended.

A method for manufacturing the resin composition of this embodiment will be explained.
The method for producing a resin composition includes a mixing step of mixing the raw material components described above.

The mixing step is a step of mixing raw material components to produce a mixture. The mixing method is not limited, and known methods can be used depending on the components used.
Specifically, in the mixing step, the raw material components included in the resin composition described above are uniformly mixed using a mixer or the like. Next, the mixture is melt-kneaded using a kneader such as a roll, kneader, or extruder to prepare a mixture.

The method for producing a resin composition may include a molding step of molding the obtained mixture.

The molding method is not limited, and any known method can be used depending on the shape of the resin composition. The shape of the resin composition is not limited, and includes, for example, granule shape, powder shape, tablet shape, sheet shape, and the like. The resin composition for semiconductor encapsulation may be in the form of powder, granules, or tablets, for example.

The shape of the resin composition can be selected depending on the molding method.
The molding process for producing a granular resin composition includes, for example, a process of melt-kneading and then pulverizing the cooled mixture. Note that, for example, the resin composition formed into granules may be sieved to adjust the size of the granules. Further, for example, the resin composition in the form of granules may be processed by a method such as a centrifugal milling method or a hot cut method to adjust the degree of dispersion or fluidity.
Further, the molding step for producing a powdered resin composition includes, for example, a step of pulverizing the mixture to form a granular resin composition, and then further pulverizing the granular resin composition.
Further, the molding process for producing a tablet-shaped resin composition includes, for example, a process of pulverizing the mixture to form a granular resin composition, and then compressing the granular resin composition into tablets.

A structure using the resin composition of this embodiment will be explained.

The structure of this embodiment includes a cured product of a resin composition.
As an example of a structure, an example of an electronic device will be given using FIG.
FIG. 1 is a cross-sectional view showing an electronic device 100.
The electronic device 100 in FIG. 1 includes a base material 30, an electronic component 20 provided on the base material 30, and a sealing resin layer 50 that seals the electronic component 20. The sealing resin layer 50 is composed of a cured product of the above resin composition.
The electronic component 20 may be electrically connected to the outside by a bonding wire 40.

Specifically, the electronic component 20 is fixed onto a base material 30 via a die attach material 10, and the electronic device 100 is connected to an electrode pad (not shown) provided on the electronic component 20 via a bonding wire 40. The outer lead 34 is connected to the outer lead 34. The bonding wire 40 can be set taking into consideration the electronic component 20 and the like to be used, and for example, a Cu wire can be used.

The method for forming the sealing resin layer is not limited, and examples thereof include transfer molding, compression molding, injection molding, and the like. By these methods, a resin composition can be molded and cured to form a sealing resin layer.

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 image sensors.
Among these, semiconductor elements for which the resin composition of this embodiment is useful are semiconductor elements in which metal parts are exposed. Thereby, corrosion of the metal portion can be suppressed. A transistor is an example of a semiconductor element in which such a metal portion is exposed. Among transistors, the resin composition of this embodiment can be effectively used for sealing MIS transistors whose gate electrodes are exposed.

Examples of the base material include, but are not limited to, wiring boards such as interposers, lead frames, and the like.

If electrical connection between the electronic component and the base material is required, the connection may be made as appropriate. The method of electrical connection is not limited, and examples thereof include wire bonding, flip-chip connection, and the like. Among these, semiconductor elements for which the resin composition of this embodiment is useful are semiconductor elements in which metal parts are exposed. Thereby, corrosion of the metal portion can be suppressed. Wire bonding is an example of such an electrical connection method in which a metal portion is exposed.

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

Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and the present invention includes modifications, improvements, etc. within a range that can achieve the purpose of the present invention.
Below, examples of reference forms will be added.
1. A latent crosslinking agent used for polymerizing an epoxy resin or/and a phenolic resin, comprising:
A latent crosslinking agent comprising an aminophosphine compound in which a trivalent P element has an NP bond.
2. 1. The latent crosslinking agent according to
A latent crosslinking agent, wherein the aminophosphine compound includes a compound having the structure of general formula (I) below.
(R ^a ) _m -P-(NR ^b R ^c ) _n ...General formula (I)
(In the above general formula (I), R ^a , R ^b , and R ^C may each independently be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group) group, and a group containing a substituted or unsubstituted heterocycle, and R ^b and R ^c may include at least one of a ring, an unsaturated bond, a nitrogen element, and an oxygen atom in the group. , R ^a , R ^b , and R ^c may be bonded to each other to form a ring, n is an integer of 1 to 3, and m is each independently 0 to 3. It is an integer of 2, and the sum of m and n is 3.)
3. 2. The latent crosslinking agent described in
A latent crosslinking agent comprising the above compound in which n is 2 in the general formula (I).
4. 2. The latent crosslinking agent described in
A latent crosslinking agent comprising the above compound in the general formula (I), where m is 1 and R ^a is a phenyl group.
5. 1. ~4. The latent crosslinking agent according to any one of
A latent crosslinking agent that constitutes a part of the crosslinked structure of the phenolic resin polymer.
6. 1. ~5. The latent crosslinking agent according to any one of
The aminophosphine compound is a latent crosslinking agent that is at least one of a liquid at 25°C and a solid at 25°C.
7. At least one of an epoxy resin and a phenolic resin;
1. ~6. A resin composition comprising the latent crosslinking agent according to any one of .
8. 7. A structure comprising a cured product of the resin composition described in .

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the description of these Examples.

Information on the raw material components in Tables 1 and 2 is shown below.
(Epoxy resin)
・Epoxy resin 1: Polycyclic aromatic epoxy resin (softening point: 54°C)
(hardening agent)
・Phenol resin 1: Polycyclic aromatic phenol resin (softening point: 74°C)

(Latent crosslinking agent)
・Latent crosslinking agent 1: 2-methylimidazole having the chemical formula shown below (melting point: 142°C, solid at 25°C)

・Latent crosslinking agent 2: Aminophosphine compound having the chemical formula shown below (melting point: 40°C, solid at 25°C)

・Latent crosslinking agent 3: Aminophosphine compound having the chemical formula shown below (melting point: 60°C, solid at 25°C)

・Latent crosslinking agent 4: Aminophosphine compound having the chemical formula below (liquid at 25°C)

<Preparation of resin composition>
The raw ingredients formulated according to Table 1 were mixed in a mortar at room temperature, and then melted and mixed for 3 minutes on a hot plate at 90°C. After cooling, it was ground again at room temperature using a mortar to obtain a powdered resin composition.

The obtained resin composition was evaluated based on the following evaluation items.

<DSC>
Using a differential scanning calorimeter (DSC-6100 manufactured by Seiko Instruments), 10 mg of the above powdered resin composition was measured under nitrogen flow at a temperature increase rate of 5° C./min in a temperature range of 0° C. to 250° C. A DSC curve was measured for.
From the obtained DSC curve, the exothermic onset temperature (Onset), the maximum exothermic peak temperature (Peak top), and the peak area up to 100°C (Area@100°C) were determined.

<Culast>
Further, 4.3 g of the obtained resin composition was put into a 25 mmφ mold and compressed at 5 tons for 1 minute to produce a tablet. The curelast torque of the obtained tablet was measured over time at a mold temperature of 100° C. using a curelastometer (Culastometer WP type, manufactured by A&D Co., Ltd.).
The value obtained when the torque value of the obtained culast torque was saturated was defined as the saturated torque value.
From the obtained culast torque, the time to reach the torque value at 90% of the saturated torque value (t (90%): time to reach 90% torque), the time to reach the torque value at 0.2% of the saturated torque value (t(0.2%): time to reach 0.2% torque), time from 0.2% saturated torque to 90% saturated torque (Δ(t(90%) - t(0.2%))) I asked for

<Viscometer>
Using a cone-plate viscometer (manufactured by Toa Kogyo Co., Ltd., serial number CV-1S), the viscosity of the powdered resin composition was measured immediately after it was placed on a hot plate at 100°C. The time immediately after being placed on the hot plate was defined as 0 s.

(FT-IR)
The following samples were heated at 5° C./min from 25° C. to 100° C. under air, and IR spectra were obtained over time using Fourier transform infrared spectroscopy (FT-IR).
・Samples 1 to 3: A mixture of latent crosslinking agent 1 and phenolic resin 1, a mixture of latent crosslinking agent 2 and phenolic resin 1, a mixture of latent crosslinking agent 3 and phenolic resin 1 In samples 1 to 3, The results showed that the peak ratio from the initial peak at 982 cm ⁻¹ and 1131 cm ⁻¹ derived from the PO(-Ph) bond increased with time.
From this result, it is inferred that latent crosslinking agents 1 to 3 are included in the crosslinked structure of the polymer of phenolic resin 1 via PO bonds.

The resin compositions of Examples 1 to 6 have lower exothermic start temperatures than Comparative Examples 1 and 2, and the resin compositions of Examples 7 and 8 have lower exothermic start temperatures than Comparative Examples 3 and 4. Since the peak area was large, it showed excellent reactivity even though it had latent properties. Examples 3 to 5 showed better curing properties at low temperatures than Examples 1 and 2 because the time required to reach 0.2% saturation torque was shorter.
Furthermore, the resin compositions of Examples 7 and 8 showed increased viscosity compared to Comparative Examples 3 and 4.
The aminophosphine compounds used in Examples 1 to 8 have superior latent properties and reactivity in low-temperature environments compared to those of comparative examples, and also function as crosslinking agents for phenolic resins, so they have excellent growth reaction promoting properties. It was found that it is a latent crosslinking agent with excellent properties.
Therefore, by using the aminophosphine compounds of Examples, a thermosetting resin composition with excellent low-temperature curing can be realized.

10 Die attach material 20 Electronic element 30 Base material 32 Die pad 34 Outer lead 40 Bonding wire 50 Sealing resin layer 100 Electronic device

Claims (6)

A latent crosslinking agent used for polymerizing an epoxy resin or/and a phenolic resin, comprising:
The trivalent P element contains an aminophosphine compound having an N-P bond,
The aminophosphine compound includes a compound having the structure of the following general formula (I),
Latent crosslinker.
(R ^a ) _m -P-(NR ^b R ^c ) _n ...General formula (I)
(In the above general formula (I), R ^a , R ^b , and R ^C may each independently be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group) group, and a group containing a substituted or unsubstituted heterocycle, and R ^b and R ^c may include at least one of a ring, an unsaturated bond, a nitrogen element, and an oxygen atom in the group. , R ^a , R ^b , and R ^c may be bonded to each other to form a ring, n is 2, m is 1, and the sum of m and n is 3.) A latent crosslinking agent used for polymerizing an epoxy resin or/and a phenolic resin, comprising:
The trivalent P element contains an aminophosphine compound having an N-P bond,
A latent crosslinking agent, wherein the aminophosphine compound includes a compound having the structure of general formula (I) below.
(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 each independently be the same or different, and include a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aliphatic group, and Any group containing a substituted aromatic group and a substituted or unsubstituted heterocycle, and R ^b and R ^c each contain at least one of a ring, an unsaturated bond, a nitrogen element, and an oxygen atom in the group. and two or more groups of R ^a , R ^b , and R ^c may be bonded to each other to form a ring, n is 2 , m is 1 , and m and the sum of n is 3.) The latent crosslinking agent according to claim 1 or 2 ,
A latent crosslinking agent that constitutes a part of the crosslinked structure of the phenolic resin polymer. The latent crosslinking agent according to any one of claims 1 to 3 ,
The aminophosphine compound is a latent crosslinking agent that is at least one of a liquid at 25°C and a solid at 25°C. At least one of an epoxy resin and a phenolic resin;
A resin composition comprising the latent crosslinking agent according to any one of claims 1 to 4 . A structure comprising a cured product of the resin composition according to claim 5 .

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