JP6999335B2 - A curable composition, a cured product of the composition, the composition and a method for producing the cured product. - Google Patents

Description

The present invention relates to a curable composition for obtaining a cured product having excellent heat resistance, the cured product thereof, and a method for producing the curable composition and the cured product.

Curable compositions containing epoxy compounds are used as materials for encapsulants, adhesives, paints, matrix resins for composite materials and the like. Among the epoxy compounds, an epoxy compound having an alicyclic skeleton is known as one that can obtain a cured product having excellent heat resistance and the like. For example, Patent Document 1 discloses an epoxy compound having an alicyclic skeleton having a specific structure capable of obtaining a resin having excellent heat resistance and the like.

Further, among these epoxy compounds, an epoxy compound having two or more alicyclic skeletons in the molecule is known as a compound capable of obtaining a cured product having excellent heat resistance, transparency and the like. Patent Document 2 discloses a curable composition containing a diepoxybicyclohexyl compound. However, the epoxy compound having an alicyclic skeleton proposed in Patent Document 2 has room for further improvement from the viewpoint of heat resistance of the cured product and the like.

Japanese Unexamined Patent Publication No. 49-126658 Japanese Unexamined Patent Publication No. 2008-31424

In applications such as adhesives, paints, encapsulants, and matrix resins for composite materials, there is still a demand for a cured resin having higher heat resistance so as to be able to meet more severe usage conditions.

Therefore, an object of the present invention is to provide a curable composition for obtaining a cured product having high heat resistance. Another object of the present invention is to provide a cured product obtained by curing the curable composition, and a method for producing the curable composition and the cured product.

As a result of diligent studies to solve the above object, the present inventors have developed a curable composition containing a polyfunctional epoxy compound, a phenol-based curing agent, and a curing accelerator, and the cured product is heat-resistant. We have found that it is excellent in properties and have completed the present invention.

That is, according to the present invention, the following invention is provided.
[1] (A) An epoxy compound having at least one norbornane structure and at least two epoxy groups,
(B) Phenolic curing agent and
(C) A curable composition containing a curing accelerator.
[2] (D) The curable composition according to [1], which further contains an epoxy compound other than the above (A).
[3] The curable composition according to [1] or [2], which further contains (E) an inorganic filler.
[4] The curable composition according to any one of [1] to [3], further containing (F) a silane coupling agent.
[5] A cured product obtained by curing the curable composition according to any one of [1] to [4].
[6] The cured product according to [5], which has a glass transition temperature of 160 ° C. or higher.
[7] A semiconductor device in which a semiconductor element is installed in the cured product according to [5] or [6].
[8] A method for producing a curable composition.
(A) An epoxy compound having at least one norbornane structure and at least two epoxy groups,
(B) Phenolic curing agent and
(C) A method for producing a curable composition, which comprises a step of mixing with a curing accelerator to obtain a mixture.
[9] The production method according to [8], wherein in the step of obtaining the mixture, (D) an epoxy compound other than the above (A) is further mixed to obtain a mixture.
[10] A method for producing a cured product, which comprises a step of heating and curing the curable composition produced by the method according to [8] or [9] at 170 to 300 ° C.

The curable composition of the present invention is a novel curable composition containing components (A) to (C) and, if desired, components (D) to (F), and the cured product of the composition has heat resistance. It has the characteristics of being good, resistant to thermal decomposition, and having a high glass transition temperature. Therefore, the curable composition of the present invention can be used in applications that require high heat resistance, such as adhesives, paints, encapsulants, and matrix resins for composite materials. In particular, it can exhibit excellent sealing performance as a semiconductor element encapsulant and contribute to high reliability of semiconductor devices.

[Curable composition]
Hereinafter, the present invention will be described in detail. The "compound" in the component (A) of the present invention includes not only the monomers represented by the respective formulas but also oligomers in which the monomers are polymerized in a small amount, that is, prepolymers before forming the cured resin. ..

(Component A)
The component (A) constituting the curable composition is an epoxy compound having at least one norbornane structure and at least two epoxy groups (hereinafter, also simply referred to as “polyfunctional epoxy compound”). As the polyfunctional epoxy compound, an alicyclic epoxy compound is preferable, and it is more preferable to have an epoxy structure bonded to a 5-membered ring, a 6-membered ring or a norbornane ring represented by the following formula (1).

As a specific polyfunctional epoxy compound, a compound represented by the following formula (2) can be exemplified.

An example of producing the polyfunctional epoxy compound of the component (A) will be described.
The compound of the following formula (2-1) can be produced, for example, as follows.

First, a compound (a) having the following norbornane structure was synthesized by a Diels-Alder reaction between butadiene and dicyclopentadiene, and then the compound (a) and metachloroperbenzoic acid were combined as shown in the following formula (3). Can be reacted to produce the compound of formula (2-1).

The compound of the following formula (2-2) can be produced, for example, as follows.

First, a compound (b) (tricyclopentadiene) having the following norbornane structure was synthesized by a Diels-Alder reaction between cyclopentadiene and dicyclopentadiene, and then the compound (b) was synthesized as shown in the following formula (4). The compound of formula (2-2) can be produced by reacting with metachloroperbenzoic acid.

The compound of the following formula (2-3) can be produced, for example, as follows.

First, a compound (c) having the following norbornane structure is synthesized by a Diels-Alder reaction between butadiene and cyclopentadiene, and then the compound (c) and metachloroperbenzoic acid are combined as shown in the following formula (5). By reacting, the compound of the formula (2-3) can be produced.

The compound of the following formula (2-4) can be produced, for example, as follows.

The compound of formula (2-4) can be produced by reacting dicyclopentadiene with potassium peroxymonosulfate (oxone). The dicyclopentadiene epoxide which is the compound of the formula (2-4) may be a commercially available product, and examples of the commercially available product include dicyclopentadiene epoxide manufactured by SHANDONG QIHUAN BIOCHEMICAL CO., LTD.

(Component B)
The component (B) constituting the curable composition is a phenolic curing agent. The phenol-based curing agent used in the present invention is a general monomer, oligomer, or polymer having two or more phenolic hydroxyl groups in one molecule, and is, for example, a phenol novolac resin, a cresol novolac resin, or a phenol aralkyl resin (preferably, a phenol aralkyl resin). Phenol aralkyl resin having a phenylene skeleton, biphenylene skeleton, etc.), naphthol aralkyl resin (preferably naphthol aralkyl resin having a phenylene skeleton, biphenylene skeleton, etc.), terpene-modified phenol resin, dicyclopentadiene-modified phenol resin, triphenol methane-type phenol. Examples thereof include, but are not limited to, resins and bisphenol compounds. The phenol-based curing agent used in the present invention is preferably a phenol novolac resin, a phenol aralkyl resin, a triphenol methane-type phenol resin, a cresol novolac resin, a dicyclopentadiene-modified phenol resin, a naphthol aralkyl resin, or a terpene-modified phenol resin. These phenolic curing agents may be used alone or in combination of two or more.

As for the blending ratio of the component (B), when the curable composition does not contain an epoxy compound (component (D)) other than the above-mentioned component (A) described later, the component contained in the curable composition of the present invention. (A) The component (B) is preferably in the range of 50 parts by mass or more and 300 parts by mass or less, and more preferably 75 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass. When the curable composition contains the component (D), the blending ratio of the component (B) in the curable composition of the present invention is 100 parts by mass in total of the above components (A) and (D). The component (B) is preferably in the range of 50 parts by mass or more and 300 parts by mass or less, and more preferably 75 parts by mass or more and 200 parts by mass or less. By containing the component (B) in this range, the curing reaction can be efficiently promoted, and a highly heat-resistant cured product can be obtained.

(Component C)
The component (C) constituting the curable composition of the present invention is a curing accelerator. As the curing accelerator, a known curing accelerator can be used, and an amine compound such as tributylamine, 1,8-diazabicyclo (5,4,0) undecene-7, 2-methylimidazole, 2-ethyl Imidazole compounds such as imidazole and 1,2-dimethylimidazole, organophosphorus compounds in which phosphorus is bound only by covalent bonds such as triphenylphosphine and tripalatorylphosphine, covalent bonds and ionic bonds such as tetraphenylphosphonium tetraphenylborate. Examples thereof include organic phosphorus compounds such as salt-type organic phosphorus compounds to which phosphorus is bound, but the present invention is not limited thereto. Further, the above-mentioned curing accelerator may be used alone or in combination of two or more. Of these, organophosphorus compounds such as triphenylphosphine, triparatrilphosphine, and tetraphenylphosphonium tetraphenylborate are preferable because they have a large effect of improving the curing rate.
As described in JP-A-55-157594, the organic phosphorus compound exhibits a function of promoting a cross-linking reaction between an epoxy group and a phenolic hydroxyl group. The organic phosphorus compound of the present invention is not particularly limited as long as it has the above-mentioned function.

The mixing ratio of the component (C) in the curable composition of the present invention is such that when the curable composition does not contain an epoxy compound (component (D)) other than the above-mentioned component (A) described later, the curing of the present invention is performed. The content of the component (C) is preferably in the range of 0.01 parts by mass or more and 20 parts by mass or less, and 0.1 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the component (A) contained in the sex composition. It is more preferable that the range is less than or equal to a part. When the curable composition contains the component (D), the blending ratio of the component (C) in the curable composition of the present invention is 100 parts by mass in total of the above components (A) and (D). The component (C) is preferably in the range of 0.01 parts by mass or more and 20 parts by mass or less, and more preferably 0.1 parts by mass or more and 10 parts by mass or less. When the blending ratio of the component (C) is within the above range, good heat resistance can be obtained.

(Component D)
The curable composition of the present invention may contain an epoxy compound other than the above component (A) (also referred to as "other epoxy compounds" in the present specification) depending on the intended use. Examples thereof include glycidyl ether type epoxides, glycidyl ester type epoxides, glycidyl amine type epoxides and alicyclic epoxides, and oligomers and polymers thereof.

The glycidyl ether type epoxide includes bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, tetramethylbiphenol diglycidyl ether, hydride bisphenol A diglycidyl ether, brominated bisphenol A diglycidyl ether and the like. Glycidyl ether of valent phenol, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methanetriglycidyl ether, tetrakis (hydroxyphenyl) ethanetetraglycidyl ether, dinaphthylliol triglycidyl ether, phenol novolac glycidyl ether, cresol novolac glycidyl ether, Xylylene skeleton-containing phenol novolac glycidyl ether, dicyclopentadiene skeleton-containing phenol novolak glycidyl ether, biphenyl skeleton-containing phenol novolak glycidyl ether, terpen skeleton-containing phenol novolak glycidyl ether, bisphenol A novolak glycidyl ether, bisphenol F novolak glycidyl ether, bisphenol S novolac glycidyl Ether, bisphenol AP novolak glycidyl ether, bisphenol C novolak glycidyl ether, bisphenol E novolak glycidyl ether, bisphenol Z novolak glycidyl ether, biphenol novolak glycidyl ether, tetramethylbisphenol A novolak glycidyl ether, dimethylbisphenol A novolak glycidyl ether, tetramethylbisphenol F Novolak glycidyl ether, dimethylbisphenol F novolak glycidyl ether, tetramethylbisphenol S novolak glycidyl ether, dimethylbisphenol S novolak glycidyl ether, tetramethyl-4,4'-biphenol novolak glycidyl ether, trishydroxyphenylmethane novolac glycidyl ether, resorcinol novolac glycidyl ether Ether, hydroquinone novolac glycidyl ether, pyrogallol novolac glycidyl ether, diisopropyridennovolac glycidyl ether, 1,1-di-4-hydroxyphenylfluorennovolac glycidyl ether, phenolized polybutadiene novolac glycidyl ether , Ethylphenol novolac glycidyl ether, butylphenol novolak glycidyl ether, octylphenol novolak glycidyl ether, naphthol novolac glycidyl ether, hydrided phenol novolac glycidyl ether, polyvalent phenol glycidyl ether such as glycidyl ether of phenol aralkyl type epoxy resin having biphenylene skeleton, Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethylol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc. Hydrate alcohols such as glycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether, polyglycerin polyglycidyl ether and other polyvalent alcohols glycidyl ether, triglycidyl isocyanurate and the like. Be done.

Examples of the glycidyl ester type epoxide include glycidyl esters and glycidyl esters of carboxylic acids such as glycidyl methacrylate, phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, and trimet acid triglycidyl ester. Examples include mold polyepers.

Examples of the glycidylamine type epoxide include N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N', N'-tetraglycidyldiaminodiphenylmethane, N, N, N', N'-tetraglycidyl. Diaminodiphenyl sulfone, N, N, N', N'-tetraglycidyldiethyldiphenylmethane and other glycidyl aromatic amines, bis (N, N-diglycidylaminocyclohexyl) methane (N, N, N', N'-tetraglycidyl Diaminodiphenylmethane hydride), N, N, N', N'-tetraglycidyl-1,3- (bisaminomethyl) cyclohexane (N, N, N', N'-tetraglycidylxylylene hydride) , Trisglycidyl melamine, triglycidyl-p-aminophenol, N-glycidyl-4-glycidyloxypyrrolidone and other glycidyl heterocyclic amines.

Examples of the alicyclic epoxide include vinylcyclohexenedioxide, limonendioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxydicyclopentyl ether, and 3,4-epoxy-6-methylcyclohexylmethyl 3', 4. '-Epoxide-6'-Methylcyclohexanecarboxylate, 3,4-Epoxidecyclohexylmethyl 3,4-Epoxidecyclohexanecarboxylate, 3,4-Epoxide-1-methylcyclohexyl 3,4-Epoxy-1-methylhexane Carboxylate, 3,4-Epoxide-3-methylcyclohexylmethyl 3,4-epoxide-3-methylhexanecarboxylate, 3,4-epoxide-5-methylcyclohexylmethyl 3,4-epoxide-5-methylcyclohexanecarboxylate , 2- (3,4-Epoxide Cyclohexyl-5,5-Spiro-3,4-Epoxy) Cyclohexane-Metadioxane, Methylenebis (3,4-Epoxide Cyclohexane), (3,3', 4,4' -Diepoxy) bicyclohexyl, 1,2-epoxy- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, tetrahydroindene diepoxide and the like can be mentioned. The curable composition of the present invention may contain one or more epoxy compounds (component (D)) other than the above-mentioned component (A) as described above.

From the viewpoint of heat resistance of the cured product, the blending ratio of the component (D) is preferably 1 to 90% by mass, more preferably 5 to 40% by mass with respect to the curable composition.

From the viewpoint of heat resistance of the cured product, the mixing ratio of the component (A) and the component (D) is 5 parts by mass or more and 200 parts by mass with respect to 100 parts by mass of the component (A). The following is preferable, and 10 parts by mass or more and 150 parts by mass or less are more preferable.
When the blending ratio of the components (A) and (D) is within the range, good heat resistance can be obtained.

In one preferred embodiment, the epoxy compound other than the above component (A) contained in the curable composition of the present invention is selected from the group consisting of glycidyl ether type epoxides, glycidyl ester type epoxides and alicyclic epoxides. It is a thing. In a more preferred embodiment, the epoxy compounds other than the above component (A) contained in the curable composition of the present invention are tetramethylbiphenol diglycidyl ether, glycidyl ether of a phenol aralkyl type epoxy resin having a biphenylene skeleton, and trishydroxy. It is selected from the group consisting of phenylmethane novolac glycidyl ether.

(Component E)
The component (E) constituting the curable composition is an inorganic filler. The inorganic filler used in the present invention is not particularly limited, and can be selected in consideration of the use of the curable composition or the cured product thereof or the properties to be imparted. Examples of such inorganic fillers include oxides such as silica, alumina, titanium oxide, zirconium oxide, magnesium oxide, cerium oxide, yttrium oxide, calcium oxide, antimony trioxide, zinc oxide and iron oxide; calcium carbonate, Carbonates such as magnesium carbonate, barium carbonate and strontium carbonate; sulfates such as barium sulfate, aluminum sulfate and calcium sulfate; nitrides such as aluminum nitride, silicon nitride, titanium nitride, boron nitride and manganese nitride; calcium hydroxide and water. Hydroxides such as aluminum oxide and magnesium hydroxide; silicon compounds such as calcium silicate, magnesium silicate and aluminum silicate; boron compounds such as aluminum borate, zirconium compounds such as barium zirconate and calcium zirconate; phosphoric acid Phosphorus compounds such as zirconium and magnesium phosphate; titanium compounds such as strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, barium titanate, potassium titanate; mica, talc, kaolin, kaolin clay, kaolinite , Halloysite, cordierite, pyrophyllite, montmorillonite, cericite, amesite, bentonite, asbestos, wollastonite, sepiolite, zonolite, zeolite, hydrotalcite, hydrated plaster, myoban, kaolin, boehmite, etc. Minerals, fly ash, dehydrated sludge, glass beads, glass fiber, silica sand, carbon black, magnesium oxysulfate, silicon oxide, silicon carbide, etc .; including metals such as copper, iron, cobalt, nickel, or any of them. Alloys: Magnetic materials such as sentust, alnico magnets, ferrite, etc., preferably silica or alumina. Here, examples of the silica include fused silica, spherical silica, crystalline silica, amorphous silica, synthetic silica, hollow silica and the like, and spherical silica and crystalline silica are preferable. The inorganic filler may be used alone or in combination of two or more.

The inorganic filler used in the present invention may be granular, and the average particle size in that case is not particularly limited, but examples thereof include 0.01 μm or more and 150 μm or less, preferably 0.1 μm or more. It is 120 μm or less, more preferably 0.5 μm or more, and 75 μm or less. Within this range, for example, when used as a sealing material for semiconductor devices, the filling property into the mold cavity becomes good. The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis by a laser diffraction type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction type particle size distribution measuring device, "LA-500", "LA-750", "LA-950", "LA-960", etc. manufactured by HORIBA, Ltd. can be used.

The blending ratio of the component (E) is not particularly limited as long as a highly heat-resistant cured product of the curable composition can be obtained, and can be appropriately set according to the intended use. For example, when the composition is used for semiconductor encapsulation, the compounding ratio shown below is preferable.
When the curable composition does not contain the component (D), the lower limit of the blending ratio of the component (E) is, for example, 150 parts by mass or more with respect to a total of 100 parts by mass of the components (A) and (B). 400 parts by mass or more is preferable, and 500 parts by mass or more is more preferable. Further, the upper limit of the blending ratio of the component (E) is 1300 parts by mass or less with respect to a total of 100 parts by mass of the components (A) and (B) when the curable composition does not contain the component (D). It is preferably 1150 parts by mass or less, and more preferably 950 parts by mass or less.
Further, the lower limit of the blending ratio of the component (E) is, when the curable composition contains the component (D), with respect to a total of 100 parts by mass of the components (A), (B), and (D). For example, 150 parts by mass or more is mentioned, 400 parts by mass or more is preferable, and 500 parts by mass or more is more preferable. Further, the upper limit of the blending ratio of the component (E) is, when the curable composition does not contain the component (D), with respect to a total of 100 parts by mass of the components (A), (B), and (D). 1300 parts by mass or less is mentioned, 1150 parts by mass or less is preferable, and 950 parts by mass or less is more preferable.
As described above, when the lower limit of the blending ratio of the component (E) is 400 parts by mass or more, it is possible to suppress an increase in the amount of moisture absorption and a decrease in strength due to curing of the cured resin assembly composition, which is therefore good. A cured product having solder crack resistance can be obtained. Further, when the upper limit of the blending ratio of the component (E) is 1300 parts by mass or less, the cured resin assembly composition has fluidity, is easily filled in the mold, and the cured product is well sealed. Demonstrate performance.

（式中、Ｙはアミノ基、メルカプト基、エポキシ基、（メタ）アクリル基、ビニル基、イソシアネート基、イミダゾリル基、ウレイド基、スルフィド基、およびイソシアヌレート基からなる群から選択される官能基を含む１価の基を示し、Ｘはヒドロキシ基、アルコキシ基から選択される官能基を示し、ｌは０、１または２を示す。） (Component F)
The (F) silane coupling agent used in the present invention is an organic component (A) a polyfunctional epoxy compound, (B) a phenolic curing agent and / or an epoxy compound other than the above (A) (component (D)). It is a component that has reactivity with both (E) and the inorganic filler and improves the affinity between the two. The (F) silane coupling agent of the present invention has a functional group Y that contributes to the bond with the organic component and a functional group X that contributes to the bond with the (E) inorganic filler, according to the following formula (6). Examples include compounds having the structures shown.

(In the formula, Y is a functional group selected from the group consisting of an amino group, a mercapto group, an epoxy group, a (meth) acrylic group, a vinyl group, an isocyanate group, an imidazolyl group, a ureido group, a sulfide group, and an isocyanurate group. Indicates a monovalent group containing, X indicates a functional group selected from a hydroxy group and an alkoxy group, and l indicates 0, 1 or 2).

In the present invention, X in the formula (6) is preferably an alkoxy group. The alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 or 2. The alkoxy group is preferably a methoxy group or an ethoxy group. The silane coupling agent has 1 to 3, preferably 2 or 3 functional groups X in one molecule that contribute to binding to the inorganic filler. Therefore, l in the formula (6) is preferably 1 or 0. When there are two or more functional groups X that contribute to binding to the inorganic filler, the functional groups X may be the same functional group or a combination of different functional groups.

In the present invention, the monovalent group represented by Y in the formula (6) is selected from the group consisting of an amino group, a mercapto group, an epoxy group, a (meth) acrylic group, a vinyl group, an isocyanate group, an imidazolyl group and a ureido group. It is preferable to contain one or more functional groups (Y ₁ ), and it is more preferable to contain one or more functional groups selected from the group consisting of an amino group and a mercapto group. Here, the amino group may be any of a primary, secondary and tertiary amino group, and is preferably a primary or secondary amino group. Here, the secondary amino group is preferably an anirino group.

（式中、Ｙ_１は、アミノ基、メルカプト基、エポキシ基、（メタ）アクリル基、ビニル基、イソシアネート基、イミダゾリル基、ウレイド基、スルフィド基およびイソシアヌレート基からなる群から選択される１種以上の官能基を示し、Ｒは炭化水素基を示す。） Further, as a monovalent group represented by Y in the formula (6), the structure of the following formula (6-1) can be mentioned.

(In the formula, Y ₁ is one selected from the group consisting of an amino group, a mercapto group, an epoxy group, a (meth) acrylic group, a vinyl group, an isocyanate group, an imidazolyl group, a ureido group, a sulfide group and an isocyanurate group. The above functional groups are shown, and R is a hydrocarbon group.)

The Y1 in the present invention is _one or more functional groups selected from the group consisting of an amino group, a mercapto group, an epoxy group, a (meth) acrylic group, a vinyl group, an isocyanate group, an imidazolyl group, a ureido group and an isocyanurate group. Groups are preferred, and one or more functional groups selected from the group consisting of primary amino groups, mercapto groups, and secondary amino groups are more preferred.
The "hydrocarbon group" represented by R in the formula (6-1) may be an alkylene group, and the alkylene group may be substituted, and the substituent is not particularly limited, but has 1 carbon number. Examples thereof include a chain alkyl group of up to 12 or an aryl group having 6 to 14 carbon atoms. Examples of the chain alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenanthryl group, and a biphenyl group.
The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The alkylene group may be linear or branched. As the alkylene group, an unsubstituted alkylene group is preferable.

Specific examples of the monovalent group represented by Y include an N- (phenyl) -amino C _1-10 alkyl group (here, the C _1-10 alkyl group represents an alkyl group having 1 to 10 carbon atoms. Similarly), Mercapto C _1-10 Alkyl Group, Amino C _1-10 Alkyl Group, N- (Amino C _1-10 Alkyl) -Amino C _1-10 Alkyl Group, N- (C _1-10 Alkylidene) -Amino C _1-10 alkyl group, (epoxy C _3-10 cycloalkyl) C _1-10 alkyl group, glycidoxy C _1-10 alkyl group, glycidyl C _1-10 alkyl group, acrylicoxy C _1-10 alkyl group, methacryloxy C _1-10 alkyl group, vinyl group, styryl group, isocyanate C _1-10 alkyl group, imidazolyl C _1-10 alkyl group, ureido C _1-10 alkyl group, tri (C _1-10 alkoxy) silyl C _1-10 alkyl Examples thereof include a tetrasulfide C _1-10 alkyl group and a di [tri (C _1-10 alkoxy) silyl C _1-10 alkyl] isocyanurate C _1-10 alkyl group. Preferred are N- (phenyl) -amino C _1-10 alkyl group, mercapto C _1-10 alkyl group, and amino C _1-10 alkyl group.

Specific examples of the (F) silane coupling agent used in the present invention are shown below. Examples of the silane coupling agent having an amino group (hereinafter, also referred to as aminosilane) include γ-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane (also referred to as γ-aminopropyltrimethoxysilane), and N-. Phenyl-3-aminopropyltrimethoxysilane (also referred to as N-phenyl-γ-aminopropyltrimethoxysilane, anilinosilane) and the like can be mentioned. Examples of the silane coupling agent having a mercapto group (hereinafter, also referred to as mercaptosilane) include 3-mercaptopropyltrimethoxysilane (also referred to as γ-mercaptopropyltrimethoxysilane) and 3-mercaptopropylmethyldimethoxysilane. be able to. Examples of the silane coupling agent having an epoxy group (hereinafter, also referred to as epoxysilane) include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4 epoxycyclohexyl). Ethyltrimethoxysilane and the like can be mentioned.
These (F) silane coupling agents may be used alone or in combination of two or more.

By adding the (F) silane coupling agent used in the present invention to a curable composition containing an inorganic filler, it is possible to improve the mechanical strength and reduce the viscosity of the curable composition at the time of melting. It will be possible.

Here, the blending ratio of the (F) silane coupling agent used in the present invention is not particularly limited, but when the curable composition does not contain the component (D), the mechanical strength of the cured product is improved. From the viewpoint of the above, 0.01 to 2 parts by mass is preferable, and 0.05 to 2 parts by mass is more preferable with respect to a total of 100 parts by mass of the components (A), (B) and (E). preferable. When the curable composition contains the component (D), the blending ratio of the (F) silane coupling agent used in the present invention is not particularly limited, but from the viewpoint of improving the mechanical strength of the cured product. Therefore, it is preferably 0.01 to 2 parts by mass, and 0.05 to 2 parts by mass with respect to a total of 100 parts by mass of the components (A), (B), (D) and (E). Is more preferable.

(Other ingredients)
When it is desired to reduce the viscosity of the composition, the curable composition of the present invention may contain a monofunctional benzoxazine compound having one benzoxazine ring as long as the performance is not impaired.
Further, for example, nanocarbon, a flame retardant, a mold release agent and the like can be blended in the curable composition of the present invention as long as the performance is not impaired.
Examples of nanocarbons include carbon nanotubes, fullerenes, and derivatives thereof.
Examples of the flame retardant include phosphoric acid esters such as red phosphorus, triphenyl phosphate, tricresyl phosphate, trixilenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, resorcinol bisphenyl phosphate and bisphenol A bisdiphenyl phosphate. , Boric acid ester and the like.
Examples of the mold release agent include silicone oil, stearic acid ester, carnauba wax and the like.

When the curable composition of the present invention is used for semiconductor encapsulation, carbon black, red iron oxide, titanium oxide, etc., in addition to the components (A) to (F), are used as long as the performance of the curable composition is not impaired. Colorants; natural waxes such as carnauba wax, synthetic waxes such as polyethylene oxide wax, higher fatty acids such as stearic acid, metal salts such as zinc stearate, and mold release agents such as paraffin; One or more kinds of low stress additives; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; and flame retardant agents such as paraffin may be appropriately blended.

[Manufacturing method of curable composition]
Next, a method for producing the curable composition of the present invention will be described.
The curable composition of the present invention is produced by kneading or mixing the components (A) to (C), and if desired, the components (D) to (F), other additives, and a solvent as appropriate. can do.
The kneading and mixing methods are not particularly limited, and for example, mixing can be performed using a planetary mixer, a twin-screw extruder, a kneader such as a heat roll or a kneader, or the like. Further, when the components (A) and (B) are in a high-viscosity liquid or solid state at room temperature, or when the component (E) is contained, the components (A) and (B) are heated and kneaded as necessary, or further added. It may be kneaded under pressure or reduced pressure conditions. The heating temperature is preferably 80 to 120 ° C. Further, since the component (F) is generally in a liquid state at room temperature, it may be mixed with the component (E) in advance, or may be mixed with the components (A), (B), (C) and the like.
Since the curable composition containing the component (E) is in the form of a solid at room temperature, it may be cooled and pulverized after heating and kneading to form a powder, or the powder may be tableted into a pellet. good. Further, the powder may be granulated into granules.

[Cursed product]
The cured product of the curable composition of the present invention has good heat resistance, is hard to be thermally decomposed, and has a high glass transition temperature.
The heat resistance of the cured product of the present invention can be evaluated by measuring the glass transition temperature. The glass transition temperature is not particularly limited as long as the effect of the present invention is exhibited, but may be 160 ° C. or higher, preferably 180 ° C. or higher, and more preferably 200 ° C. or higher. The glass transition temperature can be measured by differential scanning calorimetry (DSC). Such measurement can be easily performed by using a commercially available differential scanning calorimeter (for example, manufactured by Hitachi High-Tech Science Corporation).

[Manufacturing method of cured product]
The method for producing the cured product of the present invention is not particularly limited, but for example, it can be produced as follows.
First, the curable composition of the present invention is produced by the above method. Subsequently, the obtained curable composition can be cured by a thermosetting reaction by heating. The heating temperature at this time is, for example, 150 ° C. or higher and 330 ° C. or lower, preferably 170 ° C. or higher and 300 ° C. or lower, and more preferably 200 ° C. or higher and 250 ° C. or lower. Normally, the heating temperature of the thermosetting reaction when a phenolic curing agent is used is a low temperature, for example, 100 ° C. or higher and lower than 170 ° C., but in the present invention, the heating temperature is 170 ° C. or higher from the viewpoint of improving heat resistance. The temperature is preferably 300 ° C. or lower. The curing time may be, for example, 1 minute or more and 5 hours or less. In the case of continuous production of the cured product, a curing time of 1 minute or more and 3 minutes or less is sufficient, but it is preferable to heat the cured product for 5 minutes or more and 5 hours or less as post-curing in order to obtain sufficient strength.

[Semiconductor device]
In the semiconductor device of the present invention, the semiconductor element is installed in a cured product obtained by curing the curable composition of the present invention containing the components (A) to (C) and, if desired, the components (D) to (F). It is a semiconductor device. Here, the semiconductor element is usually supported and fixed by a lead frame which is a thin plate of a metal material. "The semiconductor element is installed in the cured product" means that the semiconductor element is sealed with the cured product of the curable composition, and the semiconductor element is covered with the cured product. Represents. In this case, the entire semiconductor element may be covered, or the surface of the semiconductor element installed on the substrate may be covered.

When various electronic components such as semiconductor elements are sealed using the cured product of the present invention to manufacture a semiconductor device, a sealing step is performed by a conventional molding method such as transfer mold, compression mold, or injection mold. By carrying out the above, a semiconductor device can be manufactured.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

<Component (A); Polyfunctional epoxy compound having a norbornene structure>
The following (A1) to (A3) were used as the component (A).
(A1) Polyfunctional Epoxy Compound 1; Compound of Formula (2-1) The compound (a) represented by the above formula (3) is referred to as "Diels-Alder reaction of butadiene and cyclopentadiene-trimer" by Shoichi Tsuchida et al. It was synthesized according to the method described in "Determining the Body-", Journal of the Petroleum Society, 1972, Vol. 15, No. 3, p189-192.
Next, the reaction of the above formula (3) was carried out as follows. 23.5 kg of chloroform and 1.6 kg of compound (a) were put into the reaction vessel, and 4.5 kg of metachloroperbenzoic acid was added dropwise while stirring at 0 ° C. The temperature was raised to room temperature, and the reaction was carried out for 12 hours.
Next, after removing the metachlorobenzoic acid produced as a by-product by filtration, the filtrate was washed 3 times with a 1N aqueous sodium hydroxide solution and then with a saturated saline solution. The organic layer was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the filtrate was concentrated to obtain a crude product.
Toluene (2 kg) was added to the crude and dissolved at room temperature. 6 kg of heptane was added dropwise thereto for crystallization, and the mixture was aged at 5 ° C. for 1 hour. The crystallized product was collected by filtration and washed with hexane. By drying under reduced pressure for 24 hours at 35 ° C., 1.4 kg of the compound represented by the following formula (2-1) was obtained as a white solid.

(A2) Polyfunctional epoxy compound 2; compound of formula (2-2) (tricyclopentadiene epoxide: TCPD-DE)
Compound (b) was synthesized in the same manner as in compound (a) according to the method described in the above document.
Next, the reaction of the above formula (4) was carried out as follows. 59.2 kg of chloroform and 4.0 kg of compound (b) were added to the reaction vessel, and 10.6 kg of metachloroperbenzoic acid was added dropwise at −10 ° C. with stirring. The temperature was raised to room temperature, and the reaction was carried out for 12 hours.
Next, after removing the meta-chlorobenzoic acid produced as a by-product by filtration, the filtrate was washed with 42.0 kg of a 5% aqueous sodium sulfite solution. The organic layer was further washed 4 times with 41.6 kg of 1N aqueous sodium hydroxide solution and then with 48.0 kg of saturated brine. The organic layer was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the filtrate was concentrated to obtain 5.1 kg of a crude product.
Toluene (3.5 kg) was added to the crude and dissolved at room temperature. 13.7 kg of heptane was added dropwise thereto for crystallization, and the mixture was aged at 5 ° C. for 1 hour. The crystallization was collected by filtration and washed with heptane. By drying under reduced pressure for 12 hours at 35 ° C., 2.8 kg of the compound represented by the following formula (2-2) was obtained as a white solid.

(A3) Polyfunctional epoxy compound 3; compound of formula (2-4) (dicyclopentadiene diepoxide: DCPD-DE)
A reaction vessel was charged with 10 kg of dicyclopentadiene, 68 kg of sodium bicarbonate, 100 L of acetone and 130 L of ion-exchanged water, cooled to 10 ° C. or lower, and then the cooling was controlled so as to maintain the temperature of the reaction solution at 30 ° C. or lower, and 84 kg of oxonone was used. Was gradually added, and the reaction was carried out for 10 hours with stirring.
Next, the reaction product was extracted twice with 100 L of ethyl acetate, and the obtained organic layers were separated and combined. Subsequently, the organic layer was washed with 100 L of a mixed aqueous solution of salt and sodium thiosulfate (20 wt% of salt + 20 wt% of sodium thiosulfate), and then further washed twice with 100 L of ion-exchanged water.
The washed organic layer was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the organic solvent was distilled off from the filtrate to obtain 11 kg of the compound represented by the following formula (2-4) as a white solid.

<Component (B); Phenolic curing agent>
The following (B1) to (B3) were used as the component (B).
(B1) Phenol-based curing agent 1; Phenol novolac resin (TD-2106, manufactured by DIC Corporation)
(B2) Phenol-based curing agent 2; Phenol aralkyl resin having a biphenylene skeleton (GPH-065, manufactured by Nippon Kayaku Co., Ltd.)
(B3) Phenolic curing agent 3; Triphenol methane type phenol resin (KTG-105, manufactured by Nippon Kayaku Co., Ltd.)

<Component (C); Curing accelerator>
The following (C1) to (C2) were used as the component (C).
(C1) Curing accelerator 1; Tetraphenylphosphonium Tetraphenylborate (TPP-K) (manufactured by Hokuko Chemical Industry Co., Ltd.)
(C2) Curing accelerator 2; tripalatrilphosphine (TPTP) (manufactured by Hokuko Chemical Industry Co., Ltd.)

（Ｄ２）その他のエポキシ化合物２；エポキシ化合物（ビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂のグリシジルエーテル）（ＮＣ－３０００、日本化薬株式会社製） <Component (D); Epoxy compounds other than component (A) (other epoxy compounds)>
The following (D1) and (D2) were used as the component (D).
The following components (D1) and (D2) having no norbornane structure were used as the other epoxy compounds 1 and 2 in (D1) and (D2).
(D1) Other Epoxy Compounds 1; Epoxy compounds represented by the following formula (7) (tetramethylbiphenol diglycidyl ether) (YX-4000H, manufactured by Mitsubishi Chemical Corporation)

(D2) Other Epoxy Compounds 2; Epoxy compounds (glycidyl ether of phenol aralkyl type epoxy resin having biphenylene skeleton) (NC-3000, manufactured by Nippon Kayaku Co., Ltd.)

(Example 1)
The polyfunctional epoxy compound 1 (A1), the phenolic curing agent 1 (B1) and the curing accelerator 2 (C2) obtained as described above are heated to 100 degrees on a hot plate so as to have the following composition. It was dissolved and mixed to obtain a curable composition.
<Composition of curable composition>
(A1) Polyfunctional epoxy compound 1 50 parts by mass (B1) Phenolic curing agent 1 47 parts by mass (C2) Curing accelerator 2 3 parts by mass

The curable composition obtained as described above was heated at 220 ° C. for 3 hours in a hot air circulation oven to obtain a cured product.

<Heat resistance (glass transition temperature; Tg)>
The glass transition temperature (Tg) of the cured product obtained as described above was measured by raising the temperature to 10 ° C./min at 10 ° C./min with a differential scanning calorimeter DSC7020 manufactured by Hitachi High-Tech Science, and the heat resistance of the cured product was measured. I made it sex. The glass transition temperature referred to here was measured based on "Midpoint glass transition temperature: T _mg " described in JIS K7121 "Measurement method of transition temperature of plastic". The measurement results are summarized in Table 1.
Sample amount: Approximately 10 mg

(Examples 2 to 8)
The composition of each example was prepared in the same manner as in Example 1 except that the blending ratio of each component was as shown in Table 1. The heat resistance (glass transition temperature) of each composition was measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Examples 1 to 3)
The compositions of each Comparative Example were prepared in the same manner as in Example 1 except that the blending ratio of each component was as shown in Table 2. The heat resistance (glass transition temperature) of each composition was measured in the same manner as in Example 1. The results are shown in Table 2.

The curable composition of each example has a heat resistance (glass transition temperature) of 160 ° C. or higher, and it can be seen that the heat resistance is highly improved. On the other hand, in Comparative Examples 1 to 3, the glass transition temperature is low and the heat resistance is inferior.
From the above results, the curable composition according to the embodiment of the present invention was cured to obtain a cured product having high heat resistance.

Claims (10)

(A) An epoxy compound having at least one norbornane structure and at least two epoxy groups and represented by the formula (2-1) or the formula (2-2) .
(B) Phenolic curing agent and
(C) A curable composition containing a curing accelerator.

(D) The curable composition according to claim 1, further containing an epoxy compound other than the above (A). (E) The curable composition according to claim 1 or 2, further containing an inorganic filler. (F) The curable composition according to any one of claims 1 to 3, further containing a silane coupling agent. A cured product obtained by curing the curable composition according to any one of claims 1 to 4. The cured product according to claim 5, wherein the glass transition temperature is 160 ° C. or higher. A semiconductor device in which a semiconductor element is installed in the cured product according to claim 5 or 6. A method for producing a curable composition.
(A) An epoxy compound having at least one norbornane structure and at least two epoxy groups and represented by the formula (2-1) or the formula (2-2) .
(B) Phenolic curing agent and
(C) A method for producing a curable composition, which comprises a step of mixing with a curing accelerator to obtain a mixture.

The production method according to claim 8, wherein in the step of obtaining the mixture, (D) an epoxy compound other than the above (A) is further mixed to obtain a mixture. A method for producing a cured product, which comprises a step of heating and curing the curable composition produced by the method according to claim 8 or 9 at 170 to 300 ° C.