JP2019044081A - Curable composition, cured product thereof, and methods for producing them - Google Patents

Abstract

To provide a curable composition for obtaining a cured product having high heat resistance, a cured product thereof, and methods for producing the curable composition and the cured product.SOLUTION: There are provided: a curable composition containing (A) an epoxy compound having at least one norbornane structure and at least two epoxy groups, (B) a phenolic curing agent, (C) a curing accelerator, and optionally (D) an epoxy compound other than (A), (E) an inorganic filler, and (F) a silane coupling agent; a cured product of the curable composition; and methods for producing the curable composition and the cured product.SELECTED DRAWING: None

Description

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

  A curable composition containing an epoxy compound is used as a material such as a sealing resin, an adhesive, a paint, and a matrix resin for a composite material. Among epoxy compounds, an epoxy compound having an alicyclic skeleton is known as a material capable of obtaining 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 excellent in heat resistance and the like.

  Among these epoxy compounds, epoxy compounds having two or more alicyclic skeletons in the molecule are known as those capable of obtaining a cured product having excellent heat resistance and transparency. 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 in terms of the heat resistance of the cured product.

Japanese Patent Laid-Open No. 49-126658 JP 2008-31424 A

  In applications such as adhesives, paints, sealing materials, and matrix resins for composites, there is still a demand for further high heat-resistant resin cured products that can be adapted to more severe use 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, a curable composition, and a method for producing the cured product.

  As a result of intensive studies to solve the above object, the present inventors have developed a curable composition containing a polyfunctional epoxy compound, a phenolic curing agent, and a curing accelerator, and the cured product is heat resistant. As a result, the present invention was completed.

That is, according to the present invention, the following inventions are provided.
[1] (A) an epoxy compound having at least one norbornane structure and at least two epoxy groups;
(B) a phenolic curing agent;
(C) A curable composition containing a curing accelerator.
[2] (D) The curable composition according to [1], further containing an epoxy compound other than (A).
[3] The curable composition according to [1] or [2], further comprising (E) an inorganic filler.
[4] The curable composition according to any one of [1] to [3], further comprising (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 comprising:
(A) an epoxy compound having at least one norbornane structure and at least two epoxy groups;
(B) a phenolic curing agent;
(C) The manufacturing method of a curable composition which has the process of mixing with a hardening accelerator and obtaining a mixture.
[9] The production method according to [8], wherein in the step of obtaining the mixture, (D) an epoxy compound other than (A) is further mixed to obtain a mixture.
[10] A method for producing a cured product, comprising 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 optionally components (D) to (F), and the cured product of the composition has heat resistance. It has the characteristics of being good, hardly thermally decomposed, and having a high glass transition temperature. Therefore, the curable composition of the present invention can be used for applications that require high heat resistance, such as adhesives, paints, sealing materials, and matrix resins for composite materials. In particular, it exhibits excellent sealing performance as a semiconductor element sealing material and can contribute to high reliability of the semiconductor device.

[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 monomer shown in each formula but also an oligomer obtained by polymerizing the monomer in a small amount, that is, a prepolymer before forming a cured resin. .

(Component A)
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”). The polyfunctional epoxy compound is preferably an alicyclic epoxy compound, and more preferably has an epoxy structure bonded to a 5-membered ring, 6-membered ring or norbornane ring represented by the following formula (1).

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

A production example of the polyfunctional epoxy compound of 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 is synthesized by a Diels-Alder reaction between butadiene and dicyclopentadiene, and then, as shown in the following formula (3), the compound (a), metachloroperbenzoic acid, Can be reacted to produce a compound of formula (2-1).

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

First, compound (b) (tricyclopentadiene) having the following norbornane structure was synthesized by Diels-Alder reaction of cyclopentadiene and dicyclopentadiene, and then compound (b) as shown in formula (4) below. Can react with metachloroperbenzoic acid to produce the compound of formula (2-2).

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. Next, as shown in the following formula (5), the compound (c) and metachloroperbenzoic acid are synthesized. The compound of Formula (2-3) can be manufactured by making it react.

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 diepoxide which is the compound of the formula (2-4) may be a commercially available product, and examples of the commercially available product include dicyclopentadiene diepoxide manufactured by SHANDONG QIHUAN BIOCHEMICAL CO., LTD.

(Component B)
Component (B) constituting the curable composition is a phenolic curing agent. The phenolic curing agent used in the present invention is a monomer, oligomer, or polymer in general having two or more phenolic hydroxyl groups in one molecule. For example, a phenol novolak resin, a cresol novolak resin, a phenol aralkyl resin (preferably, Phenol aralkyl resin having a phenylene skeleton, a biphenylene skeleton, etc.), a naphthol aralkyl resin (preferably a naphthol aralkyl resin having a phenylene skeleton, a biphenylene skeleton, etc.), a terpene-modified phenol resin, a dicyclopentadiene-modified phenol resin, a triphenolmethane phenol Examples thereof include, but are not limited to, resins and bisphenol compounds. The phenolic curing agent used in the present invention is preferably a phenol novolak resin, a phenol aralkyl resin, a triphenolmethane type phenol resin, a cresol novolak 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 a mixture ratio of a component (B), when a curable composition does not contain epoxy compounds (component (D)) other than the said component (A) mentioned later, the component contained in the curable composition of this invention (A) It is preferable to make a component (B) into the range of 50 to 300 mass parts with respect to 100 mass parts, and it is more preferable to set it as 75 to 200 mass parts. Moreover, when a curable composition contains a component (D), the mixture ratio of the component (B) in the curable composition of this invention is with respect to a total of 100 mass parts of the said component (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 advanced, and a highly heat-resistant cured product can be obtained.

(Component C)
Component (C) constituting the curable composition of the present invention is a curing accelerator. As the curing accelerator, known curing accelerators can be used, and amine compounds 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 tripalatolylphosphine, and covalent and ionic bonds such as tetraphenylphosphonium tetraphenylborate And organic phosphorus compounds such as salt-type organic phosphorus compounds to which phosphorus is bonded, but are not limited thereto. Moreover, the above-described curing accelerators may be used alone or in combination of two or more. Of these, organic phosphorus compounds such as triphenylphosphine, tripalatolylphosphine, 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 crosslinking reaction between an epoxy group and a phenolic hydroxyl group. The organophosphorus compound of the present invention is not particularly limited as long as it has the function.

  The blending ratio of the component (C) in the curable composition of the present invention is such that the curable composition does not contain an epoxy compound (component (D)) other than the component (A) described later. The component (C) is preferably 0.01 parts by mass or more and 20 parts by mass or less, and preferably 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 composition. It is more preferable to set it as the range below a part. Moreover, when a curable composition contains a component (D), the mixture ratio of the component (C) in the curable composition of this invention is with respect to a total of 100 mass parts of the said component (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 in the range of 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 (also referred to as “other epoxy compound” in the present specification) other than the component (A) depending on the application. Examples include glycidyl ether type epoxides, glycidyl ester type epoxides, glycidyl amine type epoxides and alicyclic epoxides, and oligomers and polymers thereof.

  Examples of the glycidyl ether type epoxide include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, tetramethylbiphenol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and brominated bisphenol A diglycidyl ether. Glycidyl ether of dihydric phenol, dihydroxynaphthylcresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether, tetrakis (hydroxyphenyl) ethanetetraglycidyl ether, dinaphthyltriol triglycidyl ether, phenol novolac glycidyl ether, cresol novolac glycidyl ether, Phenolic novolac containing xylylene skeleton Sidyl ether, dicyclopentadiene skeleton-containing phenol novolac glycidyl ether, biphenyl skeleton-containing phenol novolak glycidyl ether, terpene skeleton-containing phenol novolac glycidyl ether, bisphenol A novolac glycidyl ether, bisphenol F novolac glycidyl ether, bisphenol S novolak glycidyl ether, bisphenol AP novolak Glycidyl ether, bisphenol C novolac glycidyl ether, bisphenol E novolac glycidyl ether, bisphenol Z novolac glycidyl ether, biphenol novolac glycidyl ether, tetramethylbisphenol A novolac glycidyl ether, dimethyl bisphenol A novolac glycidyl Ether, tetramethylbisphenol F novolac glycidyl ether, dimethyl bisphenol F novolac glycidyl ether, tetramethyl bisphenol S novolac glycidyl ether, dimethyl bisphenol S novolac glycidyl ether, tetramethyl-4,4'-biphenol novolac glycidyl ether, trishydroxyphenylmethane novolak Glycidyl ether, resorcinol novolak glycidyl ether, hydroquinone novolak glycidyl ether, pyrogallol novolac glycidyl ether, diisopropylidene novolac glycidyl ether, 1,1-di-4-hydroxyphenylfluorene novolac glycidyl ether, phenolized polybutadiene novolac glycidyl ether Glycidyl ethers of polyhydric phenols such as glycidyl ether of ethylphenol novolac glycidyl ether, butylphenol novolak glycidyl ether, octylphenol novolak glycidyl ether, naphthol novolac glycidyl ether, hydrogenated phenol novolac glycidyl ether, 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, cyclohexane dimethylol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc. Price Examples include glycidyl ether of cole, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether, glycidyl ether of polyhydric alcohol such as polyglycerin polyglycidyl ether, triglycidyl isocyanurate, etc. .

  Glycidyl ester type epoxides include glycidyl methacrylate, phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, trimetic acid triglycidyl ester and the like. Examples include mold polyepoxides.

  Examples of the glycidylamine type epoxide include N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl. Glycidyl aromatic amines such as diaminodiphenylsulfone, N, N, N ′, N′-tetraglycidyldiethyldiphenylmethane, bis (N, N-diglycidylaminocyclohexyl) methane (N, N, N ′, N′-tetraglycidyl) Hydride of diaminodiphenylmethane), N, N, N ′, N′-tetraglycidyl-1,3- (bisaminomethyl) cyclohexane (hydride of N, N, N ′, N′-tetraglycidylxylylenediamine) , Trisglycidylmelamine, triglycidyl-p-aminophenol, N-glycine Glycidyl heterocyclic amines such as Gilles 4-glycidyloxy pyrrolidone.

  Examples of the alicyclic epoxide include vinylcyclohexene dioxide, limonene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether, 3,4-epoxy-6-methylcyclohexylmethyl 3 ′, 4. '-Epoxy-6'-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl 3,4-epoxy-1-methylhexane Carboxylate, 3,4-epoxy-3-methylcyclohexylmethyl 3,4-epoxy-3-methylhexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl 3,4-epoxy-5-methylcyclo Hexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, methylenebis (3,4-epoxycyclohexane), (3,3 ′, 4 , 4′-diepoxy) bicyclohexyl, 1,2-epoxy- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, tetrahydroindene diepoxide and the like. The curable composition of the present invention may contain one or more epoxy compounds (component (D)) other than the above-described component (A).

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

From the viewpoint of heat resistance of the cured product, the blending ratio of the component (A) and the component (D) is 5 parts by mass or more and 200 parts by mass of the component (D) 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 component (A) contained in the curable composition of the present invention is selected from the group consisting of a glycidyl ether type epoxide, a glycidyl ester type epoxide and an alicyclic epoxide. Is. In a more preferred embodiment, the epoxy compound other than the component (A) contained in the curable composition of the present invention includes 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 novolak glycidyl ether.

(Component E)
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 its cured product or the properties to be imparted. Examples of the inorganic filler 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 The Phosphorus compounds such as conium 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, Sericite, Amesite, Bentonite, Asbestos, Wollastonite, Sepiolite, Zonolite, Zeolite, Hydrotalcite, Hydrated Gypsum, Alum, Diatomaceous Earth, Boehmite, etc. Minerals, fly ash, dehydrated sludge, glass beads, glass fiber, silica sand, carbon black, magnesium oxysulfate, silicon oxide, silicon carbide, etc .; copper, iron, cobalt, nickel Metal or alloy including any of its like; sendust, alnico magnet, a magnetic material and the like such as ferrite, 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, preferably spherical silica and crystalline silica. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  The inorganic filler used in the present invention may be granular, and the average particle size in that case is not particularly limited, and examples 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. If it is this range, when using for the sealing material use of a semiconductor element, for example, the filling property to a mold cavity will become favorable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis with a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring device, “LA-500”, “LA-750”, “LA-950”, “LA-960” manufactured by Horiba, Ltd., and the like can be used.

The blending ratio of component (E) is not particularly limited as long as a highly heat-resistant cured product of the curable composition is obtained, and can be appropriately set depending on the application. For example, when using a composition for the semiconductor sealing use, 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 100 parts by mass in total of the components (A) and (B). 400 mass parts or more are preferable, and 500 mass parts or more are more preferable. Moreover, the upper limit of the mixture ratio of a component (E) is 1300 mass parts or less with respect to a total of 100 mass parts of a component (A) and (B), when a curable composition does not contain a component (D). 1150 parts by mass or less is preferable, and 950 parts by mass or less is more preferable.
Moreover, when the curable composition contains the component (D), the lower limit of the blending ratio of the component (E) is 100 parts by mass in total of the components (A), (B), and (D). For example, 150 mass parts or more are mentioned, 400 mass parts or more are preferable and 500 mass parts or more are more preferable. Moreover, when the curable composition does not contain the component (D), the upper limit of the blending ratio of the component (E) is 100 parts by mass in total of the components (A), (B), and (D). 1300 mass parts or less are mentioned, 1150 mass parts or less are preferable and 950 mass parts or less are more preferable.
As described above, when the lower limit value of the blending ratio of the component (E) is 400 parts by mass or more, it is possible to suppress an increase in moisture absorption and a decrease in strength due to the curing of the composition for curable resin assembly, and thus it is favorable. A cured product having solder crack resistance can be obtained. Moreover, if the upper limit of the mixture ratio of a component (E) is 1300 mass parts or less, the composition for cured resin group has fluidity | liquidity, it is easy to fill a metal mold | die, and cured | curing material has favorable sealing 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) polyfunctional epoxy compound, (B) a phenolic curing agent and / or an epoxy compound other than the above (A) (component (D)). And (E) a component that has reactivity with both inorganic fillers and improves the affinity between them. The (F) silane coupling agent of the present invention has the functional group Y contributing to the bond with the organic component and the functional group X contributing to the bond with the (E) inorganic filler, represented by the following formula (6). And compounds having the structure shown.

Wherein Y is a functional group selected from the group consisting of amino group, mercapto group, epoxy group, (meth) acryl group, vinyl group, isocyanate group, imidazolyl group, ureido group, sulfide group, and isocyanurate group. And X represents a functional group selected from a hydroxy group and an alkoxy group, and l represents 0, 1 or 2.)

  In the present invention, X in 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 further 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 that contribute to bonding with the inorganic filler in one molecule. Therefore, l in formula (6) is preferably 1 or 0. When two or more functional groups X that contribute to bonding with the inorganic filler are present, 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 formula (6) is selected from the group consisting of an amino group, a mercapto group, an epoxy group, a (meth) acryl group, a vinyl group, an isocyanate group, an imidazolyl group, and a ureido group. preferably contains one or more functional groups (Y ₁₎ that, an amino group, and more preferably contains one or more functional groups selected from the group consisting of a mercapto group. Here, the amino group may be any of primary, secondary, and tertiary amino groups, and is preferably a primary or secondary amino group. Here, the secondary amino group is preferably an anilino 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。） Moreover, as a monovalent group which Y in Formula (6) shows, the structure of following formula (6-1) is mentioned.

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

Y ₁ in the present invention is one or more functional groups selected from the group consisting of amino group, mercapto group, epoxy group, (meth) acryl group, vinyl group, isocyanate group, imidazolyl group, ureido group and isocyanurate group. A group is preferable, and one or more functional groups selected from the group consisting of a primary amino group, a mercapto group, and a secondary amino group are more preferable.
Examples of the “hydrocarbon group” represented by R in the formula (6-1) include an alkylene group, and the alkylene group may be substituted, but the substituent is not particularly limited. -12 chain alkyl group or C6-C14 aryl group is mentioned. 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 still more preferably 1 to 3. The alkylene group may be linear or branched. The alkylene group is preferably an unsubstituted alkylene group.

Specific examples of the monovalent group represented by Y include an N- (phenyl) -amino C _1-10 alkyl group (wherein the C _1-10 alkyl group represents an alkyl group having 1 to 10 carbon atoms. The same), 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, acryloxy C _1-10 alkyl group, methacryloxy C _1-10 alkyl group, a vinyl group, a styryl group, an isocyanate _{C 1-10} alkyl group, imidazolyl _{C 1-10} alkyl group, ureido _{C 1-10} A Kill group, tri _{(C 1-10} alkoxy) silyl _{C 1-10} alkyl tetrasulfide _{C 1-10} alkyl group, di [tri _{(C 1-10} alkoxy) silyl _{C 1-10} alkyl] isocyanurates _{C 1-10} alkyl Groups. N- (phenyl) -amino C _1-10 alkyl group, mercapto C _1-10 alkyl group, and amino C _1-10 alkyl group are preferable.

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), N- And phenyl-3-aminopropyltrimethoxysilane (also referred to as N-phenyl-γ-aminopropyltrimethoxysilane or anilinosilane). 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), 3-mercaptopropylmethyldimethoxysilane, and the like. be able to. Examples of silane coupling agents having an epoxy group (hereinafter also referred to as epoxy silane) include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4 epoxycyclohexyl). Examples thereof include ethyltrimethoxysilane.
These (F) silane coupling agents may be used individually by 1 type, or may use 2 or more types together.

  By adding the silane coupling agent (F) used in the present invention to a curable composition containing an inorganic filler, the mechanical strength can be improved or the viscosity of the curable composition when melted can be reduced. It becomes 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, the amount is preferably 0.01 to 2 parts by mass, more preferably 0.05 to 2 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (E). preferable. Moreover, when a curable composition contains a component (D), the compounding ratio of the (F) silane coupling agent used by this invention is not specifically limited, From a viewpoint of the mechanical strength improvement of hardened | cured material From 0.01 to 2 parts by mass, preferably 0.05 to 2 parts by mass with respect to 100 parts by mass in total of components (A), (B), (D) and (E) Is more preferable.

(Other ingredients)
The curable composition of the present invention may contain a monofunctional benzoxazine compound having one benzoxazine ring as long as the viscosity of the composition is to be reduced, as long as the performance is not impaired.
Moreover, nanocarbon, a flame retardant, a mold release agent, etc. can be mix | blended with the curable composition of this invention in the range which does not impair the performance, for example.
Examples of nanocarbon include carbon nanotubes, fullerenes, and derivatives thereof.
Examples of the flame retardant include phosphate esters such as red phosphorus, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, resorcinol bisphenyl phosphate, and bisphenol A bisdiphenyl phosphate. And boric acid esters.
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, bengara, titanium oxide, etc., in addition to the components (A) to (F), as long as the performance of the curable composition is not impaired. Colorants; natural waxes such as carnauba wax; synthetic waxes such as oxidized polyethylene wax; higher fatty acids such as stearic acid; metal salts such as zinc stearate; and mold release agents such as paraffin; silicone oil and silicone rubber One or more kinds of low stress additives; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; and flame retardants such as phosphazene may be appropriately blended.

[Method for producing curable composition]
Next, the manufacturing method of the curable composition of this invention is demonstrated.
The components (A) to (C) and, if desired, components (D) to (F), other additives, and a solvent are appropriately added and kneaded or mixed to produce the curable composition of the present invention. can do.
The kneading and mixing methods are not particularly limited, and for example, they can be mixed using a planetary mixer, a twin screw extruder, a kneader such as a heat roll or a kneader, and the like. In addition, when the components (A) and (B) are in a highly viscous liquid or solid state at room temperature or contain the component (E), they are heated and kneaded as necessary, and further added. Kneading may be performed under pressure or reduced pressure conditions. The heating temperature is preferably 80 to 120 ° C. In addition, since the component (F) is generally in a liquid state at normal temperature, it may be mixed with the component (E) in advance or with the components (A), (B), (C) and the like.
Since the curable composition containing the component (E) is solid at room temperature, it may be cooled and pulverized after heating and kneading to form a powder, or the powder may be compressed into a pellet. Good. Alternatively, the powder may be granulated into granules.

[Cured product]
The cured product of the curable composition of the present invention is characterized by good heat resistance, hardly pyrolyzing, and 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, more preferably 200 ° C. or higher. The glass transition temperature can be measured by differential scanning calorimetry (DSC). Such a measurement can be easily performed by using a commercially available differential scanning calorimeter (for example, manufactured by Hitachi High-Tech Science Co., Ltd.).

[Method for producing cured product]
Although the manufacturing method of the hardened | cured material of this invention is not specifically limited, For example, it can manufacture as follows.
First, the curable composition of this invention is manufactured by the said method. Subsequently, the obtained curable composition can be cured by a thermosetting reaction by heating. As for the heating temperature at this time, 150 to 330 degreeC is mentioned, for example, Preferably it is 170 to 300 degreeC, More preferably, it is 200 to 250 degreeC. Usually, the heating temperature of the thermosetting reaction in the case of using a phenolic curing agent is a low temperature, for example, 100 ° C. or higher and lower than 170 ° C. In the present invention, from the viewpoint of improving heat resistance, the heating temperature is 170 ° C. or higher. It is preferable to set it to 300 ° C. or lower. As for hardening time, 1 minute or more and less than 5 hours are mentioned, for example. In the case of continuously producing a cured product, a curing time of 1 minute or more and 3 minutes or less is sufficient, but in order to obtain a sufficient strength, it is preferable to further heat for 5 minutes or more and 5 hours or less as post-curing.

[Semiconductor device]
In the semiconductor device of the present invention, a semiconductor element is placed in a cured product obtained by curing the curable composition of the present invention containing the components (A) to (C) and optionally 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 placed on the substrate may be covered.

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

  EXAMPLES The present invention will be specifically described below 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 converted into “Diels-Alder reaction of butadiene and cyclopentadiene-trimer”. The body was synthesized according to the method described in “Determining the Body—”, Journal of Petroleum Society, 1972, Vol. 15, No. 3, p189-192 ”.
Next, the reaction of the above formula (3) was performed as follows. To the reaction vessel, 23.5 kg of chloroform and 1.6 kg of compound (a) were added, and 4.5 kg of metachloroperbenzoic acid was added dropwise with stirring at 0 ° C. The temperature was raised to room temperature and the reaction was carried out for 12 hours.
Next, after removing metachlorobenzoic acid by-produced by filtration, the filtrate was washed with a 1N aqueous sodium hydroxide solution three times and then with a saturated saline solution. The organic layer was dried over magnesium sulfate, the magnesium sulfate was removed by filtration, and the filtrate was concentrated to obtain a crude product.
2 kg of toluene was added to the crude product and dissolved at room temperature. 6 kg of heptane was added dropwise thereto for crystallization, and aging was carried out at 5 ° C. for 1 hour. The crystallized product was collected by filtration and washed with hexane. By drying under reduced pressure at 35 ° C. for 24 hours, 1.4 kg of a 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 diepoxide: TCPD-DE)
The compound (b) was synthesized in the same manner as the compound (a) according to the method described in the above document.
Next, the reaction of the above formula (4) was performed as follows. To the reaction vessel, 59.2 kg of chloroform and 4.0 kg of compound (b) were added, and 10.6 kg of metachloroperbenzoic acid was added dropwise with stirring at −10 ° C. The temperature was raised to room temperature and the reaction was carried out for 12 hours.
Next, metachlorobenzoic acid by-produced by filtration was removed, and the filtrate was washed with 42.0 kg of 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, the magnesium sulfate was removed by filtration, and the filtrate was concentrated to obtain 5.1 kg of a crude product.
To the crude product, 3.5 kg of toluene was added and dissolved at room temperature. 13.7 kg of heptane was added dropwise thereto for crystallization, and aging was carried out at 5 ° C. for 1 hour. The crystallized product was collected by filtration and washed with heptane. By drying under reduced pressure at 35 ° C. for 12 hours, 2.8 kg of a 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 baking soda, 100 L of acetone and 130 L of ion-exchanged water, cooled to 10 ° C. or lower, and controlled to maintain the temperature of the reaction solution at 30 ° C. or lower. Was gradually added and reacted for 10 hours with stirring.
Next, extraction of the reaction product with 100 L of ethyl acetate was performed twice, and the obtained organic layers were separated and combined. Subsequently, the organic layer was washed with 100 L of a mixed aqueous solution of sodium chloride and sodium thiosulfate (sodium 20 wt% + sodium thiosulfate 20 wt%), and then further washed twice with 100 L of ion-exchanged water.
The organic layer after washing 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 a 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) Phenolic 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) Phenol-based 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 Co., Ltd.)
(C2) Curing accelerator 2; Tripalatolylphosphine (TPTP) (made by Hokuko Chemical 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 Compound Other than Component (A) (Other Epoxy Compound)>
The following (D1) and (D2) were used as the component (D).
(D1), (D2) As the other epoxy compounds 1 and 2, the following components (D1) and (D2) having no norbornane structure were used.
(D1) Other epoxy compound 1; epoxy compound (tetramethylbiphenol diglycidyl ether) represented by the following formula (7) (YX-4000H, manufactured by Mitsubishi Chemical Corporation)

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

Example 1
On the hot plate which heated the polyfunctional epoxy compound 1 (A1), the phenol type hardening | curing agent 1 (B1), and the hardening accelerator 2 (C2) which were obtained as mentioned above at 100 degree | times so that it might become the following composition. The mixture 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 circulating 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 with a differential scanning calorimeter DSC7020 manufactured by Hitachi High-Tech Science Inc. at a rate of 10 ° C./min. It was sex. The glass transition temperature here was measured based on “intermediate glass transition temperature: T _mg ” described in JIS K7121 “Plastic Transition Temperature Measurement Method”. The measurement results are summarized in Table 1.
Sample amount: about 10mg

(Examples 2 to 8)
A 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. About each composition, it carried out similarly to Example 1, and measured heat resistance (glass transition temperature). The results are shown in Table 1.

(Comparative Examples 1-3)
A composition of each comparative example was prepared in the same manner as in Example 1 except that the blending ratio of each component was as shown in Table 2. About each composition, it carried out similarly to Example 1, and measured heat resistance (glass transition temperature). 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, Comparative Examples 1 to 3 have a low glass transition temperature and are inferior in heat resistance.
From the above results, it was possible to obtain a highly heat-resistant cured product by curing the curable composition according to the embodiment of the present invention.

Claims (10)

(A) an epoxy compound having at least one norbornane structure and at least two epoxy groups;
(B) a phenolic curing agent;
(C) A curable composition containing a curing accelerator.   (D) The curable composition of Claim 1 which further contains epoxy compounds other than said (A).   (E) The curable composition of Claim 1 or 2 which further contains an inorganic filler.   (F) The curable composition according to any one of claims 1 to 3, further comprising a silane coupling agent.   Hardened | cured material formed by hardening | curing the curable composition as described in any one of Claims 1-4.   The cured product according to claim 5, wherein the glass transition temperature is 160 ° C or higher.   The semiconductor device with which the semiconductor element is installed in the hardened | cured material of Claim 5 or 6. A method for producing a curable composition comprising:
(A) an epoxy compound having at least one norbornane structure and at least two epoxy groups;
(B) a phenolic curing agent;
(C) The manufacturing method of a curable composition which has the process of mixing with a hardening accelerator and obtaining a mixture.   The method according to claim 8, wherein in the step of obtaining the mixture, (D) an epoxy compound other than (A) is further mixed to obtain a mixture. The manufacturing method of hardened | cured material which has the process of heating and hardening the said curable composition manufactured by the method of Claim 8 or 9 at 170-300 degreeC.