JP6765252B2 - Compositions, semiconductor encapsulation compositions, and cured products of these compositions - Google Patents

Description

The present invention relates to compositions containing maleimide compounds, alkenyl group-containing compounds, and phosphonium compounds. In particular, the present invention relates to a composition which is excellent in curability and fluidity and whose cured product exhibits excellent heat resistance, and a cured product obtained by curing the composition.

Conventionally, thermosetting resin compositions such as epoxy resin compositions have been used as semiconductor encapsulation materials, printed wiring board materials, fiber-reinforced composite materials, adhesive materials, and the like. In recent years, in applications such as electrical and electronic parts, further improvement is required for various properties of such epoxy resin compositions. For example, when an epoxy resin composition is used for an electronic component related to an in-vehicle semiconductor, an electronic component used for a display device using a high voltage, a large battery, etc. used in a harsher environment, a high glass transition is achieved. There is a need for an epoxy resin composition that can provide a cured product with temperature. However, the epoxy resin composition has a limit in the heat resistance that can be obtained due to its structure, and does not meet the requirements.

Maleimide resin is known as a resin having higher heat resistance than epoxy resin. However, the maleimide resin has drawbacks such as poor curability, hardness and brittleness, and poor moisture resistance. In order to solve these problems, there are attempts to use maleimide compounds, alkenyl compounds and epoxy resins in combination.

For example, Patent Document 1 discloses a resin composition for encapsulating a semiconductor, which contains a polymaleimide compound, a polyallylphenol compound, and a polyepoxy compound, and further contains triphenylphosphine, which is an organic phosphine compound, as a curing accelerator. Has been done. However, when a normal phosphonium compound is used as a curing accelerator, there is a problem that the curability of the maleimide group is inferior.

Patent Document 2 discloses a sealing composition containing an epoxy resin, an alkenylphenol-based compound, and a bismaleimide compound, and further using dicumylperoxide and triphenylphosphine as a curing accelerator. However, when dicumylperoxide, which is a radical polymerization initiator, and triphenylphosphine, which is an organic phosphine system, are used in combination, the maleimide compound tends to gel at a low reaction rate, the viscosity becomes high, and the fluidity during curing is not sufficient. There was a problem.

Apart from the above techniques, an imidazole-based curing catalyst has been studied as an alternative substance to the organic phosphine-based curing catalyst having poor curability of the maleimide group. However, while the curability is improved, the moisture resistance is lowered, and the performance with a good balance of heat resistance, curability, moisture resistance and the like cannot be exhibited.

Japanese Patent Application Laid-Open No. 2-92918 Japanese Patent Application Laid-Open No. 8-151430

As described above, none of the conventional compositions containing a maleimide compound, an alkenyl group-containing compound, and a curing accelerator are excellent in various properties such as heat resistance and satisfy both curability and fluidity.

Therefore, an object of the present invention is to provide a composition having excellent heat resistance of the obtained cured product and excellent curability and fluidity.

The present invention, maleimide compounds, alkenyl group-containing compound and R ^{1 4} _P + ^X - ^(wherein, R ¹ is independently, which may have a substituent phenyl group or an aliphatic having 1 to 10 carbon atoms The above-mentioned problems are solved by providing a composition containing a phosphonium compound represented by () representing a hydrocarbon group and X ⁻ representing an anion containing a nitrogen atom in its molecular structure.

The present invention also provides a cured product of the above composition.

Further, the present invention provides a composition for a semiconductor encapsulant containing the above composition and an inorganic filler.

INDUSTRIAL APPLICABILITY The present invention provides a composition having excellent curability and fluidity, and the cured product having excellent heat resistance (for example, a glass transition temperature of 300 ° C. or higher). The present invention also provides a cured product obtained by curing the composition.

FIG. 1 is a graph in which the fluidity of the compositions obtained in Examples and Comparative Examples is taken on the X-axis and the curability is taken on the Y-axis.

The composition of the present invention contains the following as its constituent components.
-Maleimide compound.
-Alkenyl group-containing compound.
· ^R ₁ 4 ^P + X ^- phosphonium compound represented by.
(In the formula, R ¹ independently represents a phenyl group which may have a substituent or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and X ⁻ represents an anion containing a nitrogen atom in its molecular structure. Represent.)
Hereinafter, each of these components will be described.

[Maleimide compound]
The type of maleimide compound used in the composition of the present invention is not particularly limited as long as it is a compound having two or more maleimide groups in one molecule. That is, the maleimide compound can be at least a bismaleimide compound. Examples of maleimide compounds include 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 1,6-bismaleimide- (2,4,4-trimethyl) hexane, N, N'-. Skeletons of compounds such as decamethylene bismaleimide, N, N'-octamethylene bismaleimide, N, N'-hexamethylene bismaleimide, N, N'-trimethylene bismaleimide, N, N'-ethylene bismaleimide. May have an aliphatic (acyclic) structure. Alternatively, maleimide compounds include, for example, bis [(2,5-dioxo-2,5-dihydropyrrole-1-yl) methyl] bicyclo [2.2.1] heptane, N, N'-m-phenylene bismaleimide, 4 , 4'-diphenylmethane bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 4,4'-diphenylsulfide bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1 , 3-Phenylene bismaleimide, 2,2'-bis [4- (4-maleimide phenoxy) phenyl] propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 3 , 3'-dimethyl-4,4'-diphenylmethanebismaleimide, 1,3-bis (3-maleimidephenoxy) benzene, 1,3-bis (4-maleimidephenoxy) benzene, 1,3-bis (3-maleimide) The skeleton of the compound, such as phenoxy) benzene, may have an aliphatic cyclic structure or an aromatic cyclic structure.

Among them, bis [(2,5-dioxo-2,5-dihydropyrrole-1-yl) methyl] bicyclo [2.2.1] heptane, 1,6-bismaleimide- (2,2,4-trimethyl) It is preferable that the skeleton of the compound has an aliphatic (acyclic) structure selected from the group consisting of hexane, N, N'-hexamethylene bismaleimide. Alternatively, 4,4'-diphenylmethane bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 4,4'-diphenylsulfide bismaleimide, 4-methyl-1,3-phenylenebis. Maleimide, 1,3-phenylene bis maleimide, 2,2'-bis [4- (4-maleimide phenoxy) phenyl] propane, 1,3-bis (4-maleimide phenoxy) benzene, 1,3-bis (3-bis) Maleimidephenoxy) It is preferable that the skeleton of the compound selected from the group consisting of benzene has an aliphatic cyclic structure or an aromatic cyclic structure.

In the present invention, one type of maleimide compound may be used alone, but two or more types of a plurality of types of bismaleimide compounds may be mixed and used. From the viewpoint of improving heat resistance, a maleimide compound having an aliphatic cyclic structure or an aromatic cyclic structure in the skeleton of the compound is preferable.

[Alkenyl group-containing compound]
The alkenyl group-containing compound used in the composition of the present invention is not particularly limited as long as it is a compound having two or more alkenyl groups in one molecule. Alkenyl group, the general formula C _{n H 2n-1 -} is represented by an aliphatic group having an unsaturated double bond. From the viewpoint of reactivity, the alkenyl group is preferably -CH ₂ -CH = CH ₂ (allyl group) or -CH = CH-CH ₃ , and more preferably an allyl group.

The alkenyl group-containing compound used in the present invention is preferably an alkenyl group-containing phenol compound from the viewpoint of improving the heat resistance of the cured product of the composition of the present invention, and particularly has an aromatic ring in one molecule. It is preferable that the phenol compound has two or more bonded alkenyl groups, or the phenol compound has two or more alkenyl ether groups in which the hydrogen atom of the hydroxyl group bonded to the aromatic ring is replaced with an alkenyl group in one molecule.

Examples of the phenol compound having two or more alkenyl groups bonded to the aromatic ring in one molecule include 2,2-bis [4-hydroxy-3- (2-allyl) phenyl] propane 2,2-bis [4. Dialkenyl bisphenol compounds such as −hydroxy-3- (2-propenyl) phenyl] propane and bis [4-hydroxy-3- (2-propenyl) phenyl] methane, and orthoallylphenol and formaldehyde are subjected to polycondensation reaction. Examples thereof include the obtained orthoallylphenol novolak resin (MEH-8000H manufactured by Meiwa Kasei Co., Ltd.).

As a phenol compound having two or more alkenyl ether groups bonded to an aromatic ring in one molecule, for example, it can be obtained by reacting a commercially available phenol resin with an alkenyl compound having a halogen group such as allyl chloride. The alkenyl group bonded to the aromatic ring in the above-mentioned one molecule by transferring a phenol compound having two or more alkenyl ether groups bonded to the aromatic ring in one molecule obtained by the above reaction to Kreisen. A phenol compound having two or more of can be obtained.

The alkenyl group-containing compound used in the present invention is an alkenyl group-containing phenol aralkyl resin or an alkenyl ether group-containing phenol aralkyl resin having a biphenyl structure in its molecular structure from the viewpoint of flame retardancy and low water absorption. Is more preferable.

The alkenyl group-containing phenol aralkyl resin is preferably represented by, for example, the following formula (2).

式中、
Ａはアルケニル基を表し、
Ｒは水素原子、炭素数１〜１０の飽和若しくは不飽和脂肪族炭化水素基、アルコキシ基、アリール基又はアラルキル基を表し、それぞれ同一でも異なっていてもよく、
ｊ、ｋ及びｌは、それぞれ独立に１〜２の整数を表し、
ｐ、ｑ及びｒは、それぞれ独立に０〜３の整数を表し、
ｓ、ｔ及びｕは、それぞれ独立に１〜２の整数を表し、
ｊ＋ｐ＋ｓ≦５、ｋ＋ｑ＋ｔ≦４、且つｌ＋ｒ＋ｕ≦５であり、
ｎは０〜２０の数を表す。
但し、複数あるＡで表されるアルケニル基のうち一部のアルケニル基が水素原子に置換されていてもよい。

During the ceremony
A represents an alkenyl group
R represents a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group or an aralkyl group, and may be the same or different from each other.
j, k, and l each independently represent an integer of 1 to 2.
p, q and r independently represent integers 0 to 3, respectively.
s, t and u each independently represent an integer of 1 to 2.
j + p + s ≦ 5, k + q + t ≦ 4, and l + r + u ≦ 5.
n represents a number from 0 to 20.
However, some of the alkenyl groups represented by A may be substituted with hydrogen atoms.

In the formula (2), preferred groups as R are hydrogen atoms, methyl groups and phenyl groups, and from the viewpoint of reactivity with maleimide compounds and epoxy compounds, more preferable groups as R are hydrogen atoms. Further, in the formula (2), j, k and l are independently 1 or 2, respectively, that the reactivity with the epoxy group (reactivity between the epoxy group and the hydroxyl group) and the heat resistance of the cured product (crosslink density). From the viewpoint of high flame retardancy and low water absorption, it is preferably 1 each. It is preferable that p, q and r are independently 1 from the viewpoint of not sterically hindering the reactivity with the maleimide compound or the epoxy compound. More preferably, p, q and r are 0, respectively. In the formula (2), a hydrogen atom is bonded to the carbon atom on the benzene ring which is not bonded to any of the hydroxyl group, the alkenyl group A, the methylene group (-CH _2- ) and the substituent R. It shall be. Regarding s, t and u, 1 or 2 are independently set in terms of reactivity with the maleimide compound (reactivity between the maleimide group and the alkenyl group) and heat resistance of the cured product (high crosslink density). From the viewpoint of handleability at room temperature (25 ° C.), it is more preferable that the values are 1 independently of each other.

In the formula (2), j + p + s is preferably j + p + s = 4, more preferably j + p + s = 3, and even more preferably j + p + s = 2. For k + q + t, k + q + t = 4, more preferably k + q + t = 3, and even more preferably k + q + t = 2. Regarding l + r + u, l + r + u = 4, more preferably l + r + u = 3, and even more preferably l + r + u = 2. n is preferably a number from 0 to 10.

The alkenyl ether group-containing phenol aralkyl resin is represented by, for example, the following formula (3).

式中、
Ａはアルケニル基を表し、
Ｒは水素原子、炭素数１〜１０の飽和若しくは不飽和脂肪族炭化水素基、アルコキシ基、アリール基又はアラルキル基を表し、それぞれ同一でも異なっていてもよく、
ｊ、ｋ及びｌは、それぞれ独立に１〜２の整数を表し、
ｐ、ｑ及びｒは、それぞれ独立に０〜３の整数を表し、
ｋ＋ｑ≦４であり、
ｎは０〜２０の数を表す。
但し、複数あるＡで表されるアルケニル基のうち一部のアルケニル基が水素原子に置換されていてもよい。

During the ceremony
A represents an alkenyl group
R represents a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group or an aralkyl group, and may be the same or different from each other.
j, k, and l each independently represent an integer of 1 to 2.
p, q and r independently represent integers 0 to 3, respectively.
k + q ≦ 4
n represents a number from 0 to 20.
However, some of the alkenyl groups represented by A may be substituted with hydrogen atoms.

In the formula (3), preferred groups as R are hydrogen atoms, methyl groups and phenyl groups, and from the viewpoint of reactivity with maleimide compounds and epoxy compounds, more preferable groups as R are hydrogen atoms. Further, in the formula (3), j, k and l are independently 1 or 2, respectively, that the reactivity with the epoxy group (reactivity between the epoxy group and the hydroxyl group) and the heat resistance of the cured product (crosslink density). From the viewpoint of high flame retardancy and low water absorption, it is preferably 1 each. It is preferable that p, q and r are independently 1 from the viewpoint of not sterically hindering the reactivity with the maleimide compound or the epoxy compound. More preferably, p, q and r are each 0. In the equation (2), alkenyl ether group (AO-), a methylene group (-CH 2 _-) and the carbon atoms on the benzene ring which is not bound to any of the substituents R, bonded hydrogen atoms It is assumed that

In the formula (3), k + q is preferably k + q = 3, more preferably k + q = 2, and even more preferably k + q = 1. n is preferably a number from 0 to 10.

The alkenyl group-containing compound used in the present invention is not particularly limited in its softening point, and an appropriate softening point may be selected according to the specific use of the cured product obtained from the composition of the present invention. For example, in the use of a semiconductor encapsulant, from the viewpoint of handling, it is preferable that it is solid at room temperature (25 ° C.), so that the softening point is in the range of 50 ° C. or higher and 150 ° C. or lower, particularly 60 ° C. or higher and 120 ° C. or lower. Is preferable. The softening point of the alkenyl group-containing compound is measured by the METTLER method or the like.

The number average molecular weight of the alkenyl group-containing compound used in the present invention is not particularly limited, and an appropriate number average molecular weight may be selected according to the specific use of the cured product obtained from the composition of the present invention. .. For example, in the application of the semiconductor encapsulant, the number average molecular weight is preferably 150 or more and 3000 or less, particularly 300 or more and 1500 or less, provided that the range of n in the formula (2) or the formula (3) is satisfied. .. The number average molecular weight can be calculated from the molecular weight obtained in terms of polystyrene using a gel permeation chromatography (GPC) method.

The alkenyl group-containing compound used in the present invention is not particularly limited in its alkenyl group equivalent, and has a softening point of the alkenyl group-containing compound, handleability when used as a resin composition, and curing obtained from the resin composition of the present invention. An appropriate alkenyl group equivalent may be selected according to the specific use of the substance, the balance of physical properties, the availability in industry, and the like. Preferably, the alkenyl group equivalent is 80 g / eq or more and 1000 g / eq or less, and more preferably 90 g / eq or more and 500 g / eq or less. The allyl group equivalent of the phenol resin is measured by the iodine valence titration method based on JIS K0070.

When the alkenyl group-containing compound used in the present invention has a hydroxyl group in its molecular structure, the hydroxyl group equivalent is not limited, and an appropriate hydroxyl group equivalent may be selected according to the degree of curing of the resin composition. .. Preferably, the hydroxyl group equivalent is 80 g / eq or more and 300 g / eq or less, and more preferably 90 g / eq or more and 280 g / eq or less. The hydroxyl group equivalent of the phenolic resin is measured by a method according to JIS K0070.

The content of the alkenyl group-containing compound contained in the composition of the present invention is not particularly limited. From the viewpoint of improving both curability and fluidity of the composition, it is preferably 30 parts by mass or more and 40 parts by mass or less, preferably 32 parts by mass or more, with respect to 100 parts by mass of the maleimide compound contained in the composition. 38 parts by mass or less is more preferable.

From the viewpoint of heat resistance of the composition, the ratio of the number of maleimide groups of the maleimide compound contained in the composition to the number of alkenyl groups of the alkenyl group-containing compound [(mass of alkenyl group-containing compound / alkenyl of alkenyl group-containing compound). Base equivalent) / (mass of maleimide compound / maleimide group equivalent of maleimide compound)] is preferably 0.2 or more and 1.0 or less.

[Phoenium compound]
Phosphonium compounds used in the present invention, as mentioned above R ¹ ₄ P ⁺ X ^- is represented by. This phosphonium compound mainly functions as a curing accelerator in the composition of the present invention.

In the phosphonium compound used in the present invention, R ¹ is independently a phenyl group which may have a substituent or an aliphatic hydrocarbon group having 1 to 10 carbon atoms. It is preferably a phenyl group which may have a substituent, and more preferably a phenyl group. Examples of the substituent include a methyl group and an ethyl group. One preferred aspect is, R ¹ ₄ P ⁺ X ^- in a three R ¹ is a phenyl group wherein the remaining one of R ^1, aliphatic selected from methyl, ethyl or butyl group It is a group. Other preferred aspects is, R ¹ ₄ P ⁺ X ^- in a four R ¹ are all phenyl groups in the formula is a tetraphenylphosphonium structure.

In the phosphonium compound used in the present invention, X ⁻ is an anion containing a nitrogen (N) atom in its molecular structure. Since X ⁻ is an anion containing a nitrogen (N) atom in its molecular structure, both curability and fluidity of the composition of the present invention can be improved.

In the phosphonium compounds used in the present invention, X is preferably thiocyanate ([S-C = N] - Structure) anion, isothiocyanate ([N = C = S] - Structure) anion, or dicyanamide ([N (C _{≡N) 2]} ^- structure) is an anion, more preferably dicyanamide _{([N (C≡N) 2]} - structure) is an anion.

In particular, among the phosphonium compounds used in the present invention, preferred ones are represented by the following formula (1).

The melting point of the phosphonium compound used in the present invention is preferably 100 ° C. or higher and 240 ° C. or lower, more preferably 100 ° C. or higher, from the viewpoint of kneadability with a maleimide compound, an alkenyl group-containing compound, and an epoxy compound and moldability during molding of the composition. It is 110 ° C. or higher and 230 ° C. or lower, more preferably 120 ° C. or higher and 220 ° C. or lower.

The content of the phosphonium compound contained in the composition of the present invention is not particularly limited. From the viewpoint of improving both the fluidity and curability of the composition of the present invention, it is preferably 1 mol% or more and 12 mol% or less with respect to the maleimide compound contained in the composition, and 3 mol% or more. It is more preferably 12 mol% or less, and preferably 7 mol% or more and 11 mol% or less. Further, from the viewpoint of making the composition excellent in moldability in addition to fluidity and curability, it is preferable that the composition contains 3 mol% or more and 20 mol% or less with respect to the maleimide group in the maleimide compound. It is more preferably contained in an amount of 5 mol% or more and 15 mol% or less.

The composition of the present invention containing each of the above components is excellent in curability and fluidity. Therefore, the composition of the present invention is suitably used as a curable composition that cures by applying energy such as heat. The cured product obtained by applying energy such as heat to the composition of the present invention has excellent heat resistance (for example, a glass transition temperature of 300 ° C. or higher). In addition, the composition of the present invention has excellent curability, so that the molding cycle can be shortened. As a result, the manufacturing cost can be reduced. Further, since the composition of the present invention is excellent in fluidization, the fluidity is unlikely to decrease even if the inorganic filler is highly filled. As a result, physical properties such as expansion coefficient and heat conduction of the cured product obtained from the composition of the present invention can be improved.

The composition of the present invention may contain an epoxy compound in addition to the above-mentioned components. The epoxy compound used in the present invention is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. The type of epoxy compound is not particularly limited, and an epoxy compound known in the art can be used. As the epoxy compound, an appropriate epoxy compound may be selected according to the specific use of the cured product obtained from the resin composition of the present invention. Specifically, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, phenol aralkyl novolac type epoxy resin, biphenyl aralkyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc. Examples thereof include an epoxy resin having two or more epoxy groups in one molecule, such as a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, and a halogenated epoxy resin. One of these epoxy resins may be used alone, or two or more of these epoxy resins may be used in combination. For example, in the use of a semiconductor encapsulant, the epoxy resin is preferably a solid at room temperature (25 ° C.), and a biphenyl type epoxy compound such as YX-4000 manufactured by Mitsubishi Chemical Corporation can be preferably used.

The epoxy compound used in the present invention is not particularly limited in its softening point, and an appropriate softening point may be selected according to the specific use of the cured product obtained from the composition of the present invention. For example, in the use of a semiconductor encapsulant, from the viewpoint of handling, it is preferable that it is solid at room temperature (25 ° C.), so that the softening point is in the range of 50 ° C. or higher and 150 ° C. or lower, particularly 60 ° C. or higher and 120 ° C. or lower. It is preferable to have. The softening point of the epoxy resin is measured by the same method as the softening point of the alkenyl group-containing compound described above.

The epoxy equivalent of the epoxy compound used in the present invention is not particularly limited, and an appropriate epoxy equivalent may be selected according to the degree of curing of the composition of the present invention. Preferably, the epoxy equivalent is 100 g / eq or more and 500 g / eq or less, and more preferably 150 g / eq or more and 300 g / eq or less. The epoxy equivalent of the epoxy compound is measured by JIS K7236.

The content of the epoxy compound contained in the composition of the present invention is not particularly limited. From the viewpoint of improving both curability and fluidity of the composition of the present invention, it is preferably 20 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the maleimide compound contained in the composition. It is more preferably more than parts by mass and 28 parts by mass or less.

When the alkenyl group-containing compound used in the present invention has a hydroxyl group in the molecular structure, the epoxy compound contained in the composition is considered from the viewpoint of the reaction between the hydroxyl group and the epoxy group and the water absorption of the composition. The ratio of the number of epoxy groups to the number of hydroxyl groups of the alkenyl group-containing compound [(mass of alkenyl group-containing compound / hydroxyl group equivalent of alkenyl group-containing compound) / (mass of epoxy compound / epoxy equivalent of epoxy compound)] is It is preferably 0.8 or more and 1.2 or less.

[Resin composition]
In addition to the components described above, the composition of the present invention may contain, for example, a mold release agent, a colorant, a coupling agent, a flame retardant, and the like, if necessary. Alternatively, these agents can be used by reacting them with the maleimide compound and the alkenyl group-containing compound used in the present invention in advance. The blending ratio of these agents can be appropriately determined according to the specific use of the cured product obtained from the composition of the present invention.

If necessary, a filler may be added to the composition of the present invention. As the filler, either an organic filler or an inorganic filler can be used. As the inorganic filler, for example, amorphous silica, crystalline silica, alumina, calcium silicate, talc, mica, etc. can be used. In particular, it is preferable to use amorphous silica and crystalline silica from the viewpoint of heat dissipation and cost.

The particle size of the filler is not particularly limited, but it is desirable that the average particle size is 0.01 μm or more and 150 μm or less in consideration of the filling rate. The average particle size is measured by, for example, a cyclic particle size distribution meter. The blending ratio of the filler in the composition of the present invention is not particularly limited, and may be appropriately determined according to the specific use of the cured product obtained from the composition of the present invention. For example, the blending ratio of the filler in the composition is preferably 30% by mass or more and 95% by mass or less, and more preferably 50% by mass or more and 90% by mass or less. By setting the blending ratio of the filler within this range, it is possible to suppress an excessive increase in the water absorption rate of the cured product of the composition, and the fluidity of the composition is less likely to be impaired. The average particle size of the filler can be measured by a laser diffraction type particle size distribution measuring device or the like.

In the production of the composition of the present invention, a predetermined amount of the above-mentioned components is uniformly stirred and mixed, and kneaded, cooled and pulverized by a kneader, a roll, an extruder or the like which has been preheated to 70 ° C. or higher and 95 ° C. or lower. It can be obtained by a method such as There is no particular limitation on the blending order of the ingredients.

The composition of the present invention can be cured by heating it to obtain a cured product. The heating conditions for obtaining the cured product are usually about 100 ° C. or higher and 300 ° C. or lower, preferably 120 ° C. or higher and 200 ° C. or lower. The heating time is preferably about 1 minute or more and 15 hours or less.

[Composition for semiconductor encapsulant]
The composition of the present invention can be suitably used as a sealing material for semiconductor devices. Depending on the sealing mode, the encapsulant for the semiconductor element includes an encapsulant that seals the gap between the semiconductor element and the circuit board and the periphery of the semiconductor element, and an undercoat that seals only the gap between the semiconductor element and the circuit board. There is a fill material. The composition of the present invention can be suitably used in both of these sealing modes, but the sealing material is in a solid state such as a tablet shape, and the gap between the semiconductor element and the circuit board and the semiconductor element. It can be particularly preferably used as a sealing material for sealing the periphery of the tablet. When the composition of the present invention is used as a sealing material for a semiconductor element, it is preferably in the form of a composition for a semiconductor sealing material containing the composition and an inorganic filler. The types of inorganic fillers and the like are as described above.

The composition of the present invention can be effectively used not only as a sealing material for semiconductor elements, but also as a molding material, a material for powder coating, an adhesive, a printed circuit board, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "%" and "parts" mean "mass%" and "parts by mass", respectively.

Prior to the explanation of Examples and Comparative Examples, the method for measuring the characteristics used in these examples is shown below.
(1) Liquidity (spiral flow)
The fluidity of the thermosetting composition containing the inorganic filler was measured under the following conditions.
Equipment: Transfer molding machine (Takara Seisakusho Co., Ltd., TTM-MS MS55)
Measurement conditions: Mold temperature 175 ° C., injection pressure 6.9 MPa, holding time 120 seconds Measuring method: The sample was injected into a spiral flow measurement mold according to EMMI-1-66, and the flow length was measured.
(2) Gel time Measured using a WP type curast meter (JSR Trading Co., Ltd.).
The time when the torque reached 0.04 Nm was defined as the gel time.
(3) Curability (curast meter)
The gel time and the torque 2 minutes after the start of measurement were measured under the following conditions and used as an index of curability.
Equipment: WP type curast meter (JSR Trading)
Measurement temperature: 175 ° C
(4) Glass transition temperature (DMA method)
The compositions obtained in Examples and Comparative Examples were molded into a shape having a thickness of 1 mm, a width of 2.4 mm and a length of 40 mm, and cured at 180 ° C. for 8 hours to prepare a test piece. The storage elastic modulus of the test piece was measured under the following conditions using a dynamic viscoelasticity measuring device RSA-G2 manufactured by TA Instruments. The peak of Tan δ obtained by the measurement was taken as the glass transition temperature.
(Measurement condition)
Temperature rise conditions: 3 ° C / min Upper limit of measurement: 350 ° C
Atmosphere: Air measurement jig: Single cantilever

[Examples 1 and 2]
Bismaleimide compound (BMI-1000 manufactured by Daiwa Kasei Kogyo, maleimide group equivalent 179 g / eq), epoxy resin (Mitsubishi Chemical YX-4000, epoxy equivalent 187 g / eq), containing allyl group represented by the following formula (4) Table 1 shows the powders of phenol aralkyl resin (hydroxyl equivalent 260 g / eq, allyl group equivalent 260 g / eq) and tetraphenylphosphonium disianamide (TPP-DCA manufactured by Hokuko Chemical Co., Ltd., melting point 208-209 ° C.) as a curing accelerator. Mixed in proportion. The unit of the numerical value in the column of composition composition in Table 1 is a mass part unless otherwise specified. Next, silica filler (MSR-2212MS manufactured by Tatsumori) as an inorganic filler was mixed so as to be 83% of the mass of the composition, and then kneaded with two rolls at 80 ° C. to have a thermosetting property containing the inorganic filler. A composition was prepared.
The fluidity (spiral flow), gel time, curability (curastometer), and glass transition temperature Tg (DMA method) of the obtained thermosetting composition were measured. The results are listed in Table 1 below.

[Comparative Examples 1 to 7]
Triphenylphosphine (TPP manufactured by Hokuko Chemical Industries, Ltd.), phosphorus irid compound (1- (triphenylphosphoraniliden) -2-propanone (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as TPP-2P)), or imidazole (Shikoku Kasei) as a curing accelerator A thermosetting composition containing an inorganic filler was prepared in the same manner as in Examples 1 and 2 except that 2E4MZ) was used.
The fluidity (spiral flow), gel time, curability (curastometer), moldability and glass transition temperature (DMA method) of the obtained thermosetting composition were measured. The results are shown in Table 1.

Regarding the fluidity (spiral flow) and curability (curastometer (torque after 2 minutes)) of the compositions of Examples 1 and 2 and Comparative Examples 1 to 7, the fluidity (spiral flow) was taken as the X-axis and cured. A graph showing the property (currosis meter (torque after 2 minutes)) on the Y-axis is shown in FIG.

As shown in FIG. 1, the thermosetting compositions of Examples 1 and 2 using tetraphenylphosphonium disianamide, which is a phosphonium compound, as a curing accelerator were compared with the compositions of Comparative Examples 1 to 7. Therefore, it can be seen that both fluidity and curability are excellent.

[Example 3 and Comparative Example 8]
The present example and the comparative example are examples in which the epoxy compound was not blended in the composition. Specifically, the compositions having the formulations shown in Table 2 below were prepared. As the alkenyl group-containing compound, MEH-8000H (manufactured by Meiwa Kasei) obtained by reacting orthoallylphenol with formaldehyde was used. The reactivity of the prepared composition was evaluated by the gelation time at 175 ° C. The gelling time was measured by an automatic gelling tester (manufactured by Cyber Co., Ltd.). The gelling time was defined as the time when the maximum torque value reached 10%. The results are listed in Table 2 below.

As is clear from the results shown in Table 2, it can be seen that the composition of Example 3 has better reactivity than the composition of Comparative Example 8.

The composition of the present invention can be effectively used not only as a sealing material for semiconductor elements, but also as a molding material, a material for powder coating, an adhesive, a printed circuit board, and the like.

Claims (4)

A maleimide compound, a phenolic resin having a biphenyl structure represented by the following formula (2), an alkenyl ether group-containing phenol aralkyl resin having a biphenyl structure represented by the following formula (3), and the following formula (1) . A composition comprising a phosphonium compound.

During the ceremony
A represents an alkenyl group
R represents a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group or an aralkyl group, and may be the same or different from each other.
j, k, and l each independently represent an integer of 1 to 2.
p, q and r independently represent integers 0 to 3, respectively.
s, t and u each independently represent an integer of 1 to 2.
j + p + s ≦ 5, k + q + t ≦ 4, and l + r + u ≦ 5.
n represents a number from 0 to 20.
However, some of the alkenyl groups represented by A may be substituted with hydrogen atoms.

During the ceremony
A represents an alkenyl group
R represents a hydrogen atom, a saturated or unsaturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an aryl group or an aralkyl group, and may be the same or different from each other.
j, k, and l each independently represent an integer of 1 to 2.
p, q and r independently represent integers 0 to 3, respectively.
k + q ≦ 4
n represents a number from 0 to 20.
However, some of the alkenyl groups represented by A may be substituted with hydrogen atoms. The composition according to claim 1 , further containing an epoxy compound. A composition for a semiconductor encapsulant containing the composition according to claim 1 or 2 and an inorganic filler. A cured product of the composition according to claim 1 or 2 .

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