Thermosetting composition, semiconductor device fixation composition, and thermally conductive film formation composition

Abstract

The present invention provides a thermosetting composition having excellent thixotropy and forming a cured product with excellent thermal conductivity, a semiconductor device fixing composition comprising this thermosetting composition, and a thermally conductive film forming composition. [Solution] A thermosetting composition containing the following components (A) and (B), A thermosetting composition in which the content of component (B) is 5 to 500 parts by mass per 100 parts by mass of component (A). (A) Component: See formula (a-1) below TIFF2026060313000011.tif11157〔R 1 This represents an unsubstituted or substituted alkyl group having 1 to 16 carbon atoms, or an unsubstituted or substituted aryl group having 6 to 20 carbon atoms. Silane compound polymer having repeating units represented by [repeating unit (1)] (B) Component: Boron nitride filler

Description

Technical Field

[0001] The present invention relates to a thermosetting composition having excellent thixotropy, a composition for fixing semiconductor elements, and a composition for forming a thermally conductive film.

Background Art

[0002] Conventionally, curable compositions have been variously improved according to their uses and have been widely used industrially as raw materials for optical components and molded bodies, adhesives, coating agents, and the like. In recent years, curable compositions containing polysilsesquioxane compounds have attracted attention because cured products having excellent heat resistance, transparency, etc. are formed.

[0003] For example, Patent Documents 1 to 3 describe curable compositions containing polysilsesquioxane compounds and the use of curable compositions as encapsulating materials.

[0004] In recent years, various fillers have been added to curable compositions to impart further functions to the curable compositions. For example, Patent Document 4 describes a concrete protection material containing silica particles and having good thixotropy.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0006] When fixing various elements using a curable composition, it is necessary to accurately apply a predetermined amount of the curable composition to the predetermined location; therefore, such a curable composition usually requires excellent thixotropy. Furthermore, it is believed that the thermal conductivity of the fixing material for the element reduces the occurrence of element failures.

[0007] As described above, Patent Document 4 states that a curable composition containing silica particles has good thixotropy. However, according to the inventors' research, a thermosetting composition that results in a cured product with excellent thermal conductivity could not be obtained even when silica particles were used as a filler.

[0008] This invention was made under such circumstances, and aims to provide a thermosetting composition that exhibits excellent thixotropy and results in a cured product with excellent thermal conductivity, a semiconductor device fixing composition comprising this thermosetting composition, and a thermally conductive film forming composition. [Means for solving the problem]

[0009] In order to solve the above problems, the inventors of this invention have diligently studied thermosetting compositions containing silane compound polymers. As a result, we discovered that a thermosetting composition containing a silane compound polymer having repeating units derived from a trifunctional silane compound and a boron nitride filler results in a cured product with excellent thixotropy and thermal conductivity, thus completing the present invention.

[0010] Thus, the present invention provides the following thermosetting compositions [1] to

[12] , the semiconductor device fixing composition

[13] , and the thermally conductive film forming composition

[14] .

[0011] [1] A thermosetting composition containing the following components (A) and (B), A thermosetting composition in which the content of component (B) is 5 to 500 parts by mass per 100 parts by mass of component (A). (A) Component: See formula (a-1) below

[0012] [ka]

[0013] [R 1 This represents an unsubstituted or substituted alkyl group having 1 to 16 carbon atoms, or an unsubstituted or substituted aryl group having 6 to 20 carbon atoms. Silane compound polymer having repeating units represented by [repeating unit (1)] (B) Component: Boron nitride filler [2] The thermosetting composition according to [1], wherein the amount of repeating unit (1) in component (A) is 90 to 100 mol% of the total amount of repeating units in component (A). [3] The thermosetting composition according to [1] or [2], wherein the mass-average molecular weight (Mw) of component (A) is 1,000 to 10,000. [4] A thermosetting composition according to any one of [1] to [3], wherein component (A) is thermosetting. [5] The thermosetting composition according to any one of [1] to [4], wherein the content of component (A) is 5 to 90% by mass of the total amount of components constituting the thermosetting composition (excluding the solvent). [6] Particle size of component (B) (D 50 A thermosetting composition according to any one of [1] to [5], wherein the thickness is 0.1 to 30 μm. [7] (B) Component with particle size (D 50 Component (B1) has a particle size greater than 3.0 μm and less than or equal to 30 μm, and component (B) has a particle size (D 50 A thermosetting composition according to [6], comprising component (B2) having a size of 0.1 μm or more and 3.0 μm or less. [8] Particle size (D 50 Component (C1) is a filler with a particle size greater than 3.0 μm and less than or equal to 30 μm [excluding component (B)], and component (B) is a filler with a particle size (D 50 A thermosetting composition according to [6], comprising component (B2) having a size of 0.1 μm or more and 3.0 μm or less. [9] (B) Component with particle size (D 50(B1) component with a particle size (D 50 ) greater than 3.0 μm and less than or equal to 30 μm, and a (C2) component which is a filler (excluding the (B) component) with a particle size (D 〔10〕The thermosetting composition according to any one of 〔1〕~〔9〕, further containing the following (D) component. (D) component: silane coupling agent 〔11〕The thermosetting composition according to 〔10〕, wherein the content of the (D) component is 5 to 50 parts by mass with respect to 100 parts by mass of the (A) component. 〔12〕The thixotropic index (viscosity at a shear rate of 2 s -1 ) / viscosity at a shear rate of 200 s -1 ) is 1.5 or more, and the thermosetting composition according to any one of 〔1〕~〔11〕. 〔13〕A composition for fixing a semiconductor element, comprising the thermosetting composition according to any one of 〔1〕~〔12〕. 〔14〕A composition for forming a thermally conductive film, comprising the thermosetting composition according to any one of 〔1〕~〔12〕.

Advantages of the Invention

[0014] According to the present invention, there are provided a thermosetting composition excellent in thixotropy, a thermosetting composition that becomes a cured product excellent in thermal conductivity, a composition for fixing a semiconductor element, and a composition for forming a thermally conductive film, each comprising the thermosetting composition.

Embodiments for Carrying Out the Invention

[0015] In this specification, for preferred numerical ranges (for example, ranges such as content), the lower limit value and the upper limit value described stepwise can be combined independently of each other. For example, from the description "preferably 10 to 90, more preferably 30 to 60", it is also possible to combine the "preferred lower limit value (10)" and the "more preferred upper limit value (60)" to obtain "10 to 60".

[0016] 〔(A) component: silane compound polymer〕 The thermosetting composition of the present invention contains the following (A) component. (A) Component: Silane compound polymer having repeating units represented by the following formula (a-1) [Repeating unit (1)]

[0017] [ka]

[0018] [R 1 This represents an unsubstituted or substituted alkyl group having 1 to 16 carbon atoms, or an unsubstituted or substituted aryl group having 6 to 20 carbon atoms.

[0019] The thermosetting composition of the present invention contains a silane compound polymer of component (A) (hereinafter sometimes referred to as "silane compound polymer (A)"), and therefore its cured product has high adhesive strength.

[0020] In formula (a-1), R 1 This represents an unsubstituted or substituted alkyl group having 1 to 16 carbon atoms, or an unsubstituted or substituted aryl group having 6 to 20 carbon atoms.

[0021] R 1 The unsubstituted or substituted alkyl group having 1 to 16 carbon atoms preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Note that this carbon number refers to the carbon number of the part excluding the substituent (the alkyl group part). Therefore, R 1 If R is a "carbon 1 to carbon 16 alkyl group having substituents", 1 The number of carbon atoms can sometimes exceed 16.

[0022] R 1 The unsubstituted C1-C16 alkyl group may be a linear alkyl group or a branched alkyl group. 1 Examples of unsubstituted C1-C16 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, and n-decyl groups.

[0023] R 1 The number of substituent atoms (excluding hydrogen atoms) of a C1-C16 alkyl group having the substituent is usually 1-30, preferably 1-20. Examples of substituents on C1-C16 alkyl groups include halogen atoms such as fluorine, chlorine, and bromine; aryl groups such as phenyl groups; alkoxy groups such as methoxy and ethoxy groups; cyano groups; amino groups; acryloyloxy groups; methacryloyloxy groups; epoxy groups; and the like.

[0024] R 1 The number of carbon atoms in the unsubstituted or substituted aryl group having 6 to 20 carbon atoms is preferably 6 to 15, and more preferably 6 to 10. Note that this number of carbon atoms refers to the number of carbon atoms in the portion excluding the substituent (the aryl group portion). Therefore, R 1 If R is a "substituted aryl group having 6 to 20 carbon atoms", 1 The number of carbon atoms can sometimes exceed 20.

[0025] R 1 Examples of unsubstituted aryl groups having 6 to 20 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, tolyl, and xylyl groups.

[0026] R 1 The number of substituent atoms (excluding hydrogen atoms) of an aryl group having 6 to 20 carbon atoms is usually 1 to 30, preferably 1 to 20. Examples of substituents on aryl groups having 6 to 20 carbon atoms include halogen atoms such as fluorine, chlorine, and bromine; alkoxy groups such as methoxy and ethoxy groups; cyano groups; amino groups; acryloyloxy groups; methacryloyloxy groups; epoxy groups; and the like.

[0027] Among these, R 1 Preferably, the group is an unsubstituted C1-C12 alkyl group, a C1-C12 fluoroalkyl group, or an unsubstituted C6-C20 aryl group. R1 Since silane compound polymers (A) of unsubstituted C1-C12 alkyl groups exhibit excellent thermosetting properties, such silane compound polymers (A) are suitably used as curing components in thermosetting compositions. Furthermore, the refractive index of the cured product of the thermosetting composition can be adjusted by introducing C1-C12 fluoroalkyl groups or unsubstituted C6-C20 aryl groups into the silane compound polymer (A).

[0028] The amount of repeating units (1) in the silane compound polymer (A) is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, of the total amount of repeating units in the silane compound polymer (A).

[0029] When a silane compound polymer (A) has repeating units other than repeating unit (1) [repeating unit (2)], examples of repeating unit (2) include repeating units derived from monofunctional silane compounds such as trimethylmethoxysilane, repeating units derived from difunctional silane compounds such as dimethyldimethoxysilane, repeating units derived from trifunctional silane compounds (excluding repeating unit (1)), and repeating units derived from tetrafunctional silane compounds such as tetramethoxysilane.

[0030] The mass-average molecular weight (Mw) of the silane compound polymer (A) is preferably 1,000 to 10,000, more preferably 1,200 to 9,000, and even more preferably 1,500 to 8,000. The molecular weight distribution (Mw / Mn) of the silane compound polymer (A) is not particularly limited, but is usually 1.0 to 10.0, preferably 1.1 to 6.0. Silane compound polymers (A) having a mass-average molecular weight or molecular weight distribution (Mw / Mn) within the above range are suitably used as curable components in thermosetting compositions. The mass-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, as standard polystyrene equivalent values ​​obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the solvent.

[0031] The silane compound polymer (A) is preferably thermosetting. The thermosetting silane compound polymer (A) is suitably used as a curing component in a thermosetting composition. In this invention, "thermosetting property" in silane compound polymers and compositions refers to the property of curing by heating alone, even without the presence of a curing catalyst.

[0032] The structure of the silane compound polymer (A) may be any of the following: ladder structure, double-decker structure, cage structure, partially cleaved cage structure, cyclic structure, or random structure. Furthermore, if the silane compound polymer (A) is a copolymer, it may be any of the following: a random copolymer, a block copolymer, a graft copolymer, an alternating copolymer, etc., but a random copolymer is preferred from the viewpoint of ease of manufacture, etc.

[0033] The content of the silane compound polymer (A) is preferably 5 to 90% by mass, more preferably 10 to 65% by mass, and even more preferably 20 to 50% by mass, of the total amount of components constituting the thermosetting composition (excluding the solvent). By using a thermosetting composition containing a silane compound polymer (A) within the above range, a cured product with excellent thermal conductivity and impact resistance can be efficiently formed. In the thermosetting composition of the present invention, the silane compound polymer (A) can be used alone or in combination of two or more types.

[0034] The method for producing the silane compound polymer (A) is not particularly limited. For example, the silane compound polymer (A) used in the present invention can be produced by performing a step (step PO) in which a trifunctional alkoxysilane compound (monomer) corresponding to a desired repeating unit is hydrolyzed and polycondensed in the presence of water and a catalyst, and a step (step PU) in which the silane compound polymer (A) obtained in step PO is purified.

[0035] Step PO is a process of hydrolyzing and polycondensing a trifunctional alkoxysilane compound corresponding to a desired repeating unit in the presence of water and a catalyst.

[0036] In the PO process, a trifunctional alkoxysilane compound, for example, is a compound represented by the following formula (a-2).

[0037] [ka]

[0038] In formula (a-2), R 1 The above has the same meaning. OR represents an alkoxy group. ORs may be the same or different from each other.

[0039] The alkoxy group represented by OR preferably has 1 to 6 carbon atoms, and more preferably 1 to 3. Examples of alkoxy groups represented by OR include methoxy groups, ethoxy groups, and propoxy groups.

[0040] Specific examples of trifunctional alkoxysilane compounds represented by formula (a-2) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, pentafluoroethyltrimethoxysilane, pentafluoroethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 2-cyanoethyltrimethoxysilane, 2-cyanoethyltriethoxysilane, 3-cyanopropyltrimethoxysilane, and 3-cyanopropyltriethoxysilane. These trifunctional alkoxysilane compounds can be used individually or in combination of two or more.

[0041] In the PO process, in addition to the trifunctional alkoxysilane compound mentioned above, monofunctional alkoxysilane compounds such as trimethylmethoxysilane, difunctional alkoxysilane compounds such as dimethyldimethoxysilane, trifunctional alkoxysilane compounds other than those represented by formula (a-2), and tetrafunctional alkoxysilane compounds such as tetramethoxysilane may be used as monomers.

[0042] In the method for producing the silane compound polymer (A), the amount of the compound represented by formula (a-2) is preferably 90 to 100 mol%, and more preferably 95 to 100 mol%, relative to the total amount of monomers.

[0043] In step PO, it is preferable to add an amount of water to the reaction system that is sufficient to hydrolyze the hydrolyzable group contained in the monomer (for example, "OR" in formula (a-2)). The amount of water added is preferably such that the molar ratio M of water to alkoxy groups, as derived by the following formula (F1), is 0.95 or higher, more preferably 0.97 to 5.0, even more preferably 0.99 to 3.0, and particularly preferably 1.0 to 1.5.

[0044]

number

[0045] In formula (F1), M H2O M is the amount of water (in moles) added to the reaction system. OR This represents the total number of alkoxy groups (total number of moles) in the monomer. For example, if 3.0 mol of water is added to 1.0 mol of a trifunctional alkoxysilane compound, the molar ratio M is 3.0 / 3.0 (=1.0).

[0046] A molar ratio M of 0.95 or higher allows the monomer hydrolysis reaction to proceed sufficiently, making it easier to obtain a silane compound polymer (A) with excellent thermosetting properties.

[0047] Examples of catalysts used in process (PO) include acid catalysts and base catalysts. In process (PO), either an acid catalyst or a base catalyst may be used alone, or both acid catalysts and base catalysts may be used. Examples of acid catalysts include inorganic acids such as phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, and nitric acid; and organic acids such as formic acid, citric acid, acetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. Among these, at least one selected from phosphoric acid, hydrochloric acid, boric acid, sulfuric acid, formic acid, citric acid, acetic acid, and methanesulfonic acid is preferred.

[0048] Examples of base catalysts include aqueous ammonia; organic bases such as trimethylamine, triethylamine, lithium diisopropylamide, lithium bis(trimethylsilyl)amide, pyridine, 1,8-diazabicyclo[5.4.0]-7-undecene, aniline, picoline, 1,4-diazabicyclo[2.2.2]octane, and imidazole; organic hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; metal alkoxides such as sodium methoxide, sodium ethoxide, sodium t-butoxide, and potassium t-butoxide; metal hydrides such as sodium hydride and calcium hydride; metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; metal carbonates such as sodium carbonate, potassium carbonate, and magnesium carbonate; and metal bicarbonates such as sodium bicarbonate and potassium bicarbonate.

[0049] The amount of catalyst used is typically 0.05 to 10 mol%, preferably 0.1 to 5 mol%, relative to the total amount of monomer. By adjusting the amount of catalyst used, the polycondensation reaction can be controlled appropriately, and a silane compound polymer (A) with the desired molecular weight can be obtained.

[0050] The PO process can be carried out, for example, by placing a trifunctional alkoxysilane compound, water, and a catalyst in a reaction vessel and stirring the resulting mixture. In addition to these components, an organic solvent may also be present in the reaction vessel. Examples of organic solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol, and t-butyl alcohol. These solvents can be used individually or in combination of two or more. When an organic solvent is used in the PO process, the amount of organic solvent used is preferably 0.05 to 8 times, more preferably 0.1 to 5 times, and even more preferably 0.2 to 1.5 times, by volume, relative to the trifunctional alkoxysilane compound.

[0051] The reaction conditions for process PO are not particularly limited. The reaction temperature for process PO is typically 0 to 95°C, preferably 5 to 80°C. The reaction time for process PO is typically 30 minutes to 50 hours, preferably 1 to 24 hours.

[0052] Process PO may be carried out under constant conditions from start to finish (i.e., it may have one step), or it may have multiple steps with different reaction conditions.

[0053] Step PU is a process for purifying the obtained silane compound polymer (A). By performing process PU, a high-purity silane compound polymer (A) can be obtained. Such a silane compound polymer (A) is more suitable as a curing component in thermosetting compositions used for fixing semiconductor devices.

[0054] One example of a process PU is a purification process using solvent extraction. A purification process using solvent extraction may include, for example, the following steps: (Step PU-I) Add water-immiscible organic solvent or water as needed to the reaction mixture obtained in step PO, stir, and then allow to stand to separate the organic phase and the aqueous phase. (Step PU-II) The organic phase produced in Step PU-I is separated and, if necessary, the organic phase is washed with water. (Step PU-III) The organic phase separated in Step PU-II is concentrated and dried.

[0055] In step PU-I, a water-immiscible organic solvent or water is added to the reaction mixture as needed, so that the reaction mixture obtained in step PO separates into an organic phase and an aqueous phase. The amount of solvent added and the type of organic solvent are not particularly limited, as long as the reaction mixture obtained in step PO separates into an organic phase and an aqueous phase.

[0056] The silane compound polymer (A) is usually contained in the organic phase. Therefore, in step PU-II, the organic phase produced in step PU-I is separated. After this, the organic phase may be washed with water according to a conventional method.

[0057] Step PU-III can be carried out according to conventional methods, such as concentration treatment using an evaporator and vacuum drying treatment.

[0058] [Component (B): Boron nitride filler] The thermosetting composition of the present invention contains the following component (B). (B) Component: Boron nitride filler

[0059] The thermosetting composition of the present invention contains a boron nitride filler (hereinafter sometimes referred to as "filler (B)") and therefore exhibits excellent thixotropy. Furthermore, because the thermosetting composition of the present invention contains filler (B), the cured product exhibits excellent thermal conductivity after curing.

[0060] Examples of filler (B) include hexagonal boron nitride and cubic boron nitride, with hexagonal boron nitride being preferred due to its excellent thermal conductivity.

[0061] The filler (B) may be in any shape, such as flaky, flattened, disc-shaped, or spherical.

[0062] Particle size of filler (B) (D 50 The particle size is preferably 0.1 to 30 μm, and more preferably 0.5 to 25 μm. Particle size (D 50 A thermosetting composition containing a filler (B) of 0.1 to 30 μm exhibits superior thixotropy. In this invention, the particle size (D 50 ) refers to the volume-based cumulative 50% particle diameter obtained by laser diffraction and scattering methods.

[0063] Furthermore, as will be described later, the filler (B) has a particle size (D 50 Fillers (B1) whose particle size is greater than 3.0 μm and less than or equal to 30 μm, and particle size (D 50 By distinguishing between fillers (B2) with a particle size of 0.1 μm or more and 3.0 μm or less, it is sometimes possible to efficiently improve both the thixotropy of the thermosetting composition and the thermal conductivity of the cured product.

[0064] The content of filler (B) is preferably 5 to 500 parts by mass, more preferably 10 to 300 parts by mass, and even more preferably 15 to 250 parts by mass, per 100 parts by mass of component (A). By having a filler (B) content within the above range, it becomes easier to obtain a thermosetting composition with excellent thixotropy. Furthermore, by using a thermosetting composition with a filler (B) content within the above range, it is possible to efficiently form a cured product with excellent thermal conductivity and impact resistance. In the thermosetting composition of the present invention, filler (B) can be used alone or in combination of two or more types.

[0065] [(C) component: Filler other than component (B)] The thermosetting composition of the present invention may contain fillers other than component (B) (hereinafter sometimes referred to as "filler (C)").

[0066] As described above, using filler (B) can efficiently improve both the thixotropy of the thermosetting composition and the thermal conductivity of the cured product. Furthermore, by using filler (C) in combination, it may be possible to further improve one of these properties or improve other properties.

[0067] Silicon dioxide is a filler (C) that primarily improves the thixotropy of thermosetting compositions.

[0068] Fillers (C) that primarily improve the thermal conductivity of the cured product include aluminum hydroxide, aluminum oxide, magnesium oxide, magnesium carbonate, zinc oxide, aluminum nitride, silicon nitride, and silicon carbide.

[0069] Examples of filler (C) shapes include flaky, plate-like, membranous, cylindrical, prismatic, elliptical, flattened, and spherical shapes. Particle size (D) of filler (C) 50 The thickness is, for example, 30 μm or less, preferably 0.001 to 25 μm. Filler (C) shape and particle size (D 50 ) can be appropriately determined according to the purpose of adding filler (C).

[0070] Furthermore, as will be described later, the filler (C) is the particle size (D 50 Filler (C1) has a particle size greater than 3.0 μm and less than or equal to 30 μm, and particle size (D 50 By distinguishing between fillers (C2) with a diameter of 3.0 μm or less, it may be possible to efficiently improve both the thixotropy of the thermosetting composition and the thermal conductivity of the cured product.

[0071] The content of filler (C) is preferably 5 to 1000 parts by mass, and more preferably 10 to 800 parts by mass, per 100 parts by mass of component (A). By keeping the filler (C) content within the above range, it becomes easier to obtain a cured product with excellent impact resistance. In the thermosetting composition of the present invention, the filler (C) can be used alone or in combination of two or more types.

[0072] [(D) Component: Silane coupling agent] The thermosetting composition of the present invention may contain a silane coupling agent. Cured products of thermosetting compositions containing silane coupling agents tend to exhibit superior adhesive strength at room temperature and high temperatures. Therefore, thermosetting compositions containing silane coupling agents are suitably used as fixing agents for components with small bonding areas, such as semiconductor devices. On the other hand, thermosetting compositions that do not contain silane coupling agents are suitably used as forming materials for films with relatively large bonding areas, such as thermally conductive films.

[0073] A silane coupling agent is a silane compound having a silicon atom, a functional group, and a hydrolyzable group bonded to the silicon atom. A functional group is a group that has reactivity with other compounds (mainly organic substances). Examples include vinyl groups, allyl groups, epoxy groups, amino groups, substituted amino groups, acrylic groups, methacrylic groups, mercapto groups, isocyanate groups, groups with an isocyanurate structure, groups with a urea structure, and groups with an acid anhydride structure. Component (D) can be used alone or in combination of two or more components.

[0074] If the thermosetting composition of the present invention contains a silane coupling agent, the amount is preferably 5 to 50 parts by mass, and more preferably 15 to 40 parts by mass, per 100 parts by mass of component (A). Cured products of thermosetting compositions containing 5 parts by mass or more of silane coupling agent per 100 parts by mass of component (A) tend to exhibit superior adhesive strength at room temperature and high temperatures. Thermosetting compositions containing 50 parts by mass or less of silane coupling agent per 100 parts by mass of component (A) tend to be less prone to cracking caused by by-products such as alcohol during the curing reaction.

[0075] As silane coupling agents, silane coupling agents having a nitrogen atom in the molecule and silane coupling agents having an acid anhydride structure in the molecule are preferred.

[0076] Examples of silane coupling agents having a nitrogen atom in the molecule include trialkoxysilane compounds represented by formula (d-1), dialkoxyalkylsilane compounds represented by formula (d-2), or dialkoxyarylsilane compounds.

[0077] [ka]

[0078] In the above formula, R a R represents alkoxy groups with 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and t-butoxy groups. a They may be identical or different. R b This represents an alkyl group having 1 to 6 carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, or t-butyl group; or an aryl group with or without substituents, such as a phenyl group, 4-methylphenyl group, 1-naphthyl group, or 4-chlorophenyl group.

[0079] R c This represents an organic group with 1 to 10 carbon atoms that contains a nitrogen atom. Also, R c It may also be bonded to other groups containing silicon atoms. R c Specific examples of organic groups having 1 to 10 carbon atoms include N-(2-aminoethyl)-3-aminopropyl group, 3-aminopropyl group, N-(1,3-dimethylbutylidene)-3-aminopropyl group, 3-ureidopropyl group, and N-phenyl-3-aminopropyl group.

[0080] Among the compounds represented by the above formula (d-1) or formula (d-2), Rc However, examples of compounds in which the organic group is bonded to a group containing other silicon atoms include isocyanurate-based silane coupling agents that are bonded to other silicon atoms via an isocyanurate skeleton, and urea-based silane coupling agents that are bonded to other silicon atoms via a urea skeleton.

[0081] Among these, isocyanurate-based silane coupling agents and urea-based silane coupling agents are preferred because they easily yield cured products with superior adhesive strength, and further, those having four or more alkoxy groups bonded to silicon atoms in the molecule are preferred. Having four or more alkoxy groups bonded to silicon atoms means that the total number of alkoxy groups bonded to the same silicon atom and alkoxy groups bonded to different silicon atoms is four or more.

[0082] Examples of isocyanurate-based silane coupling agents having four or more alkoxy groups bonded to silicon atoms include compounds represented by the following formula (d-3). Examples of urea-based silane coupling agents having four or more alkoxy groups bonded to silicon atoms include compounds represented by the following formula (d-4).

[0083] [ka]

[0084] In the formula, R a The above has the same meaning. t1 to t5 each represent an integer from 1 to 10, preferably from 1 to 6, and particularly preferably 3.

[0085] Among these, it is preferable to use 1,3,5-N-tris(3-trimethoxysilylpropyl) isocyanurate, 1,3,5-N-tris(3-triethoxysilylpropyl) isocyanurate (hereinafter referred to as "isocyanurate compounds"), N,N'-bis(3-trimethoxysilylpropyl) urea, N,N'-bis(3-triethoxysilylpropyl) urea (hereinafter referred to as "urea compounds"), and combinations of the above isocyanurate compounds and urea compounds as silane coupling agents having a nitrogen atom in the molecule.

[0086] When the thermosetting composition of the present invention contains a silane coupling agent having a nitrogen atom in its molecule, the amount is not particularly limited, but is preferably less than 50 parts by mass, more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less, per 100 parts by mass of component (A). There is no particular lower limit for the content of the silane coupling agent having a nitrogen atom in its molecule, but it is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of component (A). Therefore, the content of the silane coupling agent having a nitrogen atom in its molecule is preferably 0.1 parts by mass or more and less than 50 parts by mass per 100 parts by mass of component (A).

[0087] Silane coupling agents having an acid anhydride structure within the molecule are organosilicon compounds that possess both an acid anhydride group and a hydrolyzable group within a single molecule. Specifically, examples include compounds represented by the following formula (d-5).

[0088] [ka]

[0089] In the formula, Q represents a group having an acid anhydride structure, and R d R represents an alkyl group having 1 to 6 carbon atoms, or a phenyl group with or without a substituent. erepresents an alkoxy group or halogen atom with 1 to 6 carbon atoms, i and k represent integers from 1 to 3, and j represents an integer from 0 to 2, so i + j + k = 4. When j is 2, R d They may be the same or different. When k is 2 or 3, multiple R e The elements may be identical or different. When i is 2 or 3, the multiple Q elements may be identical or different. Q is the following formula

[0090] [ka]

[0091] Examples of bases include those represented by (Q1), where h represents an integer from 0 to 10, and * represents a combination.

[0092] Examples of silane coupling agents having an acid anhydride structure within the molecule include tri(carbon 1-6)alkoxysilyl(carbon 2-8)alkyl succinic anhydrides such as 2-(trimethoxysilyl)ethyl succinic anhydride, 2-(triethoxysilyl)ethyl succinic anhydride, 3-(trimethoxysilyl)propyl succinic anhydride, and 3-(triethoxysilyl)propyl succinic anhydride; Di(C1-C6)alkoxymethylsilyl(C2-C8)alkyl succinic anhydrides, such as 2-(dimethoxymethylsilyl)ethyl succinic anhydride; 2-(methoxydimethylsilyl)ethyl succinic anhydride, etc., (C1-C6) alkoxydimethylsilyl (C2-C8) alkyl succinic anhydride;

[0093] Trihalogenosilyl (2-8 carbon atoms) alkyl succinic anhydrides, such as 2-(trichlorosilyl)ethyl succinic anhydride and 2-(tribromosilyl)ethyl succinic anhydride; Dihalogenomethylsilyl(C2-C8) alkyl succinic anhydrides, such as 2-(dichloromethylsilyl)ethyl succinic anhydride; Examples include 2-(chlorodimethylsilyl)ethyl succinic anhydride and halogenodimethylsilyl (2-8 carbon atoms) alkyl succinic anhydride; etc.

[0094] Among these, tri(1-6 carbon atoms)alkoxysilyl(2-8 carbon atoms)alkyl succinic anhydride is preferred as a silane coupling agent having an acid anhydride structure in its molecule, and 3-(trimethoxysilyl)propyl succinic anhydride or 3-(triethoxysilyl)propyl succinic anhydride is particularly preferred.

[0095] When the thermosetting composition of the present invention contains a silane coupling agent having an acid anhydride structure in its molecule, the amount is not particularly limited, but is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of component (A). There is no particular lower limit for the content of the silane coupling agent having an acid anhydride structure in the molecule, but it is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more, per 100 parts by mass of component (A). Therefore, the content of the silane coupling agent having an acid anhydride structure in the molecule is preferably 0.1 to 30 parts by mass per 100 parts by mass of component (A).

[0096] 〔solvent〕 The thermosetting composition of the present invention may contain a solvent. Since the concentration of the thermosetting composition does not change easily during application, it is preferable to use a solvent with a high boiling point. Suitable solvents include polyether solvents such as dipropylene glycol dimethyl ether (boiling point 171°C), diethylene glycol dimethyl ether (boiling point 162°C), and diethylene glycol ethyl methyl ether (boiling point 176°C); γ-butyrolactone (boiling point 204°C), ethyl lactate (boiling point 154°C), 3-methoxybutyl acetate (boiling point 171°C), diethylene glycol monoethyl ether acetate (boiling point 217°C), and diethylene glycol monobutyl Examples include ester solvents such as ether acetate (boiling point 247°C); alcohol solvents such as tripropylene glycol monobutyl ether (boiling point 276°C); ketone solvents such as cyclohexanone (boiling point 156°C); amide solvents such as N,N-dimethylformamide (boiling point 153°C), N,N-dimethylacetamide (boiling point 165°C), and N-methylpyrrolidone (boiling point 202°C); and sulfoxide solvents such as dimethyl sulfoxide (boiling point 189°C). If the thermosetting composition of the present invention contains a solvent, the amount is not particularly limited, but it is preferable that the concentration of components other than the solvent (active ingredients) be 10 to 95% by mass, and more preferably 20 to 90% by mass.

[0097] [Other ingredients] The thermosetting composition of the present invention may contain components other than those listed above, as long as they do not hinder the objectives of the present invention. Other ingredients besides those mentioned above include additives such as antioxidants, UV absorbers, and light stabilizers. The amounts of these additives can be determined as appropriate according to the purpose.

[0098] [Thermosetting composition] The thermosetting composition of the present invention can be prepared, for example, by mixing component (A) and component (B) above, and optionally other components, in a predetermined ratio, and then degassing. The mixing method and degassing method are not particularly limited, and known methods can be used.

[0099] The thermosetting composition of the present invention contains filler (B) and therefore exhibits excellent thixotropy. The thixometric index of the thermosetting composition of the present invention (shear rate is 2s) -1 The viscosity / shear rate at that time is 200s -1 The viscosity at this point is preferably 1.5 or higher, more preferably 2.0 or higher. There is no particular upper limit, but it is usually 25 or lower.

[0100] In this invention, the thixotropic index is defined as the value obtained using a rheometer with a cone plate having a cone radius of 50 mm and a cone angle of 0.5°, at a temperature of 25°C and a shear rate of 2s. -1 The viscosity at that time, the temperature at 25°C, and the shear rate at 200 s. -1 The viscosity was measured at each of the following times, and the shear rate was 2s -1 The viscosity at which the shear rate is 200 s -1 This refers to the value obtained by dividing by the viscosity at that time.

[0101] Thermosetting compositions with a thixotropy index of 1.5 or higher exhibit excellent thixotropy. Thixotropy refers to the property of a material where its viscosity decreases and it deforms easily when force is applied, and its viscosity increases again when left standing (at rest). Thermosetting compositions with excellent thixotropy offer superior workability during application. In other words, when a thermosetting composition is discharged to a predetermined position using a discharge pipe, if a thermosetting composition with excellent thixotropy is discharged from the discharge pipe and then the discharge pipe is withdrawn, the amount of stringing is small or breaks immediately. Therefore, by using a thermosetting composition with this property, it is possible to prevent contamination of the surrounding area due to resin splashing or the spreading of droplets.

[0102] By heating the thermosetting composition of the present invention, the thermosetting composition hardens and becomes a cured product. The heating temperature for heat-curing the thermosetting composition of the present invention is typically 100 to 200°C. The heating time is typically 10 minutes to 20 hours, preferably 30 minutes to 10 hours.

[0103] Because the thermosetting composition of the present invention contains filler (B), its cured product exhibits excellent thermal conductivity. The thermal conductivity of the cured product of the thermosetting composition of the present invention is preferably 1.0 W / (m·K) or higher, and more preferably 1.5 to 100 W / (m·K). The thermal conductivity of the cured product of the thermosetting composition of the present invention can be measured, for example, by using the cured product obtained by curing the thermosetting composition at 120°C for 4 hours as a measurement sample.

[0104] The cured product of the thermosetting composition of the present invention preferably exhibits excellent insulating properties. A cured product with excellent insulating properties can be obtained by using a large amount of filler (B) as the filler. The surface resistivity of the cured product of the thermosetting composition of the present invention is preferably 1.0 × 10⁻⁶. 8 Ω / □ or greater, more preferably 3.0 × 10 10 Ω / □ or greater, more preferably 1.0 × 10 14 That's all. The surface resistivity of the cured product of the thermosetting composition of the present invention can be measured, for example, by using a cured product obtained by curing the thermosetting composition at 120°C for 4 hours as a measurement sample.

[0105] When the adhesive strength of the thermosetting composition of the present invention was measured by the method described in the examples, it was 1.0 N / 1 mm at 23°C. 2 Preferably, the above is 2.0 N / 1 mm 2 It is more preferable that the above conditions are met. In this specification, "1 mm 2 "1mm square" means 1mm x 1mm (a square with sides of 1mm). By increasing the proportion of silane compound polymers in the thermosetting composition or by using a silane coupling agent, it becomes easier to obtain a thermosetting composition that results in a cured product with the above-mentioned adhesive strength.

[0106] Since thermosetting compositions having these properties are easily obtained, it is preferable that the thermosetting composition of the present invention contains filler (B1) and filler (B2), filler (C1) and filler (B2), or filler (B1) and filler (C2). Furthermore, due to these properties, the thermosetting composition of the present invention is suitably used as a composition for fixing semiconductor devices and a composition for forming thermally conductive films.

[0107] [Composition for fixing semiconductor devices] Examples of compositions for fixing semiconductor devices include adhesives for fixing semiconductor devices and encapsulants for fixing semiconductor devices. Examples of semiconductor devices include light-emitting elements such as light-emitting diodes (LEDs) and laser diodes (LDs); light-receiving elements such as photodiodes, solar cells, and CMOS image sensors; composite optical elements; integrated circuits; and large-scale integrated circuits.

[0108] When using the thermosetting composition of the present invention as an adhesive for fixing semiconductor devices, a predetermined amount of the thermosetting composition is typically applied to one or both bonding surfaces of the materials to be bonded (such as a semiconductor device and a substrate), pressed together, and then heat-cured. This process allows for strong bonding between the materials to be bonded.

[0109] Materials that make up the substrate include: glass such as soda-lime glass and heat-resistant hard glass; ceramics; sapphire; metals such as iron, copper, aluminum, gold, silver, platinum, chromium, titanium and alloys of these metals, stainless steel (SUS302, SUS304, SUS304L, SUS309, etc.); and synthetic resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyphenylene sulfide, polyetherimide, polyimide, polyamide, acrylic resin, norbornene-based resin, cycloolefin resin, and glass epoxy resin.

[0110] When using the thermosetting composition of the present invention as a encapsulant for fixing semiconductor devices, the thermosetting composition of the present invention is typically molded into a desired shape to obtain a molded body containing a semiconductor device, and then this is heat-cured. This process yields a semiconductor device encapsulant containing a semiconductor device. The method for molding the thermosetting composition of the present invention into a desired shape is not particularly limited, and known molding methods such as conventional transfer molding or casting can be employed.

[0111] [Composition for forming thermally conductive films] When using the thermosetting composition of the present invention as a composition for forming a thermally conductive film, the thermosetting composition of the present invention is typically applied, and the resulting coating is heat-cured. This process yields a thermally conductive film on a predetermined surface. Since this thermally conductive film prevents heat accumulation, the occurrence of device failures can be reduced by appropriately positioning this film. [Examples]

[0112] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited in any way to the following examples.

[0113] [Average molecular weight measurement] The mass-average molecular weight (Mw) of the silane compound polymer was measured using the following apparatus and conditions. Device name: HLC-8220GPC manufactured by Tosoh Corporation Column: A sequential combination of "TSK guard column SuperH-H", "TSK gel SuperHM-H", "TSK gel SuperHM-H", and "TSK gel SuperH2000". Solvent: tetrahydrofuran Standard material: Polystyrene Injection volume: 20μl Measurement temperature: 40℃ Flow rate: 0.6ml / min Detector: Differential refractometer

[0114] [Manufacturing Example 1] [Synthesis of Polymer (Aa)] 77.7 mmol (17.0 g) of 3,3,3-trifluoropropyltrimethoxysilane and 181.3 mmol (32.33 g) of methyltriethoxysilane were charged into a 300 ml round-bottom flask. While stirring, an aqueous hydrochloric acid solution [0.0675 g of 35% hydrochloric acid (0.25 mol%) relative to the total amount of silane compounds) was added to 14.0 ml of distilled water], and the entire mixture was stirred at 30°C for 2 hours, then the temperature was raised to 70°C and stirred for 20 hours. While continuing to stir the contents, a mixed solution of 0.0394 g of 28% by mass aqueous ammonia (containing 0.65 mmol of NH3) and 46.1 g of propyl acetate was added to adjust the pH of the reaction solution to 6.9, and the mixture was then stirred at 70°C for 40 minutes. After allowing the reaction mixture to cool to room temperature, 50 g of propyl acetate and 100 g of water were added and liquid-liquid treated to obtain an organic phase containing the reaction product. Magnesium sulfate was added to this organic phase and dried. After removing the magnesium sulfate by filtration, the organic phase was concentrated using an evaporator, and the resulting concentrate was then vacuum-dried to obtain polymer (Aa). The mass-average molecular weight (Mw) of polymer (Aa) was 5,500, and the molecular weight distribution was 3.40.

[0115] [Manufacturing Example 2] [Synthesis of Polymer (Ab)] 400 mmol (71.37 g) of methyltriethoxysilane was placed in a 300 ml round-bottom flask. While stirring, an aqueous solution of 0.10 g of 35% hydrochloric acid (0.25 mol% relative to methyltriethoxysilane) dissolved in 21.6 ml of distilled water was added, and the entire mixture was stirred at 30°C for 2 hours, then the temperature was raised to 70°C and stirred for 5 hours. While continuing to stir the contents, 140 g of propyl acetate and 0.12 g of 28% by mass aqueous ammonia (0.5 mol% relative to methyltriethoxysilane) were added, and the mixture was stirred at 70°C for 3 hours. After allowing the reaction mixture to cool to room temperature, purified water was added and liquid-liquid treatment was performed, repeating this process until the pH of the aqueous layer reached 7. The organic layer was concentrated using an evaporator, and the concentrate was vacuum-dried to obtain polymer (Ab). The mass-average molecular weight (Mw) of polymer (Ab) was 7,800, and the molecular weight distribution (Mw / Mn) was 4.52.

[0116] [Manufacturing Example 3] [Synthesis of Polymer (Ac)] In a 300 ml round-bottom flask, 102 mmol (20.2 g) of phenyltrimethoxysilane, 18 mmol (3.15 g) of 2-cyanoethyltrimethoxysilane, and 96 ml of acetone and 24 ml of distilled water were charged as solvents. While stirring the contents, 0.15 g (1.5 mmol) of phosphoric acid was added as a catalyst, and the mixture was stirred at 25°C for a further 16 hours. After the reaction was complete, the reaction mixture was concentrated to 50 ml using an evaporator. 100 ml of ethyl acetate was added to the concentrate, and it was neutralized with saturated sodium bicarbonate aqueous solution. After standing for a while, the organic layer was separated. The organic layer was then washed twice with distilled water and dried over anhydrous magnesium sulfate. After filtering off the magnesium sulfate, the filtrate was concentrated to 50 ml using an evaporator. The resulting concentrate was added dropwise to a large amount of n-hexane to precipitate, and the precipitate was separated by decantation. The obtained precipitate was dissolved in methyl ethyl ketone and collected, and the solvent was removed under reduced pressure using an evaporator. The residue was vacuum dried to obtain the polymer (Ac). The mass-average molecular weight (Mw) of the polymer (Ac) was 1,870, and the molecular weight distribution (Mw / Mn) was 1.42.

[0117] [Example 1] (Preparation of thermosetting composition) To 100 parts by mass of polymer (Aa) obtained in Production Example 1, a mixed solvent of diethylene glycol monobutyl ether acetate (BDGAC):tripropylene glycol monobutyl ether (TPnB) = 40:60 (mass ratio) was added and the mixture was stirred. To this, 50 parts by mass of boron nitride [filler (B1-a)], 20 parts by mass of 1,3,5-N-tris[3-(trimethoxysilyl)propyl] isocyanurate, and 4 parts by mass of 3-(trimethoxysilyl)propyl succinic anhydride were added and the mixture was stirred to obtain a thermosetting composition. The concentration of the active ingredient in the thermosetting composition was 70% by mass.

[0118] [Examples 2-10, Comparative Examples 1-3] A thermosetting composition was obtained in the same manner as in Example 1, except that the components and their amounts were changed to those listed in Table 1. The details of each component in Table 1 are as follows: Polymer (Aa): Silane compound polymer obtained in Production Example 1 Polymer (Ab): Silane compound polymer obtained in Production Example 2 Polymer (Ac): Silane compound polymer obtained in Production Example 3 Filler (B1-a): Boron nitride (manufactured by Resonaq Corporation: UHP-2, particle size (D 50 )11μm) Filler (B2-a): Boron nitride (manufactured by Resonaq Corporation: UHP-S2, particle size (D 50 0.7μm) Filler (C1-a): Zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd.: LPZINC5, particle size (D 50 )5μm) Filler (C1-b): Graphene (manufactured by ADEKA Corporation: CNS-1A1, particle size (D 50 )12μm) Filler (C2-a): Zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd.: LPZINC2, particle size (D 50 )2μm) Filler (C2-b): Alumina (manufactured by Sumitomo Chemical Co., Ltd.: AA-2, particle size (D 50 )2μm) Filler (C2-c): Silica (manufactured by Nippon Aerosil Co., Ltd.: RX300, particle size (D 50 0.007μm) SC(Da):1,3,5-N-tris[3-(trimethoxysilyl)propyl]isocyanurate SC(Db):3-(trimethoxysilyl)propyl succinic anhydride

[0119] The thermosetting compositions obtained in Examples 1-10 and Comparative Examples 1-3 were subjected to the following measurements. The results are shown in Table 1.

[0120] [Thixotropic evaluation] Using a rheometer (Anton Paar MCR301), a cone plate with a radius of 50 mm and a cone angle of 0.5° was used, at a temperature of 25°C and a shear rate of 2s. -1 The viscosity at that time, the temperature at 25°C, and the shear rate at 200 s. -1 The viscosity was measured at each of the following times. From the obtained measurements, the thixotropic index (shear rate 2s) -1 The viscosity / shear rate at that time is 200s -1 The viscosity at that time was calculated.

[0121] [Thermal conductivity] A thermosetting composition was poured into a Teflon® frame measuring 10 mm (length) x 10 mm (width) x 0.2 mm (height), and heat-cured at 120°C for 4 hours to obtain a test specimen with a smooth surface. Subsequently, the thermal diffusivity of this test specimen was measured in accordance with ISO 22007-3 at 23°C and 50% relative humidity using a thermal diffusivity / thermal conductivity measuring device (ai-phase mobile, manufactured by i-phase Co., Ltd.), and the thermal conductivity was calculated based on the obtained thermal diffusivity.

[0122] [Surface resistivity measurement] A thermosetting composition was poured into a Teflon® mold measuring 30 mm (length) x 30 mm (width) x 0.2 mm (height), and heat-cured at 120°C for 4 hours to obtain a test specimen with a smooth surface. The surface resistivity (Ω / □) of the obtained test specimen was measured using a resistivity meter (Hyresta UX MCP-HT800, manufactured by Nitto Seikou Analytech Co., Ltd.) in accordance with JIS K6911-1995.

[0123] [Adhesion strength measurement (shear strength)] 1mm 2 A thermosetting composition was applied to the mirror surface of a 1mm x 1mm square silicon chip to a thickness of approximately 2μm, and the coated surface was placed on a substrate (silver-plated copper plate) and pressed down. Then, a heat curing treatment was performed at 170°C for 2 hours to obtain a substrate with a test piece attached. This substrate with a test piece attached was left on the measurement stage of a bond tester (Daisy Series 4000) for 30 seconds, and stress was applied horizontally (shear direction) to the adhesive surface at a speed of 200μm / s from a height of 100μm above the substrate. The adhesive strength (N / 1mm) between the test piece and the substrate at 25°C was measured. 2 ) was measured.

[0124] [Table 1]

[0125] The following can be seen from the examples and comparative examples. The thermosetting compositions of Examples 1 to 10 contain boron nitride fillers. Therefore, these thermosetting compositions have a high thixotropy, and the cured products exhibit good thermal conductivity. On the other hand, the thermosetting composition of Comparative Example 1 does not contain boron nitride filler, but instead contains zinc oxide and graphene. Because this thermosetting composition contains graphene, it has poor insulating properties. Comparative Example 2's thermosetting composition does not contain boron nitride filler, but instead contains silica. The cured product of this thermosetting composition has poor thermal conductivity. Comparative Example 3's thermosetting composition does not contain boron nitride filler, but instead contains zinc oxide. This thermosetting composition has poor thixotropy.

Claims

1. A thermosetting composition containing the following components (A) and (B), A thermosetting composition in which the content of component (B) is 5 to 500 parts by mass per 100 parts by mass of component (A). (A) Component: See formula (a-1) 【Chemistry 1】 [R １ This represents an unsubstituted or substituted alkyl group having 1 to 16 carbon atoms, or an unsubstituted or substituted aryl group having 6 to 20 carbon atoms. Silane compound polymer having repeating units represented by [repeating unit (1)] (B) Component: Boron nitride filler

2. The thermosetting composition according to claim 1, wherein the amount of repeating unit (1) in component (A) is 90 to 100 mol% of the total amount of repeating units in component (A).

3. The thermosetting composition according to claim 1, wherein the mass-average molecular weight (Mw) of component (A) is 1,000 to 10,000.

4. The thermosetting composition according to claim 1, wherein component (A) is thermosetting.

5. The thermosetting composition according to claim 1, wherein the content of component (A) is 5 to 90% by mass of the total amount of components constituting the thermosetting composition (excluding the solvent).

6. (B) Particle size of component (D ５０ The thermosetting composition according to claim 1, wherein the thickness is 0.1 to 30 μm.

7. (B) Component with particle size (D ５０ Component (B1) has a particle size greater than 3.0 μm and less than or equal to 30 μm, and component (B) has a particle size (D ５０ The thermosetting composition according to claim 6, comprising a component (B2) having a size of 0.1 μm or more and 3.0 μm or less.

8. Particle size (D ５０ Component (C1) is a filler with a particle size greater than 3.0 μm and less than or equal to 30 μm [excluding component (B)], and component (B) has a particle size (D ５０ The thermosetting composition according to claim 6, comprising a component (B2) having a size of 0.1 μm or more and 3.0 μm or less.

9. (B) Component with particle size (D ５０ ) is a component (B1) with a particle size greater than 3.0 μm and less than or equal to 30 μm, and particle size (D ５０ The thermosetting composition according to claim 6, comprising a component (C2) which is a filler with a size of 3.0 μm or less (excluding component (B)).

10. Furthermore, the thermosetting composition according to claim 1, further containing the following component (D). (D) Component: Silane coupling agent

11. The thermosetting composition according to claim 10, wherein the content of component (D) is 5 to 50 parts by mass per 100 parts by mass of component (A).

12. The thixotropy index (viscosity at a shear rate of 2 s －１ / viscosity at a shear rate of 200 s －１ ) is 1.5 or more, and the thermosetting composition according to claim 1.

13. A semiconductor device fixing composition comprising the thermosetting composition described in claim 1.

14. A composition for forming a thermally conductive film, comprising the thermosetting composition described in claim 1.

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