COMPOSITION, THERMALLY CONDUCTIVE SHEET, AND DEVICE WITH THERMALLY CONDUCTIVE LAYER

Abstract

A composition contains an inorganic nitride, and a compound represented by General

##STR00001##

Claims

1. A composition comprising: an inorganic nitride; and a compound represented by General Formula (1), ##STR00021## in General Formula (1), E.sup.1 to E.sup.3 each independently represent a single bond, —NH—, or —NR—, R represents a substituent, B.sup.1 to B.sup.3 each independently represent an aromatic ring group which may have a substituent and has 6 or more carbon atoms as ring member atoms, l, m, and n each independently represent an integer of 0 or greater, in a case where l is 2 or greater, l pieces of X.sup.1's may be the same as or different from each other, in a case where m is 2 or greater, m pieces of X.sup.2's may be the same as or different from each other, in a case where n is 2 or greater, n pieces of X.sup.3's may be the same as or different from each other, a total of l, m, and n is 2 or greater, and X.sup.1 to X.sup.3 each independently represent a group represented by General Formula (2); ##STR00022## in General Formula (2), * represents a bonding position, D.sup.1 represents a single bond or a divalent linking group, A.sup.1 represents an aromatic ring group which may have a substituent and has 6 or more carbon atoms as ring member atoms, or a cycloalkane ring group which may have a substituent and has 6 or more carbon atoms as ring member atoms, Q and Y.sup.1 each independently represent a specific functional group selected from the group consisting of an aldehyde group, a boronic acid group, a hydroxyl group, a monovalent group having an epoxy group, an amino group, a thiol group, a carboxylic acid group, a monovalent group having a carboxylic acid anhydride group, an isocyanate group, and a monovalent group having an oxetanyl group, p represents an integer of 0 or greater, and, q represents an integer 0 to 2; and in General Formula (2), in a case where there are a plurality of D.sup.1's, the plurality of D.sup.1's may be the same as or different from each other, in a case where there are a plurality of A.sup.1's, the plurality of A.sup.1's may be the same as or different from each other, in a case where there are a plurality of Q's, the plurality of Q's may be the same as or different from each other, in a case where there are a plurality of Y.sup.1's, the plurality of Y.sup.1's may be the same as or different from each other, in a case where there are a plurality of p's, the plurality of p's may be the same as or different from each other, and in a case where there are a plurality of q's, the plurality of q's may be the same as or different from each other, here, in a case where l is 1 or greater and at least one X.sup.1 is a hydroxyl group, an atom in B.sup.1 to which X.sup.1, which is a hydroxyl group, is directly bonded and an atom in B.sup.1 to which E.sup.1 is directly bonded are not adjacent to each other, in a case where m is 1 or greater and at least one X.sup.2 is a hydroxyl group, an atom in B.sup.2 to which X.sup.2, which is a hydroxyl group, is directly bonded and an atom in B.sup.2 to which E.sup.2 is directly bonded are not adjacent to each other, and in a case where n is 1 or greater and at least one X.sup.3 is a hydroxyl group, an atom in B.sup.3 to which X.sup.3, which is a hydroxyl group, is directly bonded and an atom in B.sup.3 to which E.sup.3 is directly bonded are not adjacent to each other.

2. The composition according to claim 1, wherein Q and Y.sup.1 each independently represent a group selected from the group consisting of an aldehyde group, a boronic acid group, a hydroxyl group, and a monovalent group having an epoxy group.

3. The composition according to claim 1, wherein E.sup.1 to E.sup.3 each represent —NH—.

4. The composition according to claim 1, further comprising an epoxy compound.

5. The composition according to claim 4, wherein an epoxy group content of the epoxy compound is 4.0 mmol/g or greater.

6. The composition according to claim 1, further comprising a phenolic compound.

7. The composition according to claim 6, wherein a hydroxyl group content of the phenolic compound is 8.0 mmol/g or greater.

8. The composition according to claim 1, further comprising a curing accelerator.

9. The composition according to claim 1, wherein the inorganic nitride is boron nitride.

10. The composition according to claim 1, wherein the composition further comprises other inorganic substances other than the inorganic nitride, and a total content of the inorganic nitride and the other inorganic substances is 70% to 85% by mass with respect to a total solid content of the composition, or the composition does not comprise the other inorganic substances, and a content of the inorganic nitride is 70% to 85% by mass with respect to the total solid content of the composition.

11. The composition according to claim 1, wherein X.sup.1 to X.sup.3 in General Formula (1) each independently have at least one of the specific functional group selected from the group consisting of an aldehyde group, a boronic acid group, a monovalent group having an epoxy group.

12. The composition according to claim 1, wherein the composition is a composition for forming a thermally conductive material.

13. A thermally conductive sheet which is formed by curing the composition according to claim 1.

14. A thermally conductive multilayer sheet comprising: the thermally conductive sheet according to claim 13; and an adhesive layer or a pressure sensitive adhesive layer which is provided on one surface or both surfaces of the thermally conductive sheet.

15. A device with a thermally conductive layer comprising: a device; and a thermally conductive layer which is disposed on the device and includes the thermally conductive sheet according to claim 13.

16. A device with a thermally conductive layer comprising: a device; and a thermally conductive layer which is disposed on the device and includes the thermally conductive multilayer sheet according to claim 14.

Description

EXAMPLES

[0465] Hereinafter, the present invention will be described in more detail based on Examples. The materials, the amount and proportion of the materials used, the details of treatments, the procedure of treatments, and the like shown in the following Examples can be appropriately changed within a range that does not depart from the gist of the present invention. Accordingly, the scope of the present invention is not limitedly interpreted by the following Examples.

Preparation and Evaluation of Composition

Various Components

[0466] Various components used in Examples and Comparative Examples will be shown below.

Phenolic Compound

[0467] Phenolic compounds used in Examples and Comparative Examples will be shown below.

[0468] Moreover, the phenolic compound A-1 used in Examples was synthesized with reference to U.S. Pat. No. 4,992,596A.

##STR00012##

Epoxy Compound

[0469] Epoxy compounds used in Examples and Comparative Examples will be shown below.

[0470] Moreover, the following B-2 is a mixture of two kinds of epoxy compounds (trade name: EPOTOHTO ZX-1059, produced by Tohto Kasei Co., Ltd).

##STR00013##

Inorganic Substances (Inorganic Nitride and other Inorganic Substances)

[0471] Inorganic substances used in Examples and Comparative Examples will be shown below.

[0472] “AA-3”: Aluminum oxide (average particle diameter: 3 μm, produced by Sumitomo Chemical Co., Ltd.)

[0473] “AA-04”: Aluminum oxide (average particle diameter: 0.4 μm, produced by Sumitomo Chemical Co., Ltd.)

[0474] “PTX-60”: Aggregation-shaped boron nitride (average particle diameter: 60 μm, produced by Momentive)

[0475] “HP40 MF100”: Aggregation-shaped boron nitride (average particle diameter: 40 μm, produced by MIZUSHIMA FERROALLOY CO., LTD.)

[0476] “SP-3”: Scale-shaped boron nitride (average particle diameter: 4 μm, produced by Denka Company Limited)

Curing Accelerator

[0477] Triphenylphosphine (PPh.sub.3) was used as the curing accelerator.

Solvent

[0478] Cyclopentanone was used as the solvent.

Dispersant

[0479] DISPERBYK-106 (polymer salt having an acidic group) was used as the dispersant.

Surface Modifier for Aluminum Oxide (Organic Silane Molecule)

[0480] The following compound was used as the surface modifier for aluminum oxide.

##STR00014##

Surface Modifier for Inorganic Nitride

[0481] Surface modifiers (specific compounds, or compounds for comparison) for an inorganic nitride used in Examples and Comparative Examples will be shown below. The following C-1 to C-25 are specific compounds, and D-1 to D-5 are compounds (compounds for comparison) which do not correspond to the specific compounds.

##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020##

Preparation of Composition

[0482] A curing liquid was prepared by formulating the epoxy compound and the phenolic compound of each combination shown in Table 1 below in the addition amount (g) listed in Table 1.

[0483] The total amount of the obtained curing liquid, the solvent, the dispersant, the surface modifier (the surface modifier for aluminum oxide and the surface modifier for an inorganic nitride), and the curing accelerator were mixed in this order, and then the inorganic substances (the inorganic nitride and the inorganic oxide) were added thereto. The obtained mixture was treated for 5 minutes with a rotating and revolving mixer (manufactured by THINKY CORPORATION, AWATORI RENTARO ARE-310) to obtain a composition (composition for forming a thermally conductive material) of each Example or Comparative Example.

[0484] Here, the addition amount of the solvent was set such that the concentration of the solid contents in the composition was 50% to 80% by mass.

[0485] Furthermore, the concentration of the solid contents in the composition was adjusted for each composition within the above range so that the viscosities of the compositions were about the same.

[0486] The addition amount of the curing accelerator was set such that the content of the curing accelerator in the composition was 1% by mass with respect to the total content of the epoxy compound and the specific compound having an epoxy group.

[0487] The addition amount (the total addition amount of the inorganic nitride and the other inorganic substances) of the inorganic substances was set to the addition amount (g) shown in Table 1.

[0488] Moreover, the inorganic substances were used after being mixed so that a ratio (mass ratio) between contents of the respective inorganic substances satisfied a relationship shown in Table 1.

[0489] The addition amount of the dispersant was set such that the content of the dispersant in the composition was 0.2% by mass with respect to the content of the inorganic substance.

[0490] The addition amount of the surface modifier for aluminum oxide was set such that the content of the surface modifier for aluminum oxide in the composition was 0.2% by mass with respect to the content (total content of AA-3 and AA-04) of the aluminum oxide. Moreover, in a case where the composition did not contain aluminum oxide, the surface modifier for aluminum oxide was not used.

[0491] The addition amount of the surface modifier for an inorganic nitride (the specific compound, or the compound for comparison) was set to the addition amount (g) shown in Table 1.

Evaluation

Thermally Conductive Properties (Preparation of Thermally Conductive Sheet)

[0492] The prepared composition was uniformly applied onto a release surface of a release-treated polyester film (NP-100A, manufactured by PANAC CO., LTD., film thickness of 100 μm) by using an applicator, and left to stand at 120° C. for 5 minutes to obtain a coating film.

[0493] Two polyester films with such a coating film were prepared, and after laminating the coating film surfaces with each other, two polyester films with a coating film were hot-pressed (treated for 1 minute at a hot plate temperature of 65° C. and a pressure of 12 MPa) in the air to obtain a semi-cured film. The obtained semi-cured film was treated with a hot press (treated for 20 minutes at a hot plate temperature of 160° C. and a pressure of 12 MPa, and then for 90 minutes at 180° C. and a normal pressure) in the air to cure the coating film, thereby obtaining a resin sheet. The polyester films on both surfaces of the resin sheet were peeled off to obtain a thermally conductive sheet having an average film thickness of 200 μm.

Preparation of Thermally Conductive Multilayer Sheet

[0494] Preparation of Adhesive Layer Film 1: Epoxy-Based Adhesive Layer, and without Filler

[0495] A coating liquid for an adhesive layer was obtained by mixing 21.6 parts by mass of B-3 as the epoxy compound, 13.3 parts by mass of A-1 as the phenolic compound, 0.21 parts by mass of triphenylphosphine (PPh.sub.3) as the curing accelerator, and 64.9 parts by mass of cyclopentanone.

[0496] The prepared coating liquid for an adhesive layer was uniformly applied onto a release surface of a release-treated polyester film (NP-100A, manufactured by PANAC CO., LTD., film thickness of 100 μm) by using an applicator, and left to stand at 120° C. for 5 minutes to obtain a coating film. Moreover, the final adhesive layer was formed so that the film thickness was 5 μm.

[0497] Preparation of Adhesive Layer Film 2: Epoxy-Based Adhesive Layer, and with Filler

[0498] A coating liquid for an adhesive layer was obtained by mixing 21.6 parts by mass of B-3 as the epoxy compound, 13.3 parts by mass of A-1 as the phenolic compound, 0.21 parts by mass of PPh.sub.3 as the curing accelerator, 35 parts by mass of alumina AA-04, and 100 parts by mass of cyclopentanone.

[0499] The prepared coating liquid for an adhesive layer was uniformly applied onto a release surface of a release-treated polyester film (NP-100A, manufactured by PANAC CO., LTD., film thickness of 100 μm) by using an applicator, and left to stand at 120° C. for 5 minutes to obtain a coating film. Moreover, the final adhesive layer was formed so that the film thickness was 5 μm.

[0500] Preparation of Adhesive Layer Film 3: Acrylic Acid Ester Copolymer Resin, and without Filler

[0501] A coating liquid for an adhesive layer was obtained by diluting an acrylic acid ester copolymer resin (HTR-280DR, produced by Nagase ChemteX Corporation, copolymer of butyl acrylate/acrylonitrile/acrylic acid, Mw: 900,000, Tg: −30.9° C., volume resistivity >10.sup.13 Ω.Math.m, and 15% by mass toluene solution) with a mixed solvent of methyl ethyl ketone and toluene.

[0502] The prepared coating liquid for an adhesive layer was uniformly applied onto a release surface of a release-treated polyester film (NP-100A, manufactured by PANAC CO., LTD., film thickness of 100 μm) by using an applicator, and left to stand at 120° C. for 5 minutes to obtain a coating film. Moreover, the final adhesive layer was formed so that the film thickness was 5 μm.

[0503] Furthermore, the layer formed of the acrylic acid ester copolymer resin is the pressure sensitive adhesive layer, but is referred to as an adhesive layer for convenience in Examples of the present specification.

[0504] Preparation of Multilayer Sheet

[0505] A semi-cured film (semi-cured film having polyester films on both surfaces thereof) was obtained by the same procedure as shown in the section of (Preparation of thermally conductive sheet).

[0506] The polyester films provided on the both surfaces of the semi-cured film were peeled off, the adhesive layer films were stacked so that the adhesive layer faced the semi-cured film, and the adhesive layers were attached using a laminator under conditions where a temperature was 120° C., a pressure was 0.7 MPa, a degree of vacuum ≤1 kPa was satisfied, and a time was 15 seconds, to obtain a multilayer sheet having adhesive coating films on the both surfaces of the semi-cured film.

[0507] Preparation of Multilayer Sheet-Cured Substance

[0508] The obtained multilayer sheet was treated with a hot press (treated for 20 minutes at a hot plate temperature of 160° C., and a pressure of 12 MPa, and then for 90 minutes at 180° C. and a normal pressure) in the air to cure the coating film and the semi-cured film, thereby obtaining a resin sheet. The polyester films on both surfaces of the resin sheet were peeled. off to obtain a multilayer sheet-cured substance (thermally conductive multilayer sheet) having an average film thickness of 200 μm.

[0509] The evaluation of thermally conductive properties was performed using each thermally conductive sheet or thermally conductive multilayer sheet which was formed of each composition. The thermal conductivity was measured by the following method, and the thermally conductive properties were evaluated according to the following standards.

[0510] (Measurement of thermal conductivity (W/m.Math.k)) (1) By using “LFA 467” manufactured by NETZSCH, the thermal diffusivity of the thermally conductive sheet in a thickness direction was measured through a laser flash method.

[0511] (2) By using a balance “XS204” manufactured by METTLER TOLEDO, the specific gravity of the thermally conductive sheet or thermally conductive multilayer sheet was measured through an Archimedes method (“solid specific gravity measuring kit” was used).

[0512] (3) By using “DSC320/6200” manufactured by Seiko Instruments Inc., the specific heat of the thermally conductive sheet or thermally conductive multilayer sheet at 25° C. was determined under a temperature rising condition of 10° C./min.

[0513] (4) The thermal conductivity of the thermally conductive sheet or thermally conductive multilayer sheet was calculated by multiplying the obtained thermal diffusivity by the specific gravity and the specific heat.

Evaluation Standard

[0514] The measured thermal conductivity was classified according to the following standards, and used as the evaluation of the thermally conductive properties.

[0515] “A+”: 15 W/m.Math.K or greater

[0516] “A”: 10 W/m.Math.K or greater and less than 15 W/m.Math.K

[0517] “B”: 8 W/m.Math.K or greater and less than 10 W/m.Math.K

[0518] “C”: 5 W/m.Math.K or greater and less than 8 W/m.Math.K

[0519] “D”: Less than 5 W/m.Math.K

[0520] The results are shown in Table 1.

Surface State (Smoothness) of Sheet

[0521] A thermally conductive sheet or thermally conductive multilayer sheet was prepared in the same manner as those produced in the tests of the section of <Thermally conductive properties>, and a surface state (smoothness) of the sheet was evaluated.

[0522] Specifically, the film thickness of the thermally conductive sheet or thermally conductive multilayer sheet was measured at any five positions, a standard deviation was determined for the measurement variation thereof, and the evaluation was performed according to the following standards. In a case where the standard deviation is small (in other words, in a case where the variation in the film thickness is small), the surface state (smoothness) of the sheet can be evaluated to be favorable.

[0523] Furthermore, the expression in which the surface state (smoothness) of the sheet is favorable also indicates that the inorganic substances (in particular, the inorganic nitride) are favorably dispersed. On the other hand, in a case where the standard deviation is large (in other words, in a case where the variation in the film thickness is large), this means that aggregation or the like occurs in the cured substance to cause surface roughness, that is, indicates that the dispersibility of the inorganic substances (in particular, the inorganic nitride) is degraded.

[0524] The film thickness was measured using “AI-PHASE MOBILE lu” manufactured by ai-Phase Co., Ltd.

Evaluation Standard

[0525] The determined standard deviation was classified according to the following standards, and used as the evaluation of the surface state (smoothness) of the sheet.

[0526] “A”: The standard deviation was smaller than 5 μm

[0527] “B”: The standard deviation was 5 μm or larger and smaller than 10 μm

[0528] “C”: The standard deviation was 10 μm or larger and smaller than 30 μm

[0529] “D”: The standard deviation was 30 μm or larger

[0530] The results are shown in Table 1.

Results

[0531] Table 1 below shows the kinds and addition amounts (g) of the phenolic compound, epoxy compound, inorganic substances, and surface modifier for an inorganic nitride, which are used in each composition, and the evaluation results.

[0532] In Table 1, a column of “Hydroxyl group content” indicates the hydroxyl group content (mmol/g) of the used phenolic compound.

[0533] A column of “Specific functional group” indicates the kind of the specific functional group included in the used specific compound. Moreover, in the column of “Specific functional group”, the description of “Epoxy group” means the “monovalent group having an epoxy group”.

[0534] In Table 1, a column of “Adhesive layer” indicates whether a test specimen (the thermally conductive sheet or the thermally conductive multilayer sheet) has an adhesive layer. The description of “None” indicates that the test specimen is a thermally conductive sheet which does not have the adhesive layer. The description of “1” indicates that the test specimen is a thermally conductive multilayer sheet having the adhesive layer formed of the adhesive layer film 1. The description of “2” indicates that the test specimen is a thermally conductive multilayer sheet having the adhesive layer formed of the adhesive layer film 2. The description of “3” indicates that the test specimen is a thermally conductive multilayer sheet having the adhesive layer formed of the adhesive layer film 3.

TABLE-US-00001 TABLE 1 Characterteristics of composition Epoxy Surface modifier for inorganic nitride Phenolic compound compound Inorganic substance (specific compound, or compound for comparision) Addition Hydroxyl group Addition Mass ratio Addition Specific Addition Evaluation amount content amount in inorganic amount functional amount Adhesive Thermal Surface Table 1-1 Kind (g) (mmol/g) Kind (g) substance (g) Kind group (g) layer conductivity state Example 1  A-1 6.26 14.2 B-1 16.74 PTX-60/AA-3/AA-04 - 47/40/13 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 2  A-1 4.9 14.2 B-1 13.1 PTX-60/AA-3/AA-04 - 47/40/13 82 C-1  Hydroxyl group/Aldehyde group 0.25 None A+ A Example 3  A-1 3.54 14.2 B-1 9.46 PTX-60/AA-3/AA-04 - 47/40/13 87 C-1  Hydroxyl group/Aldehyde group 0.26 None A+ A Example 4  A-1 6.26 14.2 B-1 16.74 PTX-60/AA-3/AA-04 - 47/40/13 77 C-1  Hydroxyl group/Aldehyde group 0.023 None A   B Example 5  A-1 6.26 14.2 B-1 16.74 PTX-60/AA-3/AA-04 - 47/40/13 77 C-1  Hydroxyl group/Aldehyde group 0.077 None A+ A Example 6  A-1 6.26 14.2 B-1 16.74 PTX-60/AA-3/AA-04 - 47/40/13 77 C-1  Hydroxyl group/Aldehyde group 0.46 None A+ A Example 7  A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 8  A-2 4.9 14.2 B-1 13.1 Only HP-40 MF100 82 C-1  Hydroxyl group/Aldehyde group 0.25 None A+ A Example 9  A-3 3.54 14.2 B-1 9.46 Only HP-40 MF100 87 C-1  Hydroxyl group/Aldehyde group 0.26 None A+ B Example 10 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.023 None A   A Example 11 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.077 None A+ A Example 12 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.46 None A+ A Example 13 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-2  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 14 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-3  Hydroxyl group/Boronic acid group 0.23 None A+ A Example 15 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-4  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 16 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-5  Hydroxyl group/Boronic acid group 0.23 None A+ A Example 17 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-6  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 18 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-7  Hydroxyl group/Boronic acid group 0.23 None A+ A Example 19 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-8  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 20 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-9  Hydroxyl group/Boronic acid group 0.23 None A+ A Example 21 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-10 Hydroxyl group/Aldehyde group 0.23 None A+ A Example 22 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-11 Hydroxyl group/Boronic acid group 0.23 None A+ A Example 23 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-12 Hydroxyl group/Aldehyde group 0.23 None A+ A Example 24 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-13 Hydroxyl group/Boronic acid group 0.23 None A+ A Example 25 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-14 Hydroxyl group 0.23 None A   A Example 26 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-15 Hydroxyl group 0.23 None A   A Example 27 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-16 Hydroxyl group 0.23 None A   A Example 28 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-17 Hydroxyl group 0.23 None A   A Example 29 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-18 Epoxy group 0.23 None A   A Example 30 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-19 Epoxy group 0.23 None A   A Example 31 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-20 Epoxy group 0.23 None A   A Example 32 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-21 Epoxy group 0.23 None A   A Example 33 A-1 6.26 14.2 B-1 16.74 Only HP-40 MF100 77 C-22 Hydroxyl group 0.23 None A   A Example 34 A-1 3.95 14.2 B-1 16.74 Only HP-40 MF100 77 C-14 Hydroxyl group 2.31 None A+ A Example 35 A-1 3.95 14.2 B-1 16.74 Only HP-40 MF100 77 C-15 Hydroxyl group 2.31 None A+ A Example 36 A-1 3.95 14.2 B-1 16.74 Only HP-40 MF100 77 C-16 Hydroxyl group 2.31 None A+ A Example 37 A-1 3.95 14.2 B-1 16.74 Only HP-40 MF100 77 C-17 Hydroxyl group 2.31 None A+ A Example 38 A-1 6.26 14.2 B-1 14.43 Only HP-40 MF100 77 C-18 Epoxy group 2.31 None A+ A Example 39 A-1 6.26 14.2 B-1 14.43 Only HP-40 MF100 77 C-19 Epoxy group 2.31 None A+ A Example 40 A-1 6.26 14.2 B-1 14.43 Only HP-40 MF100 77 C-20 Epoxy group 2.31 None A+ A Example 41 A-1 6.26 14.2 B-1 14.43 Only HP-40 MF100 77 C-21 Epoxy group 2.31 None A+ A Example 42 A-1 3.95 14.2 B-1 16.74 Only HP-40 MF100 77 C-22 Hydroxyl group 2.31 None A+ A Example 43 — — — B-1 14.14 Only HP-40 MF100 77 C-14 Hydroxyl group 8.85 None A+ A Example 44 — — — B-1 14.14 Only HP-40 MF100 77 C-15 Hydroxyl group 8.85 None A+ A Example 45 — — — B-1 13.48 Only HP-40 MF100 77 C-16 Hydroxyl group 9.51 None A+ A Example 46 — — — B-1 13.48 Only HP-40 MF100 77 C-17 Hydroxyl group 9.51 None A+ A Example 47 — — — B-1 16.49 Only HP-40 MF100 77 C-22 Hydroxyl group 6.51 None A+ A Example 48 — — — B-2 12.69 Only HP-40 MF100 77 C-16 Hydroxyl group 10.31 None A+ A Example 49 — — — B-2 15.81 Only HP-40 MF100 77 C-22 Hydroxyl group 7.19 None A+ A Example 50 — — — B-3 10.72 Only HP-40 MF100 77 C-16 Hydroxyl group 12.28 None A+ A

TABLE-US-00002 TABLE 2 Characterteristics of composition Phenolic compound Epoxy Surface modifier for inorganic nitride Hydroxyl compound Inorganic substance (specific compound, or compound for comparision) Addition group Addition Mass ratio Addition Specific Addition Evaluation amount content amount in inorganic amount functional amount Adhesive Thermal Surface Table 1-2 Kind (g) (mmol/g) Kind (g) substance (g) Kind group (g) layer conductivity state Example 51 — — — B-3 14.02 Only HP-40 MF100 77 C-22 Hydroxyl group 8.98 None A+ A Example 52 — — — B-4 11.71 Only HP-40 MF100 77 C-16 Hydroxyl group 11.29 None A+ A Example 53 — — — B-4 14.94 Only HP-40 MF100 77 C-22 Hydroxyl group 8.06 None A+ A Example 54 A-1 6.63 14.2 — — Only HP-40 MF100 77 C-18 Epoxy group 16.36 None A+ A Example 55 A-1 6.63 14.2 — — Only HP-40 MF100 77 C-19 Epoxy group 16.36 None A+ A Example 56 A-1 6.26 14.2 — — Only HP-40 MF100 77 C-20 Epoxy group 16.74 None A+ A Example 57 A-1 6.26 14.2 — — Only HP-40 MF100 77 C-21 Epoxy group 16.74 None A+ A Example 58 A-2 8.86 8.4 — — Only HP-40 MF100 77 C-20 Epoxy group 14.14 None A+ A Example 59 A-3 4.16 23.8 — — Only HP-40 MF100 77 C-20 Epoxy group 18.84 None A+ A Example 60 A-1 6.92 14.2 B-2 16.08 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 61 A-1 6.92 14.2 B-2 16.08 Only HP-40 MF100 77 C-10 Hydroxyl group/Aldehyde group 0.23 None A+ A Example 62 A-1 6.92 14.2 B-2 13.77 Only HP-40 MF100 77 C-20 Epoxy group 2.31 None A+ A Example 63 A-1 8.69 14.2 B-3 14.31 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 64 A-1 8.69 14.2 B-3 14.31 Only HP-40 MF100 77 C-10 Hydroxyl group/Aldehyde group 0.23 None A+ A Example 65 A-1 8.69 14.2 B-3 9.09 Only HP-40 MF100 77 C-20 Epoxy group 2.31 None A+ A Example 66 A-1 7.78 14.2 B-4 15.22 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 67 A-1 7.78 14.2 B-4 15.22 Only HP-40 MF100 77 C-10 Hydroxyl group/Aldehyde group 0.23 None A+ A Example 68 A-1 7.78 14.2 B-4 12.91 Only HP-40 MF100 77 C-20 Epoxy group 2.31 None A+ A Example 69 A-2 8.86 8.4 B-1 14.14 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 70 A-2 8.86 8.4 B-1 14.14 Only HP-40 MF100 77 C-10 Hydroxyl group/Aldehyde group 0.23 None A+ A Example 71 A-2 8.86 8.4 B-1 11.83 Only HP-40 MF100 77 C-20 Epoxy group 2.31 None A+ A Example 72 A-2 9.64 8.4 B-2 13.36 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 73 A-2 9.64 8.4 B-2 13.36 Only HP-40 MF100 77 C-10 Hydroxyl group/Aldehyde group 0.23 None A+ A Example 74 A-2 9.64 8.4 B-2 11.05 Only HP-40 MF100 77 C-20 Epoxy group 2.31 None A+ A Example 75 A-2 11.6 8.4 B-3 11.4 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 76 A-2 11.6 8.4 B-3 11.4 Only HP-40 MF100 77 C-10 Hydroxyl group/Aldehyde group 0.23 None A+ A Example 77 A-2 11.6 8.4 B-3 9.09 Only HP-40 MF100 77 C-20 Epoxy group 2.31 None A+ A Example 78 A-2 10.61 8.4 B-4 12.39 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 79 A-2 10.61 8.4 B-4 12.39 Only HP-40 MF100 77 C-10 Hydroxyl group/Aldehyde group 0.23 None A+ A Example 80 A-2 10.61 8.4 B-4 10.08 Only HP-40 MF100 77 C-20 Epoxy group 2.31 None A+ A Example 81 A-3 4.16 23.8 B-1 18.84 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 82 A-3 4.16 23.8 B-1 18.84 Only HP-40 MF100 77 C-10 Hydroxyl group/Aldehyde group 0.23 None A+ A Example 83 A-3 4.16 23.8 B-1 16.53 Only HP-40 MF100 77 C-20 Epoxy group 2.31 None A+ A Example 84 A-3 4.67 23.8 B-2 18.33 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 85 A-3 4.67 23.8 B-2 18.33 Only HP-40 MF100 77 C-10 Hydroxyl group/Aldehyde group 0.23 None A+ A Example 86 A-3 4.67 23.8 B-2 16.02 Only HP-40 MF100 77 C-20 Epoxy group 2.31 None A+ A Example 87 A-3 6.08 23.8 B-3 16.92 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 88 A-3 6.08 23.8 B-3 16.92 Only HP-40 MF100 77 C-10 Hydroxyl group/Aldehyde group 0.23 None A+ A Example 89 A-3 6.08 23.8 B-3 14.61 Only HP-40 MF100 77 C-20 Epoxy group 2.31 None A+ A Example 90 A-3 5.34 23.8 B-4 17.66 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A+ A Example 91 A-3 5.34 23.8 B-4 17.66 Only HP-40 MF100 77 C-10 Hydroxyl group/Aldehyde group 0.23 None A+ A Example 92 A-3 5.34 23.8 B-4 15.35 Only HP-40 MF100 77 C-20 Epoxy group 2.31 None A+ A Example 93 A-4 13.85 3.7 B-1 9.14 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A   A Example 94 A-4 13.85 3.7 B-1 9.14 Only HP-40 MF100 77 C-10 Hydroxyl group/Aldehyde group 0.23 None A   A Example 95 A-4 13.85 3.7 B-1 6.83 Only HP-40 MF100 77 C-20 Epoxy group 2.31 None A   A Example 96 A-4 14.62 3.7 B-2 8.37 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A   A Example 97 A-4 14.62 3.7 B-2 8.37 Only HP-40 MF100 77 C-10 Hydroxyl group/Aldehyde group 0.23 None A   A Example 98 A-4 14.62 3.7 B-2 6.06 Only HP-40 MF100 77 C-20 Epoxy group 2.31 None A   A Example 99 A-4 16.35 3.7 B-3 6.64 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A   A  Example 100 A-4 16.35 3.7 B-3 6.64 Only HP-40 MF100 77 C-10 Hydroxyl group/Aldehyde group 2.31 None A   A

TABLE-US-00003 TABLE 3 Characterteristics of composition Phenolic compound Epoxy Surface modifier for inorganic nitride Hydroxyl compound Inorganic substance (specific compound, or compound for comparision) Addition group Addition Mass ratio Addition Specific Addition Evaluation amount content amount in inorganic amount functional amount Adhesive Thermal Surface Table 1-3 Kind (g) (mmol/g) Kind (g) substance (g) Kind group (g) layer conductivity state Example 101 A-4 16.35 3.7 B-3 4.33 Only HP-40 MF100 77 C-20 Epoxy group 2.31 None A   A Example 102 A-4 15.51 3.7 B-4 7.49 Only HP-40 MF100 77 C-1  Hydroxyl group/Aldehyde group 0.23 None A   A Example 103 A-4 15.51 3.7 B-4 7.49 Only HP-40 MF100 77 C-10 Hydroxyl group/Aldehyde group 0.23 None A   A Example 104 A-4 15.51 3.7 B-4 5.18 Only HP-40 MF100 77 C-20 Epoxy group 2.31 None A   A Example 105 — — — B-3 10.72 Only HP-40 MF100 77 C-17 Hydroxyl group 12.28 None A+ A Example 106 — — — B-3 10.72 Only HP-40 MF100 77 C-17 Hydroxyl group 12.28 1 A   A Example 107 — — — B-3 10.72 Only HP-40 MF100 77 C-17 Hydroxyl group 12.28 2 A   A Example 108 — — — B-3 10.72 Only HP-40 MF100 77 C-17 Hydroxyl group 12.28 3 A   A Example 109 — — — B-3 10.72 HP-40 MF100/AA-3/AA-04 = 84/11/5  77 C-17 Hydroxyl group 12.28 None A+ A Example 110 — — — B-3 10.72 HP-40 MF100/AA-3/AA-04 = 77/16/7  77 C-17 Hydroxyl group 12.28 None A+ A Example 111 — — — B-3 10.72 HP-40 MF100/AA-3/AA-04 = 77/16/7  77 C-17 Hydroxyl group 12.28 2 A   A Example 112 — — — B-3 10.72 HP-40 MF100/AA-3/AA-04 = 77/16/7  77 C-17 Hydroxyl group 12.28 3 A   A Example 113 — — — B-3 10.72 HP-40 MF100/AA-3/AA-04 = 70/21/9  77 C-17 Hydroxyl group 12.28 None A+ A Example 114 — — — B-3 10.72 HP-40 MF100/AA-3/AA-04 = 58/29/13 77 C-17 Hydroxyl group 12.28 None A+ A Example 115 — — — B-3 10.72 HP-40 MF100/SP-3 = 99/1  77 C-17 Hydroxyl group 12.28 None A+ A Example 116 — — — B-3 10.72 HP-40 MF100/SP-3 = 95/5  77 C-17 Hydroxyl group 12.28 None A+ A Example 117 — — — B-3 10.72 HP-40 MF100/SP-3 = 95/5  77 C-17 Hydroxyl group 12.28 2 A   A Example 118 — — — B-3 10.72 HP-40 MF100/SP-3 = 95/5  77 C-17 Hydroxyl group 12.28 3 A   A Example 119 — — — B-3 10.72 HP-40 MF100/SP-3 = 90/10 77 C-17 Hydroxyl group 12.28 None A+ A Example 120 — — — B-3 10.72 HP-40 MF100/SP-3 = 85/15 77 C-17 Hydroxyl group 12.28 None A+ A Example 121 — — — B-3 8.91 Only HP-40 MF100 77 C-23 Hydroxyl group 14.09 None A+ A Example 122 — — — B-3 8.94 Only HP-40 MF100 77 C-24 Hydroxyl group 14.06 None A+ A Example 123 — — — B-3 8.94 Only HP-40 MF100 77 C-25 Hydroxyl group 14.06 None A+ A Example 124 — — — B-2 12.69 Only HP-40 MF100 77 C-17 Hydroxyl group 16.31 None A+ A Example 125 — — — B-3 8.91 HP-40 MF100/AA-3/AA-04 = 77/16/7  77 C-23 Hydroxyl group 14.09 None A+ A Example 126 — — — B-3 8.94 HP-40 MF100/AA-3/AA-04 = 77/16/7  77 C-24 Hydroxyl group 14.06 None A+ A Example 127 — — — B-3 8.94 HP-40 MF100/AA-3/AA-04 = 77/16/7  77 C-25 Hydroxyl group 14.06 None A+ A Example 128 — — — B-1 13.48 HP-40 MF100/AA-3/AA-04 = 77/16/7  77 C-17 Hydroxyl group 9.51 None A+ A Example 129 — — — B-2 12.69 HP-40 MF100/AA-3/AA-04 = 77/16/7  77 C-17 Hydroxyl group 10.31 None A+ A Comparative A-4 14.62 3.7 B-2 8.37 Only HP-40 MF100 77 None — 0 None D D Example 1 Comparative A-4 14.62 3.7 B-2 8.37 Only HP-40 MF100 77 D-1  — 0.23 None D D Example 2 Comparative A-4 14.62 3.7 B-2 8.37 Only HP-40 MF100 77 D-1  — 0.23 None D D Example 3 Comparative A-4 14.62 3.7 B-2 8.37 Only HP-40 MF100 77 D-1  — 0.23 None D D Example 4 Comparative A-4 14.62 3.7 B-2 8.37 Only HP-40 MF100 77 D-1  — 0.23 None D D Example 5 Comparative A-4 14.62 3.7 B-2 8.37 Only HP-40 MF100 77 D-1  — 0.23 None D D Example 6

[0535] From the results shown in the tables, it was confirmed that a thermally conductive material having excellent thermally conductive properties can be obtained by using the composition according to the embodiment of the present invention. Moreover, it was confirmed that the surface state of the thermally conductive sheet formed of the composition is also favorable.

[0536] It was confirmed that in a case where the composition contains a phenolic compound having a hydroxyl group content of 8.0 mmol/g or greater, the thermally conductive properties of the obtained thermally conductive material are superior (comparison between Examples 93 to 104 and Examples 69 to 80, and the like).

[0537] It was confirmed that in a case where the content of the inorganic substance contained in the composition is 85% by mass or less with respect to the solid content of the composition, the surface state of the obtained thermally conductive sheet is superior (comparison between Example 3 and Example 2, comparison between Example 9 and Example 8, and the like).

[0538] It was confirmed that in a case where the specific compound contains at least one of an aldehyde group or a boronic acid group, and a hydroxyl group under a condition where the composition contains both the phenolic compound and the epoxy compound, the thermally conductive properties of the obtained thermally conductive material are superior (comparison between Examples 25 to 32 and Examples 7 and 13 to 24, and the like).

[0539] It was confirmed that in a case where the content of the specific compound is 0.05% by mass or greater with respect to total solid content, the thermally conductive properties of the obtained thermally conductive material are superior (comparison between Example 4 and Example 5, comparison between Example 10 and Example 11, and the like).

[0540] It was confirmed that in a case where the content of the specific compound is 0.5% by mass or greater with respect to the content of the inorganic nitride under a condition where the specific compound is the “compound having only a monovalent group having an epoxy group as the specific functional group” or the “compound having only a hydroxyl group as the specific functional group”, the thermally conductive properties of the obtained thermally conductive material are superior (comparison between Examples 25 to 33 and Examples 34 to 41, and the like).