JP4858470B2 - Inorganic nitride particles and resin composition containing the same - Google Patents

Description

  The present invention relates to inorganic nitride particles and a resin containing inorganic nitride particles.

  In recent years, with the miniaturization and high performance of electronic devices, how to take heat dissipation measures has become an important issue. Therefore, in order to increase the thermal conductivity of the resin, a method of adding fine particles having high thermal conductivity to the resin as a filler is generally used. Inorganic nitride particles such as silicon nitride, boron nitride, and aluminum nitride having higher thermal conductivity are used as an electrically insulating filler added to form a highly thermally conductive insulating resin. The effect obtained by adding a filler having a high thermal conductivity to the resin appears significantly when the filling amount of the filler is increased.

  However, when the filler filling amount is increased, the viscosity of the resin is increased, resulting in deterioration of moldability and adhesiveness. For this reason, there is a limit to the method for improving the thermal conductivity by increasing the filling amount of the filler.

  Therefore, there is a demand for a method for improving the affinity of the resin by modifying the surface of the filler and suppressing the increase in the viscosity of the resin when the filler is filled.

  Patent Document 1 discloses a method of modifying the surface of inorganic nitride particles by reacting the surface of inorganic nitride particles with a silane, aluminate or titanate coupling agent.

  However, since silane coupling treatment uses water for the reaction, it cannot be used for surface modification of water-unstable inorganic particles. In addition, it can be used to modify the surface of boron nitride particles that are stable to water. However, since the number of —OH groups that are reaction points on the particle surface is small, the effect of surface modification can be sufficiently improved. Can not.

Patent Document 2 discloses a method of modifying particle surfaces by reacting —NH, —NH ₂ groups on the surface of boron nitride with isocyanate groups (—NCO). However, since the isocyanate group only reacts with —NH and —NH ₂ groups on the particle surface and does not react with —OH group present on the particle surface, it is not effective as a surface modification of the particle. .

Patent Document 3 discloses boron nitride in which the particle surface is coated with an aromatic polyamide by a polymerization reaction on the boron nitride surface. In this case, it is considered that the acid anhydride used in the polymerization reaction reacts with —OH, —NH, and —NH ₂ groups on the boron nitride surface to modify the boron nitride surface. However, when the inorganic nitride particles are contained in the resin to further improve the thermal conductivity of the resin, it is desirable that fewer particle surface modifiers are formed on the particle surface, and the resin used is thermosetting. It is a resin, and it is undesirable from the viewpoint of resin moldability that the particle surface is coated with a thermoplastic resin (aromatic polyamide).

JP 2006-257392 A JP 2001-192500 A JP 2007-145679 A

  An object of the present invention is to reduce the viscosity of a resin containing inorganic nitride particles and improve the moldability by modifying the surface of the inorganic nitride particles.

  The inorganic nitride particles of the present invention are characterized by being surface-modified with a functional group having a structure represented by the following formula (1) and / or (2).

  In addition, the inorganic nitride particles of the present invention are characterized by being surface-modified with a functional group having a structure represented by the following formula (3) and / or (4) (wherein Ph represents a phenyl group) Show).

  In addition, the inorganic nitride particles of the present invention are characterized by being surface-modified with a functional group having a structure represented by the following formula (5) and / or (6) (wherein Ph represents a phenyl group) R represents an alkyl group having 3 to 20 carbon atoms or an aryl group).

  According to the present invention, by using the inorganic nitride particles subjected to the above surface treatment, the affinity with the resin is improved, and the viscosity of the resin when the inorganic nitride particles are contained in the resin is lowered. And formability can be improved.

  Moreover, according to this invention, the filling amount of inorganic nitride particle | grains can be increased conventionally, and a resin molding material with high heat conductivity can be obtained.

  The present invention relates to an inorganic nitride particle and a resin molding material containing the inorganic nitride particle. In particular, the present invention relates to a heat dissipating material for efficiently dissipating heat generated from exothermic parts of various electric and electronic devices and inorganic particles contained in the heat dissipating material.

  The present invention improves the moldability of a resin containing inorganic nitride particles by modifying the particle surface by reacting an acid halide having an acid anhydride group on the surface of the inorganic nitride particles.

More specifically, the following formula (1) obtained by reacting —OH, —NH, —NH ₂ groups present on the surface of inorganic nitride particles with an aromatic acid halide having an acid anhydride group: These are inorganic nitride particles that are surface-modified with a compound having a structure represented by (2).

  In addition, in the following formulas (3) and / or (4) obtained by hydrolyzing the inorganic nitride particles surface-modified with the compound having the structure represented by the above formula (1) and / or (2) Inorganic nitride particles that are surface-modified with a compound having the structure shown.

  Furthermore, the compound which has two amino groups in the inorganic nitride particle | grains surface-modified by the compound which has a structure represented by said Formula (1) and / or (2) and / or (3) and / or (4) Inorganic nitride particles surface-modified with a compound having a structure represented by the following formula (5) and / or (6) by reacting (wherein Ph represents a phenyl group, R represents a carbon number of 3 to 20 represents an alkyl group or an aryl group).

  Affinity with resin is improved by particles having the structure shown in general formula (1), (2), (3), (4), (5) or (6), and inorganic nitride particles are contained in the resin Thus, the viscosity of the resin can be lowered, the filling amount of the inorganic nitride particles can be increased, and a resin molding material having a high thermal conductivity can be obtained.

  Also, inorganic nitride particles having the structure shown in the general formula (1), (2), (3), (4), (5) or (6) are mixed with a thermosetting resin, and cured with a diamine compound. By forming a chemical bond between the inorganic nitride particles and the thermosetting resin, a resin molding material having a higher thermal conductivity than when using non-surface treated inorganic nitride particles is used. Obtainable. In particular, the diamine used for the surface treatment is desirably aromatic, and more desirably includes a naphthyl group.

The inorganic nitride particles or resin molding material according to the present invention can be formed through the following steps.
(1) A step of reacting the surface of the inorganic nitride particles with an aromatic acid halide having an acid anhydride group to obtain a compound having an acid anhydride group represented by the general formula (1) and / or (2).
(2) The inorganic nitride particles having the structure represented by the general formula (1) and / or (2) are hydrolyzed to have a structure represented by the general formula (3) and / or (4) on the particle surface. Forming inorganic nitride particles;
(3) Particles obtained by reacting a compound having two amino groups with inorganic nitride particles having a structure represented by general formula (1) and / or (2) and / or general formula (3) and / or (4) A step of forming inorganic nitride particles having a structure represented by the general formula (5) and / or (6) on the surface.
(4) The resin monomer has a structure represented by the general formula (1) and / or (2) and / or the general formula (3) and / or (4) and / or the general formula (5) and / or (6). The process of obtaining the resin molding material by containing the inorganic nitride particle which has, and making it harden | cure.

  Examples of inorganic nitride particles that can be used in the present invention include silicon nitride, boron nitride, aluminum nitride, titanium nitride, zirconium nitride, tantalum nitride, and niobium nitride.

  In step (1), as the aromatic acid halide having an acid anhydride group, for example, trimellitic acid chloride, trimellitic acid bromide, or the like can be used.

  The solvent that can be used to react the inorganic nitride particles with the aromatic acid halide having an acid anhydride group dissolves the aromatic acid halide having an acid anhydride group, and the inorganic nitride particles are uniformly dispersed. In order to prevent the aromatic acid halide having an acid anhydride group from reacting with water and changing to a carboxylic acid, it is desirable to use a solvent excluding water in the solvent as much as possible. . For example, dehydrated tetrahydrofuran (THF), dehydrated diethyl ether and the like can be used.

  Aromatic acid halides having acid anhydride groups have two reactive sites, acid anhydrides and acid halides, but aromatic acid halides having acid anhydride groups for inorganic nitride particles When an excessive amount of is used, an acid halide group having higher reactivity reacts with the inorganic nitride particle, and an inorganic nitride particle in which an aromatic compound having an acid anhydride group is bonded to the surface is generated.

  After the reaction, the aromatic acid halide having the acid anhydride group used in excess can be washed and filtered with a solvent to obtain inorganic nitride particles bonded with the aromatic compound having the acid anhydride group on the surface. The resulting nitrided inorganic particles have acid anhydride groups and are therefore highly reactive with water. However, inorganic nitridation in which aromatic compounds having dicarboxylic acid groups are bonded to the surface obtained by reaction with water. It may be a physical particle.

  Examples of the compound having two amino groups that can be used in the step (3) include aliphatic diamines, polyether polyamines, alicyclic diamines, and aromatic diamines.

  When a resin composition is formed using inorganic nitride particles obtained by reacting a diamine compound and a thermosetting resin, the thermal conductivity of the resulting resin composition includes an aromatic diamine as a diamino compound. It is preferable that 1,5-diaminonaphthalene is contained as an aromatic diamine.

  The solvent that can be used in the reaction in the step (3) may be any solvent that can dissolve the diamine used in the reaction. For example, THF or diethyl ether can be used. The reaction may be performed under the condition that inorganic nitride particles in which a diamine and an aromatic compound having a dicarboxylic acid or acid halide group are bonded to each other are bonded. After the reaction, the excessively used diamine is washed with a solvent and filtered to obtain inorganic nitride particles to which the compound represented by the general formula (5) and / or (6) is bonded on the surface.

  Examples of the aliphatic diamine include ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and 1,7-heptane. Diamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine and the like can be used.

  Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,6-diaminotoluene, and 3,4-diaminotoluene. 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 4,5-dimethyl-o-phenylenediamine, 2,4-diaminomesitylene, 2,3-diaminopyridine, 2, 6-diaminopyridine, 3,4-diaminopyridine, 9,10-diaminophenanthrene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,7-diaminonaphthalene, 3, 3 '5,5'-tetramethylbenzidine, 3,3'-dimethyl-4,4'-diaminobifu Enyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-methylenedi-o- Toluidine, 4,4′-methylenedi-2,6-xylidine, 4,4′-methylenedi-2,6-diethylaniline, 4,4′-diamino-1,2-diphenylethane, 4,4′-diamino- 2,2′-dimethylbibenzyl, 3,4′-diamino-2,2-diphenylpropane, 4,4′-diamino-2,2-diphenylpropane, 4,4′-diaminostilbene, 4,4′- Diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-thiodianiline, 2,2′-dithiodianiline, 4,4′-dithiodianiline, 3,3′-diamy Diphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 4,4′-diaminobenzanilide, o-tolidine sulfone, 2,7-diaminofluorene, 3, 7-diamino-2-methoxyfluorene, bis-p-aminophenylaniline, 1,3-bis (4-aminophenylpropyl) benzene, 1,4-bis (4-aminophenylpropyl) benzene, 1,3- Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, Bis [4- (4-aminophenoxy) phenyl] sulfone, 9,9-bis (4-aminophene) Le) fluorene or the like can be used.

  Examples of the resin that can be used in the step (4) include thermosetting resins. Among these, it is desirable to use an epoxy resin. As the curing agent, an amine compound or a derivative thereof, an alicyclic acid anhydride, an aliphatic acid anhydride, an aromatic acid anhydride, imidazole or a derivative thereof, a phenol, a compound or a polymer thereof, or the like can be used. Two or more of these may be used in combination.

  Hereinafter, a method for producing Sample 1 and a method for measuring physical properties will be described.

  Surface modification was performed on boron nitride particles (manufactured by Electrochemical Co., Ltd .: Decabolone HGP) using trimellitic acid chloride as an aromatic acid halide having an acid anhydride group. To a solution in which 30 g of boron nitride particles were dispersed in 200 mL (milliliter) of dehydrated THF, 1 g of trimellitic acid chloride was added at room temperature and stirred for 6 hours. Boron nitride particles were suction filtered, excess trimellitic chloride was removed with THF, and then dried. Boron nitride particles surface-treated with trimellitic chloride were added and dispersed in a THF solution in which 1,5-diaminonaphthalene was dissolved, and the solvent was refluxed for 6 hours. The resulting solution was filtered with suction, excess diamine was removed with THF, and then dried to obtain surface-treated boron nitride particles.

  An epoxy resin (manufactured by Japan Epoxy Resin: Epicoat 828), a curing agent (manufactured by Nippon Kayaku: Kayahard AA) and a solvent were added to the formed surface-treated boron nitride particles to form a varnish (the BN content in the cured resin was The varnish was adjusted to be 30 vol%). The viscosity of the formed varnish was measured with a rotational viscometer (manufactured by HAAKE: Rheo Stress RS600).

  The formed varnish was impregnated into a glass cloth made of glass fiber, and then heat treated at 150 ° C. for 5 minutes to prepare a prepreg. The produced prepreg was pressed at a surface pressure of 10 MPa and 180 ° C. for 60 minutes to produce a 2ply laminate. The thermal conductivity of the produced laminate was measured by a xenon flash method using a thermal diffusivity measuring apparatus (LFA447 Nanoflash) manufactured by NETZSCH.

  The production methods of Samples 2 to 4 are as follows.

  Sample 2: A sample was prepared in the same manner as Sample 1 using o-phenylenediamine instead of 1,5-diaminonaphthalene used in Sample 1.

  Sample 3: A sample was prepared in the same manner as Sample 1 using 1,2-diaminoethane in place of 1,5-diaminonaphthalene used in Sample 1.

  Sample 4: After the particles and trimellitic chloride were reacted by the same method as Sample 1, a sample was prepared by the same method as Sample 1 without reacting with diamine.

  The varnish viscosities of Samples 1, 2, 3 and 4 are all lower than that of Sample 13 of Comparative Example 1 where no surface treatment was applied.

  The production methods of Samples 5 to 8 are as follows.

  Sample 5: Epoxy resin (manufactured by Japan Epoxy Resin: Epicoat 828) having the same blending amount as in Example, and curing on surface-treated silicon nitride particles (Electrochemical: SN-F1) formed by the same method as in Example 1. A varnish was formed by adding an agent (manufactured by Nippon Kayaku: Kayahard AA) and a solvent (the varnish was adjusted so that the boron nitride particle content in the cured resin was 30 vol%). Using the formed varnish, a prepreg and a laminate were produced in the same manner as in Example 1.

  Sample 6: A sample was prepared in the same manner as Sample 5 using o-phenylenediamine instead of 1,5-diaminonaphthalene used in Sample 5.

  Sample 7: A sample was prepared in the same manner as Sample 5 using 1,2-diaminoethane instead of 1,5-diaminonaphthalene used in Sample 5.

  Sample 8: After reacting particles and trimellitic acid chloride by the same method as Sample 5, a sample was prepared by the same method as Sample 5 without reacting with diamine.

  The viscosity of the varnish used in Samples 5, 6, 7 and 8 is lower than that of Sample 14 of Comparative Example 2 where no surface treatment was applied.

  The production methods of Samples 9 to 12 are as follows.

  Sample 9: Aluminum nitride particles (FAN-f30 manufactured by Furukawa Denshi) were subjected to surface modification using trimellitic acid chloride as an aromatic acid halide having an acid anhydride group. To a solution in which 30 g of boron nitride particles were dispersed in 200 mL of dehydrated THF, 1 g of trimellitic chloride was added at room temperature and stirred for 6 hours. The aluminum nitride particle dispersion was subjected to suction filtration, and then excess trimellitic chloride was removed with dehydrated THF, followed by drying. Aluminum nitride particles surface-treated with trimellitic acid chloride were added and dispersed in a dehydrated THF solution in which 1,5-diaminonaphthalene was dissolved, and the solvent was refluxed for 6 hours. The obtained solution was subjected to suction filtration, excess diamine was removed with dehydrated THF, and then dried to obtain surface-treated aluminum nitride particles.

  An epoxy resin (manufactured by Japan Epoxy Resin: Epicoat 828), a curing agent (manufactured by Nippon Kayaku: Kayahard AA), and a solvent were added to the formed surface-treated aluminum nitride particles in the same manner as in Example to form a varnish ( The varnish was adjusted so that the BN content in the cured resin was 30 vol%). Using the formed varnish, a prepreg and a laminate were produced in the same manner as in Example 1.

  Sample 10: A sample was prepared in the same manner as Sample 9, using o-phenylenediamine instead of 1,5-diaminonaphthalene used in Sample 9.

  Sample 11: A sample was prepared in the same manner as Sample 9 using 1,2-diaminoethane in place of 1,5-diaminonaphthalene used in Sample 9.

  Sample 12: After reacting the particles with trimellitic chloride by the same method as Sample 9, a sample was prepared by the same method as Sample 9 without reacting with diamine.

The viscosity of the varnish used in Samples 9, 10, 11 and 12 is lower than that of Sample 14 of Comparative Example 3 where no surface treatment was applied.
[Comparative Example 1]
Sample 13: An epoxy resin (manufactured by Japan Epoxy Resin: Epicoat 828) and a curing agent (Nipponization) were used in the same manner as in Example 1 without surface treatment using boron nitride particles (manufactured by Electrochemical Co., Ltd .: Decabolone HGP). Pharmaceutical: Kayahard AA) and a solvent were added to form a varnish (the varnish was adjusted so that the boron nitride particle content in the cured resin was 30 vol%). Using the formed varnish, a prepreg and a laminate were produced in the same manner as in Example 1.
[Comparative Example 2]
Sample 14: Epoxy resin (Japan Epoxy Resin: Epicoat 828) and curing agent (Japan) were used in the same manner as in Example 2 without surface treatment using silicon nitride particles (Electrochemical: SN-F1). Kayaku: Kayahard AA) and a solvent were added to form a varnish (the varnish was adjusted so that the boron nitride particle content in the cured resin was 30 vol%). Using the formed varnish, a prepreg and a laminate were produced in the same manner as in Example 1.
[Comparative Example 3]
Sample 15: An epoxy resin (manufactured by Japan Epoxy Resin: Epicoat 828) and a curing agent (Japan) were used in the same manner as in Example 3 using aluminum nitride particles (Furukawa Electronics: FAN-f30) without surface treatment. Chemicals: Kayahard AA) and a solvent were added to form a varnish (the varnish was adjusted so that the BN content in the cured resin was 30 vol%). Using the formed varnish, a prepreg and a laminate were produced in the same manner as in Example 1.

  Comparing the thermal conductivity of Samples 1 to 9 formed using the surface-treated particles, the sample using 1,5-diaminonaphthalene has the highest thermal conductivity in all Examples, and then o-phenylene. Samples using diamine, the lowest was 1,2-diaminoethane, and aromatic diamines were effective as diamines used for the surface treatment, and 1,5-diaminonaphthalene was particularly effective.

  According to the present invention, by using the inorganic nitride particles subjected to the above surface treatment, the affinity with the resin is improved, and the viscosity of the resin when the inorganic nitride particles are contained in the resin is lowered. In addition, the filling amount of the inorganic nitride particles can be increased as compared with the prior art, and a resin molding material having high thermal conductivity can be obtained.

  Further, according to the present invention, the inorganic nitride particles subjected to the above surface treatment are contained in a thermosetting resin and cured with a diamine compound, whereby chemicals are generated between the inorganic nitride particles and the thermosetting resin. A resin molding material having a high thermal conductivity can be obtained as compared with the case where inorganic nitride particles that are not subjected to surface treatment are formed by bonding. In particular, the diamine used for the surface treatment is desirably aromatic, and more desirably naphthalene.

  Furthermore, the laminated board by this invention can obtain high heat conductivity compared with the laminated board formed using the inorganic nitride particle | grains which have not performed the same amount of surface treatment.

In addition, according to the present invention, inorganic nitride particles and resin can be obtained by reacting —OH, —NH, —NH ₂ groups present on the surface of inorganic nitride particles with an aromatic acid halide having an acid anhydride group. The viscosity of the resin when the inorganic nitride particles are contained in the resin can be lowered, and the particle filling amount can be increased.

  INDUSTRIAL APPLICABILITY The present invention can be applied to technical fields related to a resin composition to which inorganic nitride particles are applied and a method for producing the same, and a laminated board or printed wiring board using a prepreg to which inorganic nitride particles are applied.

Claims (16)

An inorganic nitride particle which is surface-modified with a functional group having a structure represented by the following formula (1) and / or (2).

Inorganic nitride particles characterized by being surface-modified with a functional group having a structure represented by the following formula (3) and / or (4) (wherein Ph represents a phenyl group).

Inorganic nitride particles characterized by being surface-modified with a functional group having a structure represented by the following formula (5) and / or (6) (wherein Ph represents a phenyl group, R represents a carbon number of 1 -6 alkyl group or C6-C20 aromatic functional group).

Inorganic nitride particles having a structure represented by the following formula (7) and / or (8) (wherein Ph represents a phenyl group, Ar represents an aromatic functional group having 6 to 20 carbon atoms) ).

  An inorganic nitride particle, wherein the Ar group according to claim 4 is a phenyl group.   An inorganic nitride particle, wherein the Ar group according to claim 4 is a naphthyl group.   Inorganic nitride particles, wherein the inorganic nitride according to any one of claims 1 to 6 is boron nitride.   A resin composition comprising a thermosetting resin and the inorganic nitride particles according to claim 1.   A varnish comprising a thermosetting resin and the inorganic nitride particles according to claim 1.   A prepreg obtained by impregnating a varnish according to claim 9 into a base material formed of a sheet-like fiber cloth or nonwoven fabric. Resin molding material containing inorganic nitride particles modified with a functional group having a structure represented by the following formula (9) and / or (10) (wherein Ph is a phenyl group, Ar is a carbon number of 6 to 20) Aromatic functional groups, R ¹ and R ² represent an alkyl group having 1 to 6 carbon atoms or an aromatic functional group having 6 to 20 carbon atoms).

  A laminate comprising the prepreg according to claim 10 formed by heating and pressing. Including a step of reacting an aromatic acid halide having an acid anhydride group with inorganic nitride particles to form inorganic nitride particles having a structure represented by the following formula (1) and / or (2): A method for producing inorganic nitride particles.

Reacting the inorganic nitride particles with an aromatic acid halide having an acid anhydride group to form inorganic nitride particles having a structure represented by the following formula (1) and / or (2); A step of hydrolyzing the inorganic nitride particles to form inorganic nitride particles having a structure represented by the following formula (3) and / or (4): Method.

Reacting the inorganic nitride particles with an aromatic acid halide having an acid anhydride group to form inorganic nitride particles having a structure represented by the following formula (1) and / or (2); A step of obtaining inorganic nitride particles having a structure represented by the following formula (3) and / or (4) by hydrolyzing the inorganic nitride particles, the following formulas (1) and / or (2) and / or Alternatively, the inorganic nitride particles having a structure represented by the following formula (3) and / or (4) are reacted with an aromatic diamine to have a structure represented by the following formula (5) and / or (6). Forming the inorganic nitride particles. A method for producing the inorganic nitride particles.

  A step of forming inorganic nitride particles by the method for producing inorganic nitride particles according to claim 15, a step of adjusting a varnish containing the inorganic nitride particles, a resin monomer, a curing agent and a solvent, and a sheet-like fiber cloth Or the manufacturing method of the laminated board characterized by including the process of apply | coating this varnish to the base material containing a nonwoven fabric, and forming the prepreg by heat-press molding.