TW201341470A - Heat conductive silicone composition and cured product thereof - Google Patents

Abstract

The present invention provides a heat conductive silicone composition which is excellent in compressibility, insulativity, heat conductivity and workability and especially has a heat conductivity of 3.0 W/mK or more so as to suitably form a heat conductive resin molded article installed between a heat-generating part and a heat-dissipating part in, for example, electric equipment for heat dissipation, and also provides a cured product thereof. The present invention provides a heat conductive silicone composition characterized by containing: (A) an organic polysiloxane containing at least two alkenyl groups in one molecule; (B) an organic hydrogen polysiloxane containing at least two hydrogen atoms directly bonded to silicon atom; and (C) a heat conductive filler, and (D) a platinum group metal-based curing catalyst, wherein the heat conductive filler of the (C) component consists of the following components in specified quantity: (C-i) amorphous aluminum oxide having an average particle diameter of 10 ~ 30μm; (C-ii) spherical aluminum oxide having an average particle diameter of 30 ~ 85μm; and (C-iii) insulated inorganic filler having an average particle diameter of 0.1 ~ 6μm.

Description

Thermally conductive polyfluorene composition and hardened material thereof

More particularly, the present invention relates to a thermally conductive polyphosphonium composition useful as a heat conductive material for thermal conduction of an electronic component by means of an interface between a heat interface of a heat-generating electronic component and a heat dissipating member such as a heat sink or a circuit board, and hardening thereof. Things.

LSI chips such as CPUs, driver ICs, or memories used in electronic devices such as personal computers, digital video discs, and mobile phones are becoming more sophisticated. High speed. miniaturization. Highly integrated, it generates a large amount of heat itself, and the rise in wafer temperature due to the heat causes malfunction and destruction of the wafer. Therefore, various heat dissipation methods for suppressing the rise in temperature of the wafer during operation and heat dissipation members used therein have been proposed.

In the past, in electronic equipment and the like, in order to suppress an increase in the temperature of the wafer during operation, a heat sink using a metal plate having a high thermal conductivity such as aluminum or copper is used. The heat sink conducts heat generated by the wafer, and the heat is released from the surface by a temperature difference from the outside air.

In order to efficiently transfer the heat generated from the wafer to the heat sink, the heat sink must be adhered to the wafer, but the gap between the wafer and the heat sink is separated by the difference in height of each wafer or tolerance due to assembly processing. A flexible sheet or grease is placed through which the heat transfer from the wafer to the heat sink is achieved.

Compared with grease, the flakes are excellent in rationality, so they are made in various fields. A heat conductive sheet (thermal conductive polyoxyethylene rubber sheet) formed by heat conductive polyoxymethylene rubber or the like is used.

JP-A-47-32400 (Patent Document 1) discloses that 100 to 800 parts by mass of yttrium oxide, alumina, hydrated alumina, magnesia, and oxidation are blended in 100 parts by mass of a synthetic rubber such as a polyoxyethylene rubber. An insulating composition made of at least one metal oxide selected from zinc.

Further, as a heat-dissipating material for use in a place where no insulation is required, JP-A-56-100849 (Patent Document 2) discloses that 60 to 500 parts by mass of the addition-hardening type polyoxymethylene rubber composition is blended. A composition of cerium oxide and a thermally conductive powder such as silver, gold or bismuth.

However, these thermal conductive materials have low thermal conductivity, and when a large amount of highly thermally filled filler is filled in order to improve thermal conductivity, there is a problem that fluidity is lowered in the case of a liquid polyoxyethylene rubber composition. In the case of a kneaded polyoxymethylene rubber composition, there is an increase in plasticity and a problem of extremely poor formability.

Therefore, in order to solve such a method, it is disclosed in JP-A-1-69661 (Patent Document 3) that the alumina particles having an average particle diameter of 5 μm or less are filled in an amount of 10 to 30% by mass, and the remaining portion is a single particle having an average particle diameter of 10 μm or more. And the high thermal conductivity rubber of alumina composed of spherical corundum particles without cutting edge shape. Plastic composition. Japanese Patent Publication No. 4-328163 (Patent Document 4) discloses a rubbery organopolysiloxane having an average polymerization degree of 6,000 to 12,000 and an oily organopolyoxane having an average polymerization degree of 200 to 2,000. A thermally conductive polyxanthene rubber composition comprising 500 to 1,200 parts by mass of spherical alumina powder.

However, even if such a method is used, for example, when the alumina powder of 1,000 parts by mass or more (more than 70% by volume of alumina) is highly filled, only the combination of particles and the viscosity adjustment of the poly-xylene beads improve the formability. There are still boundaries.

On the other hand, with the advancement of electronic devices such as personal computers, word processors, and CD-ROM drives, the amount of heat generated by integrated circuit components such as LSIs and CPUs in the devices has increased. There are insufficient conditions for the cooling method. In particular, in the case of a notebook computer for carrying, a large heat sink or a cooling fan cannot be installed due to the narrow space inside the device. Further, in these devices, the integrated circuit component is mounted on the printed circuit board in advance, and the material of the substrate is made of a glass-reinforced epoxy resin or a polyimide resin having poor thermal conductivity, so that the heat-insulating insulating sheet cannot be separated in the past. The heat of the substrate escapes.

Therefore, a heat-dissipating component of a natural cooling type or a forced cooling type is provided in the vicinity of the integrated circuit component to transfer the heat generated by the component to the heat-dissipating component. When the element is directly in contact with the heat dissipating member in this manner, the heat transfer is deteriorated due to the surface unevenness, and even if the heat insulating insulating sheet is interposed, since the heat insulating sheet is slightly inferior, the element is still thermally expanded. A stress is applied between the substrate and the substrate.

Further, when a heat dissipating component is mounted on each circuit component, an extra space is required, and the device is difficult to be miniaturized. Therefore, a method in which a plurality of components are combined on one heat dissipating component and cooled is also employed.

Especially for BGA type CPUs used in notebook PCs, since the height is lower than other components and the heat is large, it is necessary to fully consider the cooling side. formula.

Therefore, there is a need for a high-hardness conductive material of low hardness which can be buried in various gaps due to the difference in height of each element. In response to this problem, a thermally conductive sheet which is excellent in thermal conductivity and has flexibility and can cope with various gaps is desired. Further, as the frequency of the drive frequency is increased year by year, the CPU performance is improved and the amount of heat generation is increased, so that a material having higher thermal conductivity is required.

In this case, a sheet formed by mixing a thermally conductive material such as a metal oxide into a polyoxynoxy resin is disclosed in JP-A No. 2-196453 (Patent Document 5), and is a polysiloxane having a necessary strength for processing. A sheet of a soft and easily deformable polysiloxane layer is laminated on the resin layer. Japanese Patent Publication No. Hei 7-266356 (Patent Document 6) discloses a porous reinforced rubber layer having a thermally conductive filler and having an Asker C hardness of 5 to 50 and a pore having a diameter of 0.3 mm or more. A thermally conductive composite sheet. JP-A-H08-238707 (Patent Document 7) discloses a sheet in which a flexible three-dimensional network or a skeleton lattice surface of a foam is coated with a thermally conductive polyoxymethylene rubber. Japanese Laid-Open Patent Publication No. Hei 9-1738 (Patent Document 8) discloses a thermally conductive composite polyfluorene having a reinforcing sheet or cloth and having at least one surface adhesiveness and an Asker C hardness of 5 to 50 and a thickness of 0.4 mm or less. Sheet. Japanese Laid-Open Patent Publication No. Hei 9-296114 (Patent Document 9) discloses an addition reaction type liquid polyoxyxene rubber and a thermally conductive insulating ceramic powder, and the thermal resistance of the cured product having an Asker C hardness of 25 or less is 3.0 ° C. Thermal spacers below /W.

Most of these thermally conductive polyanthracene cured materials require insulation, so when the thermal conductivity is in the range of 0.5 to 6 W/mK, oxidation is mainly used. Aluminum is used as a thermally conductive filler. In general, the amorphous alumina phase has a higher effect of improving the thermal conductivity than the spherical alumina, but the poor filling property of the polyfluorene oxide has a disadvantage that the viscosity of the material increases due to the filling and the workability is deteriorated. Further, alumina has a Mohs hardness of 9, as used in an abrasive, and is very hard. Therefore, in particular, when a heat conductive polyfluorene oxide composition having an amorphous alumina having a particle diameter of 10 μm or more is used, if a shear force is applied at the time of manufacture, there is a problem that the inner wall of the reaction vessel or the stirring blade is shaved. Then, the components of the reaction vessel or the stirring blade are mixed in the thermally conductive polysiloxane composition, and the insulation properties of the thermally conductive polyfluorene composition and the cured product using the same are lowered. Further, the gap between the reaction vessel and the stirring blade is widened, and the stirring efficiency is lowered, and a certain quality cannot be obtained by manufacturing under the same conditions. There is also the problem of frequent replacement of parts in order to prevent such situations.

In order to solve this problem, there is a method in which only spherical alumina powder is used. However, in order to achieve high heat conduction, it is necessary to fill a large amount of alumina compared to amorphous alumina, and the viscosity of the composition is increased to deteriorate workability. Further, since the amount of polyfluorene oxide in the composition and the cured product thereof is relatively reduced, the hardness is increased and the compressibility is poor. Furthermore, since the theoretical specific gravity of alumina is 3.98, it is quite heavy, so when a large amount of alumina is filled, the specific gravity of the composition and the cured product increases. In recent years, electronic devices have been reduced in size and weight, and in order to reduce the weight of electronic devices as a whole, it is required to be more lightweight in units of grams or milligrams under maintenance performance when viewed in parts. The large amount of filling of alumina is also disadvantageous from the viewpoint of weight reduction.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-47-32400

[Patent Document 2] JP-A-56-100849

[Patent Document 3] Japanese Patent Laid-Open No. Hei 1-61661

[Patent Document 4] JP-A-4-328163

[Patent Document 5] JP-A-2-196453

[Patent Document 6] JP-A-H07-266356

[Patent Document 7] JP-A-8-238707

[Patent Document 8] Japanese Patent Publication No. 9-1738

[Patent Document 9] JP-A-9-296114

The present invention has been made in view of the above circumstances, and an object thereof is to provide a compressibility, an insulating property, a thermal conductivity, and a processability, and in particular, a thermal conductivity of 3.0 W/mK or more is suitable for, for example, heat generation in an electronic device. A thermally conductive polyxanthine composition and a cured product thereof as a thermally conductive resin molded body for heat dissipation between a component and a heat dissipating component.

As a result of conducting a positive review to achieve the above object, the present inventors have found that the above problems can be solved by using a combination of amorphous alumina having an average particle diameter of 10 to 30 μm and spherical alumina having an average particle diameter of 30 to 85 μm in a specific ratio. . That is, by using an amorphous alumina having an average particle diameter of 10 to 30 μm, heat conductivity can be effectively improved, the specific gravity can be suppressed, and the group can be increased. The proportion of polyoxygen in the middle can promote the appearance of rubber properties. Further, by using spherical alumina having an average particle diameter of the same or higher than that of the amorphous alumina, the fluidity of the composition can be improved and the workability can be improved. Further, the abrasion of the reaction vessel or the stirring blade can be suppressed, and the insulation property can be improved.

That is, it has been found that the disadvantages of the amorphous alumina are compensated by the spherical alumina, and the disadvantages of the spherical alumina are compensated by the amorphous alumina, so that the compressibility, the insulating property, the thermal conductivity, and the workability are excellent, especially It is a thermally conductive polyfluorene composition having a thermal conductivity of 3.0 W/mK or more and a cured product, and thus the present invention has been completed.

Accordingly, the present invention provides the following thermally conductive polydecane oxide composition and cured product thereof.

[1]

A thermally conductive polydecane oxygen composition characterized by: (A) an organopolyoxyalkylene having at least two alkenyl groups in one molecule: 100 parts by mass, (B) having at least two directly bonded to a ruthenium atom The organic hydrogen polyoxyalkylene of a hydrogen atom: the molar number of the hydrogen atom directly bonded to the halogen atom is 0.1 to 5.0 times the number of moles of the alkenyl group derived from the component (A), and (C) heat conduction Filling material: 1,200-6,500 parts by mass, (D) Platinum group metal-based hardening catalyst: 0.1 to 2,000 ppm based on the mass of the platinum group metal element (A), and the thermal conductive filler of the component (C) It is made of the following components: (Ci) 500 to 1,500 parts by mass of amorphous alumina having an average particle diameter of 10 to 30 μm. (C-ii) 150 to 4,000 parts by mass of spherical alumina having an average particle diameter of 30 to 85 μm, and (C-iii) 500 to 2,000 parts by mass of an insulating inorganic filler having an average particle diameter of 0.1 to 6 μm.

[2]

The thermally conductive polyfluorene composition according to the above [1], further comprising (F-1) an alkoxydecane compound represented by the following formula (1) as (F) component and (F-2) At least one selected from the group consisting of a dimethyloxypolyoxane terminated with a trialkoxyalkylene group at a single terminal of the molecular chain represented by the following formula (2): 100 parts by mass relative to the component (A) Containing 0.01 to 300 parts by mass of R ¹ _a R ² _b Si(OR ³ ) _4-ab (1) (wherein R ^{1 is} independently an alkyl group having 6 to 15 carbon atoms, and R ^{2 is} independently unsubstituted or Substituted ones having 1 to 12 carbon atoms, R ^{3 is} independently an alkyl group having 1 to 6 carbon atoms, a is an integer from 1 to 3, and b is an integer from 0 to 2, but a+b is 1~ 3 integer), (wherein R ^{4 is} independently an alkyl group having 1 to 6 carbon atoms, and c is an integer of 5 to 100).

[3]

The thermally conductive polyfluorene composition according to the above [1] or [2], which further contains 0.1 to 100 parts by mass of the component (G) as the component (G), and has the following formula ( 3) an organic polyoxane having an kinetic viscosity at 23 ° C of 10 to 100,000 mm ² /s, (wherein R ^{5 is} independently a hydrocarbon group having 1 to 12 carbon atoms and no aliphatic unsaturated bond, and d is an integer of 5 to 2,000).

[4]

The thermally conductive polyfluorene composition according to any one of [1] to [3], which has a viscosity at 23 ° C of 800 Pa. s below.

[5]

A thermally conductive polysulfonated cured product obtained by curing the thermally conductive polydecane oxide composition according to any one of [1] to [4].

[6]

The thermally conductive polyanion cured product according to [5], which has a thermal conductivity of 3.0 W/mK or more.

[7]

The thermally conductive polyanthracene hardened material as described in [5] or [6] has a hardness of 60 or less as measured by an Asker C hardness meter.

[8]

The thermally conductive polyanthracene hardened material according to any one of the items [5] to [7], wherein the dielectric breakdown voltage is 10 kV/mm or more.

The thermally conductive polyfluorene oxide composition of the present invention is made up of spherical alumina by using amorphous alumina having an average particle diameter of 10 to 30 μm and spherical alumina having an average particle diameter of 30 to 85 μm in a specific ratio. The disadvantage of amorphous alumina, and the disadvantage of amorphous alumina to make up the spherical alumina, can provide excellent compressibility, insulation, thermal conductivity, and processability, especially thermal conductivity with thermal conductivity of 3.0 W/mK or more. Polyoxygenated hardened material.

The thermally conductive polyxanthene composition of the present invention contains the following as an essential component: (A) an alkenyl group-containing organopolyoxane, (B) an organic hydrogen polyoxyalkylene, (C) a thermally conductive filler, and (D) Platinum group metal-based hardening catalyst.

[Alkenyl group-containing organic polyoxane]

The alkenyl group-containing organopolyoxane of the component (A) is an organopolysiloxane having two or more alkenyl groups bonded to a ruthenium atom in one molecule, and is a thermally conductive polyanthracene of the present invention. The main agent. Usually the main chain Partially consists of repeating units of diorganooxane units, but these may also be those having a branched structure in one part of the molecular structure, and may also be a ring body, but the mechanical strength of the hardened material, etc. In terms of physical properties, a linear diorganopolyoxyalkylene is preferred.

The functional group bonded to the alkenyl group of the ruthenium atom is an unsubstituted or substituted one-valent hydrocarbon group, and is exemplified by, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group. An alkyl group such as a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group or a dodecyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cycloheptyl group; An aryl group such as an aryl group such as a tolyl group, a xylyl group, a naphthyl group or a biphenyl group; an aralkyl group such as a benzyl group, a phenethyl group, a phenylpropyl group or a methylbenzyl group; and a bond of a carbon atom in the group; a group in which a part or all of a hydrogen atom is substituted with a halogen atom such as fluorine, chlorine or bromine, a cyano group or the like, such as chloromethyl, 2-bromoethyl, 3-chloropropyl, 3,3,3-trifluoropropane. a group, a chlorophenyl group, a fluorophenyl group, a cyanoethyl group, a 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, etc., and a representative one having a carbon number of 1 to 10, The most representative ones are those having 1 to 6 carbon atoms, preferably methyl, ethyl, propyl, chloromethyl, bromoethyl, 3,3,3-trifluoropropyl, cyanoethyl, etc. Unsubstituted or substituted alkyl group having 1 to 3 carbon atoms, and unsubstituted phenyl, chlorophenyl or fluorophenyl groups The phenyl or substituted. Further, the functional groups other than the alkenyl group bonded to the ruthenium atom are not limited to being all the same.

Further, the alkenyl group is, for example, an alkenyl group having a usual carbon number of from 2 to 8 such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group or a cyclohexenyl group. A lower alkenyl group such as a vinyl group or an allyl group is preferred, and a vinyl group is particularly preferred. Also, the alkenyl group preferably has two in the molecule In the above, in order to obtain good flexibility of the obtained cured product, it is preferred to bond only to the ruthenium atom at the end of the molecular weight.

The organic polysiloxane has an kinetic viscosity at 23 ° C of usually 10 to 100,000 mm ² /s, preferably 500 to 50,000 mm ² /s. When the viscosity is too low, the storage stability of the obtained composition may be deteriorated, and if it is too high, the stretchability of the obtained composition may be deteriorated. Further, the dynamic viscosity is a value measured by an Ostwald viscometer (the same applies hereinafter).

The organopolyoxane of the component (A) may be used singly or in combination of two or more kinds having different viscosities.

[organic hydrogen polyoxyalkylene]

The organic hydrogen polyoxymethane of the component (B) is an organic hydrogen polyoxyalkylene having an average of two or more, preferably 2 to 100, hydrogen atoms (Si-H groups) directly bonded to the ruthenium atom in one molecule. It is a component which acts as a crosslinking agent of (A) component. In other words, the Si-H group in the component (B) and the alkenyl group in the component (A) are added by a hydroquinone alkylation reaction promoted by a platinum group metal-based curing catalyst of the component (D) described later. A three-dimensional mesh structure having a crosslinked structure. Further, when the number of Si-H groups is less than two, it cannot be hardened.

The organohydrogen polyoxyalkylene is represented by the following average structural formula (4), but is not limited thereto.

(wherein R ^{6 is} independently a hydrogen atom or an unsubstituted or substituted one-valent hydrocarbon group which does not contain an aliphatic unsaturated bond, but at least two, preferably 2 to 10 are hydrogen atoms, and e is an integer of 1 or more , preferably an integer from 10 to 200).

In the formula (4), an unsubstituted or substituted monovalent hydrocarbon group other than a hydrogen atom of R ^{6 which} does not contain an aliphatic unsaturated bond is exemplified by, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a different group. An alkyl group such as a butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group or a dodecyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or the like. An aryl group such as a cycloalkyl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group or a biphenyl group; an aralkyl group such as a benzyl group, a phenethyl group, a phenylpropyl group or a methylbenzyl group; and the like a group in which a part or all of a hydrogen atom to which a carbon atom is bonded is substituted with a halogen atom such as fluorine, chlorine or bromine, a cyano group or the like, such as a chloromethyl group, a 2-bromoethyl group, a 3-chloropropyl group, or a 3,3 group. , 3-trifluoropropyl, chlorophenyl, fluorophenyl, cyanoethyl, 3,3,4,4,5,5,6,6,6-hexafluorohexyl, etc., representative of carbon atoms The number of 1 to 10, the most representative ones are those having 1 to 6 carbon atoms, preferably methyl, ethyl, propyl, chloromethyl, bromoethyl, 3,3,3-trifluoropropyl. An unsubstituted or substituted alkyl group having 1 to 3 carbon atoms such as a cyanoethyl group, and a phenyl group, a chlorophenyl group, a fluorophenyl group, or the like. Of an unsubstituted or substituted phenyl. Further, R ^{6 is} not limited to all the same.

The amount of the component (B) added is such that the Si-H group derived from the component (B) is 0.1 to 5.0 moles, preferably 0.3 to 2.0 moles, based on the alkenyl group 1 mole derived from the component (A). The amount of the ear is preferably 0.5 to 1.0 mole. The amount of the Si-H group derived from the component (B) cannot be hardened when the alkenyl group 1 derived from the component (A) is less than 0.1 mol, or cannot be maintained due to insufficient strength of the cured product. There is a case where the shape of the molded body is unworkable. Further, when it exceeds 5.0 mol, the softness of the cured product disappears and the cured product becomes brittle.

[thermal conductive filler]

The thermally conductive filler of the component (C) is mainly composed of the following (C-i) to (C-iii) components.

(C-i) an amorphous alumina having an average particle diameter of 10 to 30 μm, (C-ii) a spherical alumina having an average particle diameter of 30 to 85 μm, and (C-iii) an insulating inorganic filler having an average particle diameter of 0.1 to 6 μm.

Further, in the present invention, the average particle diameter is a value of a cumulative average particle diameter (median diameter) based on a volume basis measured by a particle size analyzer Microtrack MT3300EX manufactured by a Japanese machine.

The amorphous alumina of the (C-i) component can further increase the thermal conductivity. The average particle diameter of the amorphous alumina is 10 to 30 μm, preferably 15 to 25 μm. When the average particle diameter is less than 10 μm, the effect of improving the thermal conductivity is lowered, and the viscosity of the composition is increased, and the workability is deteriorated. Further, when the average particle diameter is more than 30 μm, the abrasion of the reaction vessel or the stirring blade is remarkable, and the insulation of the composition is lowered. The amorphous alumina of the component (C-i) may be used alone or in combination of two or more. Further, as the amorphous alumina, a general commercial product can be used.

The spherical alumina of the component (C-ii) increases the thermal conductivity of the composition while suppressing the contact of the amorphous alumina with the reaction vessel or the stirring blade, thereby providing a barrier effect of suppressing abrasion. The average particle diameter is 30 to 85 μm, preferably 40 to 80 μm. When the average particle diameter is less than 30 μm, the barrier effect is lowered, and the abrasion of the reaction vessel or the stirring blade due to the amorphous particles is remarkable. On the other hand When the average particle diameter is more than 85 μm, the alumina in the composition tends to settle easily, and the uniformity of the composition is impaired. The spherical alumina of the component (C-ii) may be used singly or in combination of two or more. Further, as the spherical alumina, a general commercial product can be used.

The insulating inorganic filler of the component (C-iii) also serves to improve the thermal conductivity of the composition, but its main role is to adjust the viscosity of the composition, prevent sedimentation, improve slidability, and improve filling. In addition, it also plays a role in coloring, improvement in flame retardancy, improvement in strength, and improvement in compression set. In order to ensure the insulation of the composition, it is necessary for the filler to have insulation. The average particle diameter of the component (C-iii) is 0.1 to 6 μm, and it is preferably 0.5 to 4 μm in order to exhibit the above characteristics. When the average particle diameter is less than 0.1 μm, the viscosity of the composition is remarkably large, and the formability is largely impaired. Further, when the average particle diameter is more than 6 μm, the slidability of the composition is impaired, and the sedimentation of the filler proceeds rapidly, so that the thermal conductivity of the molded body and the formability of the composition are impaired.

As the insulating inorganic filler of the component (C-iii), for example, alumina other than the above (Ci) and (C-ii) components, cerium oxide, magnesium oxide, red iron oxide, cerium oxide, titanium oxide, or zirconia can be used. Metal oxides such as aluminum nitride, tantalum nitride, boron nitride, metal hydroxides such as aluminum hydroxide or magnesium hydroxide, artificial diamonds, etc., and the shapes may be spherical or In order to be indefinite, one type or a combination of two or more types may be used. Further, as the insulating inorganic filler, a general commercial product can be used.

The blending amount of the component (C-i) is 500 to 1,500 parts by mass, preferably 700 to 1,200 parts by mass, per 100 parts by mass of the component (A). Too little thermal conductivity is difficult to increase, too much composition loses fluidity, damages forming Sex. Further, the abrasion of the reaction vessel or the stirring blade is remarkable, and the insulation of the composition is lowered.

The blending amount of the component (C-ii) is 150 to 4,000 parts by mass, preferably 200 to 3,000 parts by mass, per 100 parts by mass of the component (A). When the amount is too small, the improvement of the thermal conductivity is difficult. When too much, the composition loses fluidity and the formability is impaired.

The blending amount of the component (C-iii) is 500 to 2,000 parts by mass, preferably 600 to 1,800 parts by mass, per 100 parts by mass of the component (A). When the amount is too small, the slidability of the composition is impaired, and the sedimentation of the filler proceeds rapidly, thereby impairing the thermal conductivity of the molded body and the formability of the composition. When too much, the viscosity of the composition is remarkably large, and the formability is greatly impaired.

In addition, the amount of the component (C) (that is, the total amount of the components (Ci) to (C-iii)) is required to be 1,200 to 6,500 parts by mass, preferably 1,500, per 100 parts by mass of the component (A). ~5,500 parts by mass. When the amount is less than 1,200 parts by mass, the thermal conductivity of the obtained composition is deteriorated, and the viscosity of the composition is extremely low viscosity, which is a lack of storage stability. When the amount exceeds 6,500 parts by mass, the composition lacks stretchability and becomes hardness. A molded product that is high and weak.

By using the component (C) in the above-mentioned blending ratio, the effects of the above-described invention can be more advantageously and surely achieved.

[Platinum group metal-based hardening catalyst]

The platinum group metal-based curing catalyst of the component (D) is a catalyst for promoting an addition reaction of an alkenyl group derived from the component (A) and a Si-H group derived from the component (B), and is exemplified as a hydroquinone alkyl group. It is known to use the catalyst for the reaction. Specific examples thereof include platinum group metal monomers such as platinum (including platinum black), ruthenium, and palladium, and H ₂ PtCl ₄ . nH ₂ O, H ₂ PtCl ₆ . nH ₂ O, NaHPtCl ₆ . nH ₂ O, KaHPtCl ₆ . nH ₂ O, Na ₂ PtCl ₆ . nH ₂ O, K ₂ PtCl ₄ . nH ₂ O, PtCl ₄ . nH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ . nH ₂ O (however, n is an integer of 0 to 6, preferably 0 or 6), such as platinum chloride, chloroplatinic acid and chloroplatinate, and alcohol-modified platinum chloride ( Refer to the specification of U.S. Patent No. 3,220,972, the chloroplatinic acid and olefin complexes (refer to the specification of U.S. Patent No. 3,159,601, the specification of U.S. Patent No. 3,159,662, the specification of U.S. Patent No. 3,775,452), such as platinum black, palladium, etc. The platinum group metal is supported on a support such as alumina, ceria, or carbon, a ruthenium-olefin complex, a chloroform (triphenylphosphine) ruthenium (Wilkinson catalyst), and a platinum chloride. And a platinum chloride acid or a platinum chloride salt and a vinyl group-containing decane, especially a complex of a vinyl group-containing cyclic siloxane.

The amount of the component (D) to be used is 0.1 to 2,000 ppm, preferably 50 to 1,000 ppm, based on the mass of the platinum group metal element of the component (A).

[Reaction Control Agent]

The thermally conductive polyfluorene composition of the present invention may further use an addition reaction controlling agent as the component (E). As the addition reaction controlling agent, a conventional addition reaction controlling agent used in a general addition reaction hardening type polyoxo composition can be used. For example, it is an acetylene compound such as 1-ethynyl-1-hexanol, 3-butyn-1-ol, ethynylmethylene carbitol, or various nitrogen compounds, organophosphorus compounds, hydrazine compounds, organochlorine compounds, and the like. .

The amount of the component (E) to be used is preferably 0.01 to 1 part by mass, more preferably about 0.1 to 0.8 part by mass, per 100 parts by mass of the component (A). When the amount of the mixture is too large, the hardening reaction cannot be performed, which may impair the forming efficiency.

[surface treatment agent]

In the thermally conductive polyanthracene composition of the present invention, in order to prepare the heat conductive filler of the component (C) by hydrophobization during preparation of the composition, the wettability of the organopolyoxyalkylene of the component (A) is improved. The thermally conductive filler of the component (C) is uniformly dispersed in a matrix formed of the component (A), and a surface treatment agent of the component (F) is formulated. The component (F) is preferably a component (F-1) and a component (F-2) shown below.

The component (F-1) is an alkoxydecane compound represented by the following formula (1).

R ¹ _a R ² _b Si(OR ³ ) _4-ab (1)

(wherein R ^{1 is} independently an alkyl group having 6 to 15 carbon atoms, and R ^{2 is} independently an unsubstituted or substituted hydrocarbon group having 1 to 12 carbon atoms, and R ^{3 is} independently a carbon number of 1 to 6 Alkyl, a is an integer from 1 to 3, and b is an integer from 0 to 2, but a+b is an integer from 1 to 3.

In the above formula (1), the alkyl group represented by R ¹ is exemplified by, for example, a hexyl group, an octyl group, a decyl group, a decyl group, a dodecyl group, a tetradecyl group or the like. When the number of carbon atoms of the alkyl group represented by R ¹ is in the range of 6 to 15, the wettability of the component (A) is sufficiently improved, the handleability is good, and the low-temperature characteristics of the composition are good.

The unsubstituted or substituted one-valent hydrocarbon group represented by R ² is exemplified by, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl. An alkyl group such as heptyl, octyl, decyl, decyl or dodecyl, a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cycloheptyl group, a phenyl group, a tolyl group, a xylyl group or a naphthyl group. An aryl group such as a biphenyl group, an aralkyl group such as a benzyl group, a phenethyl group, a phenylpropyl group or a methylbenzyl group, and a part or all of a hydrogen atom bonded to a carbon atom of the group is partially or partially fluorine-containing. a halogen atom such as chlorine or bromine, or a substituted group such as a cyano group, such as chloromethyl, 2-bromoethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, chlorophenyl or fluorophenyl. Cyanoethyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, etc., representative of the number of carbon atoms 1 to 10, the most representative is the number of carbon atoms ~6, preferably methyl, ethyl, propyl, chloromethyl, bromoethyl, 3,3,3-trifluoropropyl, cyanoethyl, etc., unsubstituted with 1 to 3 carbon atoms Or a substituted alkyl group, and an unsubstituted or substituted phenyl group such as a phenyl group, a chlorophenyl group, a fluorophenyl group or the like. R ^{3 is} exemplified by methyl, ethyl, propyl, butyl, hexyl and the like.

The component (F-2) is a dimethylpolyoxane terminated with a trialkoxyalkylene group at the end of the molecular chain represented by the following formula (2).

(wherein R ^{4 is} independently an alkyl group having 1 to 6 carbon atoms, and c is 5 to 100, preferably 5 to 70, more preferably an integer of 10 to 50).

In the above formula (2), the alkyl group represented by R ⁴ may be the same as the alkyl group represented by R ³ in the above formula (1).

The surface treatment agent of the component (F) may be blended with either the (F-1) component or the (F-2) component.

The amount of the component (F) to be blended is preferably from 0.01 to 300 parts by mass, more preferably from 0.1 to 200 parts by mass, per 100 parts by mass of the component (A). When the proportion of this component is large, there is a possibility of inducing oil separation.

[Organic Polyoxane]

In order to impart characteristics such as viscosity adjustment of the thermally conductive polyfluorene composition, the thermal conductive polyfluorene composition of the present invention may have a dynamic viscosity at 23 ° C represented by the following general formula (3) as a component (G). 10~100,000mm ² /s organic polyoxygen,

(wherein R ^{5 is} independently a hydrocarbon group having 1 to 12 carbon atoms and no aliphatic unsaturated bond, and d is an integer of 5 to 2,000). The component (G) may be used alone or in combination of two or more.

In the above formula (3), R ^{5 is} independently an unsubstituted or substituted one-valent hydrocarbon group having 1 to 12 carbon atoms and having no aliphatic unsaturated bond. R ^{5 is} exemplified by, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, decyl, fluorene. An alkyl group such as a cycloalkyl group, a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cycloheptyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group or a biphenyl group; An aralkyl group such as phenethyl, phenylpropyl or methylbenzyl, and a part or all of a hydrogen atom bonded to a carbon atom of the group are substituted by a halogen atom such as fluorine, chlorine or bromine, or a cyano group. a group such as chloromethyl, 2-bromoethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, chlorophenyl, fluorophenyl, cyanoethyl, 3,3,4, 4,5,5,6,6,6-nonafluorohexyl, etc., representatively having a carbon number of 1 to 10, the most representative ones having a carbon number of 1 to 6, preferably a methyl group An unsubstituted or substituted alkyl group having 1 to 3 carbon atoms, such as ethyl, propyl, chloromethyl, bromoethyl, 3,3,3-trifluoropropyl or cyanoethyl, and benzene The unsubstituted or substituted phenyl group such as a chlorophenyl group or a fluorophenyl group is preferably a methyl group or a phenyl group.

The above d is preferably an integer of 5 to 2,000, preferably an integer of 10 to 1,000, based on the viewpoint of the desired viscosity.

Further, the dynamic viscosity of the component (G) at 23 ° C is preferably from 10 to 100,000 mm ² /s, preferably from 100 to 10,000 mm ² /s. When the dynamic viscosity is less than 10 mm ² /s, the cured product of the obtained composition is liable to seep. When the dynamic viscosity is more than 100,000 mm ² /s, the resulting thermally conductive polyfluorene composition tends to be inferior in flexibility.

When the component (G) is added to the thermally conductive polyfluorene composition of the present invention, the amount thereof to be added is not particularly limited as long as it is a desired effect, but it is preferably 0.1 part by mass based on 100 parts by mass of the component (A). ~100 parts by mass, more It is preferably 1 to 50 parts by mass. When the amount of addition is within this range, the thermally conductive polyfluorene composition before curing tends to maintain good fluidity and workability, and the thermally conductive filler of the component (C) is easily filled in the composition.

[Other ingredients]

In the thermally conductive polyfluorene composition of the present invention, other components may be further blended within the range not impairing the object and the effects of the present invention. For example, it is possible to adjust a heat resistance improving agent such as iron oxide or cerium oxide; a viscosity adjusting agent such as cerium oxide; a coloring agent; and an optional component such as a releasing agent.

[Modulation of thermally conductive polyfluorene composition]

The thermally conductive polyfluorene composition of the present invention can be prepared by uniformly mixing the above components in accordance with a conventional method.

[Viscosity of composition]

The viscosity of the thermally conductive polyfluorene composition of the present invention is 800 Pa at 23 ° C. Below s, preferably 700Pa. s below. When the viscosity is too high, the formability is impaired. Further, in the present invention, the viscosity is based on a B-type viscosity meter.

[Manufacturing method of thermally conductive polyfluorene cured product]

The curing conditions for forming the thermally conductive polydecane oxide composition may be the same as those of the conventional addition reaction-curable polyoxyxene rubber composition. For example, the curing can be sufficiently cured at normal temperature, but it may be heated as needed. Better in 100~120 °C Hardened for 8~12 minutes. Thus, the polyoxygenated hardened material of the present invention is excellent in thermal conductivity.

[The thermal conductivity of the molded body]

The thermal conductivity of the molded article (thermally conductive polysulfide cured product) of the present invention is preferably 3.0 W/mK or more, preferably 4.0 W/mK or more, as measured by a hot disc method at 25 °C. When the thermal conductivity is less than 3.0 W/mK, there is a case where it cannot be applied to a heating element having a large amount of heat. Further, the thermal conductivity can be adjusted by adjusting the type of the thermally conductive filler or a combination of the particle diameters.

[Insulation breakdown voltage of molded body]

The dielectric breakdown voltage of the molded article of the present invention is preferably 10 kV or more, more preferably 13 kV or more, in accordance with JIS K 6249, when the dielectric breakdown voltage of a molded body having a thickness of 1 mm is measured. When the insulation damage voltage is 10 kV/mm or less, it is difficult to ensure stable insulation during use. Moreover, the dielectric breakdown voltage can be adjusted by adjusting the type or purity of the filler.

[hardness of formed body]

The hardness of the molded article of the present invention is 60 or less, preferably 40 or less, more preferably 30 or less, and more preferably 5 or more, as measured by an Asker C hardness meter at 25 °C. When the hardness exceeds 60, the shape of the heat dissipating body cannot be deformed, and it is not possible to apply stress to the heat dissipating body, and it is difficult to exhibit good heat dissipation characteristics. Also, the hardness can be changed by (A) The ratio of the component to the component (B) is adjusted to adjust the crosslinking density.

[Examples]

The present invention will be specifically described below by showing examples and comparative examples, but the present invention is not limited to the following examples. Further, the dynamic viscosity was measured at 23 ° C using an Ostwald viscometer. Further, the average particle diameter is a value of a cumulative average particle diameter (median diameter) of a volume basis measured by a particle size analyzer Microtrack MT3300EX manufactured by Nikkiso Co., Ltd.

The components (A) to (F) used in the following examples and comparative examples are shown below.

(A) Ingredients:

An organopolyoxane represented by the following formula (5).

(wherein X is a vinyl group and f is a number of the following viscosity).

(A-1) Dynamic viscosity: 600mm ² / s

(A-2) Dynamic viscosity: 30,000 mm ² /s

(B) Ingredients:

An organohydrogenpolyoxyalkylene represented by the following formula (6).

(wherein g is 28 and h is 2).

(C) ingredients:

The average particle diameter is as follows: amorphous alumina, spherical alumina, and amorphous aluminum hydroxide.

(C-1) Amorphous aluminum hydroxide having an average particle diameter of 1 μm

(C-2) Unshaped alumina having an average particle diameter of 1.5 μm

(C-3) Spherical alumina having an average particle diameter of 1.5 μm

(C-4) Unshaped alumina having an average particle diameter of 3.6 μm

(C-5) Unshaped alumina having an average particle diameter of 18 μm

(C-6) Unshaped alumina having an average particle diameter of 50 μm

(C-7) Spherical alumina having an average particle diameter of 17 μm

(C-8) Spherical alumina having an average particle diameter of 45 μm

(C-9) Spherical alumina having an average particle diameter of 70 μm

(D) Ingredients:

5 mass% of a solution of chloroplatinic acid 2-ethylhexanol.

(E) Ingredients:

Ethylene methylene carbitol is used as an addition reaction controlling agent.

(F) component: (F-2) component

A dimethylpolyoxane terminated with a trimethoxydecyl group at a single terminal end, which has an average degree of polymerization of 30, represented by the following formula (7).

(G) component

The plasticizer is dimethyl polyoxyalkylene represented by the following formula (8).

(where j is 80).

[Examples 1 to 3, Comparative Examples 1 to 3]

In Examples 1 to 3 and Comparative Examples 1 to 3, the components (A) to (G) were prepared by using the specific amounts shown in Table 1 below, and were subjected to work hardening, and were measured according to the following methods. Or observe the viscosity of the composition, the thermal conductivity of the hardened material, the hardness, the dielectric breakdown voltage, the specific gravity, and the wear of the reactor. The results are shown in Table 1.

[modulation of composition]

Specific examples shown in Examples 1 to 3 and Comparative Examples 1 to 3 of Table 1 below The components (A), (C), (F), and (G) were added in an amount and kneaded in a planetary kneader for 60 minutes.

Then, the components (D) and (E) were added thereto in the specific amounts shown in the following Examples 1 to 3 and Comparative Examples 1 to 3, and then an effective amount of the phenyl group manufactured by Shin-Etsu Chemical Co., Ltd. was added. The KF-54 of the polyoxygenated oil was used as a promoter to add a release agent to the release sheet of the separator, and kneaded for 30 minutes.

Next, the component (B) was added thereto in the specific amounts shown in Examples 1 to 3 and Comparative Examples 1 to 3 of the following Table 1, and kneaded for 30 minutes to obtain a composition.

[Forming method]

The compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were placed in a mold of 60 mm × 60 mm × 6 mm, and molded at 120 ° C for 10 minutes using a press molding machine.

[Evaluation method]

Viscosity of the composition:

The viscosities of the compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were measured under a 23 ° C environment using a B-type viscometer.

Thermal conductivity:

The composition obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was cured into a sheet having a thickness of 6 mm by using a press molding machine at 120 ° C for 10 minutes, and two sheets of the sheet were used as a thermal conductivity meter ( Trade name: TPA-501, manufactured by Kyoto Electronics Industry Co., Ltd.) The thermal conductivity of the sheet was measured.

hardness:

The compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were cured into a sheet having a thickness of 6 mm in the same manner as above, and the sheets were stacked and measured by an Asker C hardness meter.

Insulation breakdown voltage:

The composition obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was cured into a sheet having a thickness of 1 mm by a press molding machine at 120 ° C for 10 minutes, and the dielectric breakdown voltage was measured in accordance with JIS K 6249.

proportion:

The composition obtained in Examples 1 to 3 and Comparative Examples 1 to 3 was cured into a sheet having a thickness of 1 mm by a press molding machine at 120 ° C for 10 minutes, and the specific gravity of the cured product was measured by a water displacement method.

The abrasion of the reactor:

According to the above-described modulation method, at the stage of modulating the composition, if it is confirmed that the black component of the reactor planer is mixed, it is marked as "Yes", and if it is not confirmed, it is marked as "None". Since the alumina and aluminum hydroxide used in the examples and the comparative examples were white powders, the composition was originally white, so that the mixing of the black components was easy to see.

When the total mass portion of the thermally conductive filler of Comparative Example 1 exceeds 6,500 parts by mass, the wettability of the composition is insufficient, and the uniformity of the grease cannot be obtained. Composition. When the amorphous alumina having an average particle diameter of 10 to 30 μm containing no (C-i) component of Comparative Example 2 was observed, a decrease in thermal conductivity or an increase in hardness was observed. When the amorphous alumina having an average particle diameter of more than 30 μm (that is, a thermally conductive filler other than the components (Ci) to (C-iii)) was used as in Comparative Example 3, the abrasion of the reactor was remarkably observed, and The effect is that the dielectric breakdown voltage of the formed sheet is significantly reduced.

When the amount of the component (C) is in the range of 1,200 to 6,500 parts by mass relative to 100 parts by mass of the component (A), and the component (C) is composed of the following composition, the viscosity of the composition and the heat conduction of the cured product are as described in the examples. The rate, hardness, specific gravity, and dielectric breakdown voltage were all good results, and no abrasion of the reactor was observed. (Ci) 500 to 1,500 parts by mass of amorphous alumina having an average particle diameter of 10 to 30 μm, (C-ii) 150 to 4,000 parts by mass of spherical alumina having an average particle diameter of 30 to 85 μm, and (C-iii) 500 to 2,000 parts by mass of an insulating inorganic filler having an average particle diameter of 0.1 to 6 μm.

Claims (8)

A thermally conductive polydecane oxygen composition characterized by: (A) an organopolyoxyalkylene having at least two alkenyl groups in one molecule: 100 parts by mass, (B) having at least two directly bonded to a ruthenium atom The organic hydrogen polyoxyalkylene of a hydrogen atom: the molar number of the hydrogen atom directly bonded to the halogen atom is 0.1 to 5.0 times the number of moles of the alkenyl group derived from the component (A), and (C) heat conduction Filling material: 1,200-6,500 parts by mass, (D) Platinum group metal-based hardening catalyst: 0.1 to 2,000 ppm based on the mass of the platinum group metal element (A), and the thermal conductive filler of the component (C) It is made up of (Ci) 500 to 1,500 parts by mass of amorphous alumina having an average particle diameter of 10 to 30 μm, and (C-ii) 150 to 4,000 parts by mass of spherical alumina having an average particle diameter of 30 to 85 μm. C-iii) 500 to 2,000 parts by mass of the insulating inorganic filler having an average particle diameter of 0.1 to 6 μm. The thermally conductive polyfluorene composition of claim 1, which further comprises, as the component (F), an alkoxydecane compound represented by the following formula (1) and (F-2) as (F): At least one selected from the group consisting of a monoalkyl end group having a monoalkyloxyalkylene group terminated by a trialkoxyalkylene group represented by the formula (2): 0.01% by mass based on 100 parts by mass of the component (A) 300 parts by mass, R ¹ _a R ² _b Si(OR ³ ) _4-ab (1) (wherein R ^{1 is} independently an alkyl group having 6 to 15 carbon atoms, and R ^{2 is} independently an unsubstituted or substituted carbon Atomic number 1 to 12 one-valent hydrocarbon group, R ^{3 is} independently an alkyl group having 1 to 6 carbon atoms, a is an integer of 1 to 3, b is an integer of 0 to 2, but a + b is an integer of 1 to 3 ), (wherein R ^{4 is} independently an alkyl group having 1 to 6 carbon atoms, and c is an integer of 5 to 100). The thermally conductive polyfluorene composition of claim 1, which further contains 0.1 to 100 parts by mass of the component (A) as the component (G) and is represented by the following formula (3) at 23 ° C. An organic polyoxane having a viscosity of 10 to 100,000 mm ² /s, (wherein R ^{5 is} independently a hydrocarbon group having 1 to 12 carbon atoms and no aliphatic unsaturated bond, and d is an integer of 5 to 2,000). The thermally conductive polyfluorene composition of claim 1, which has a viscosity of 800 Pa at 23 ° C. s below. A thermally conductive polysulfonated cured product obtained by hardening the thermally conductive polydecaneoxy composition according to any one of claims 1 to 4. The thermally conductive polyanthracene of claim 5 has a thermal conductivity of 3.0 W/mK or more. The thermally conductive polyanthracene hardened material of claim 5, which has a hardness of 60 or less as measured by an Asker C hardness meter. The thermally conductive polyanthracene hardened material of claim 5, which has an insulation breakdown voltage of 10 kV/mm or more.