JP6156337B2 - HEAT CONDUCTIVE SHEET AND METHOD FOR PRODUCING THE HEAT CONDUCTIVE SHEET - Google Patents

Description

  The present invention relates to a heat conductive sheet and a method for producing the heat conductive sheet.

  In recent years, the density of wiring on multilayer wiring boards and semiconductor packages has increased, the mounting density of electronic components has increased, and the integration of semiconductor elements has increased, resulting in greater heat generation per unit area. It is becoming desirable to improve

  2. Description of the Related Art Generally, a heat dissipation device that dissipates heat by using a heat conductive grease or a heat conductive sheet and sandwiching it between a heat generator such as a semiconductor package and a heat radiator such as aluminum or copper is generally used. However, the thermal conductive sheet is superior to the thermal conductive grease in workability when assembling the heat dissipation device. In order to improve heat dissipation, the heat conductive sheet is required to have high heat conductivity, but the heat conductivity of the conventional heat conductive sheet is not necessarily sufficient.

  Therefore, in order to further improve the thermal conductivity of the thermal conductive sheet, various thermal conductive composite compositions and molded products obtained by mixing high thermal conductivity graphite powder, boron nitride, etc. in the matrix material are proposed. Has been.

There has been reported a heat conductive sheet in which a heat conductive material is oriented in a direction perpendicular to the sheet surface in a matrix material to improve the heat conductivity in the film thickness direction (for example, Patent Documents 1 and 2). .
Patent Document 1 discloses a heat conductive sheet in which an inorganic filler (boron nitride) 10 is oriented in a direction substantially perpendicular to the sheet surface 1 as shown in FIG.
Patent Document 2 describes a structure in which carbon fibers dispersed in a gel material are oriented perpendicular to the sheet surface.

Japanese Patent Laid-Open No. 2002-26202 JP 2005-82721 A

  However, in either case of Patent Document 1 or Patent Document 2, since the thermally conductive inorganic material is exposed on the sheet surface, the adhesiveness (tackiness) of the surface is low, and the heat generator and the heat radiator such as aluminum or copper There is a point that workability is poor because it is difficult to temporarily fix in the mounting process.

In Patent Document 1, in order to avoid this, a step of impregnating a plasticizer after slicing is provided. However, although the binder resin is softened and tackiness is improved, there is a problem that the strength of the sheet is lowered.
In addition, a kneaded product of an inorganic material and an organic material has a problem in that tensile strength is weak because peeling at an interface easily occurs and bubbles are also mixed.

  Furthermore, when a heat-dissipating sheet in which a thermally conductive inorganic material is oriented perpendicularly to the sheet surface is used between a heat-generating member and a heat-dissipating functional member such as a heat-dissipating fin, when pressure is applied in the mounting process, There is also a problem that the inorganic material is bent and the heat conduction performance is lowered.

  The object of the present invention is high thermal conductivity in the film thickness direction of the heat conductive sheet, and has both tackiness and strength that facilitate the mounting process, and is also a heat conductive inorganic material for pressure application in the mounting process. Is to provide a thermal conductive sheet that maintains thermal conductivity without buckling.

  Another object of the present invention is to provide a method for producing a heat conductive sheet having high heat conductivity in the film thickness direction of the heat conductive sheet and having both tackiness and strength that facilitate the mounting process.

  As a result of intensive studies, the present inventors have found that both the tack property and the heat conduction can be obtained by appropriately adjusting the orientation angle of the inorganic material with respect to the film thickness direction of the heat conduction sheet.

  The present invention relates to the following.

(1) A heat conductive sheet comprising a composition containing a heat conductive inorganic material in the form of a scale, oval, plate or rod, and an organic polymer compound, the surface direction of the scale of the inorganic material The heat conducting sheet in which the major axis direction of the ellipsoid, the major axis direction of the plate, or the major axis direction of the rod are oriented with an inclination relative to the thickness direction of the heat conducting sheet.

(2) The surface direction of the scale of the inorganic material, the long axis direction of the ellipse, the long axis direction of the plate, or the long axis direction of the rod is inclined within a range of 5 to 60 ° with respect to the thickness direction of the heat conductive sheet. The heat conductive sheet according to (1), which is oriented.

(3) The heat conductive sheet according to (1) or (2), wherein the heat conductive inorganic material having a scale shape, an oval shape, a plate shape, or a rod shape is graphite.

(4) The heat conductive sheet according to any one of (1) to (3), manufactured by a manufacturing method including the following steps (a) to (d):
(A) kneading the inorganic material and the organic polymer compound to prepare a composition;
(B) applying a pressure to the composition to produce a primary sheet oriented in a direction substantially parallel to the main surface of the inorganic material;
(C) a step of laminating the primary sheet to form a laminate,
(D) (A) The laminate is sliced at an angle of 5 to 60 ° with respect to the normal line coming out of the primary sheet surface to form a sheet, and (c) the laminate is formed. Any one of the above (a) to (c), in which a sheet is obtained by slicing at a substantially perpendicular angle with respect to the normal line coming out of the primary sheet surface and then roll-pressing. The process to perform.

(5) A method for producing a heat conductive sheet comprising the following steps (a) to (d).
(A) A step of preparing a composition by kneading a heat conductive inorganic material having a scale shape, an oval shape, a plate shape or a rod shape with an organic polymer compound.
(B) A step of applying a pressure to the composition to produce a primary sheet in which the inorganic material is oriented in a direction substantially parallel to a main surface.
(C) A step of laminating the primary sheets to form a laminate.
(D) (A) The laminate is sliced at an angle of 5 to 60 ° with respect to the normal line coming out of the primary sheet surface to form a sheet, and (c) the laminate is formed. Any one of the above (a) to (c), in which a sheet is obtained by slicing at a substantially perpendicular angle with respect to the normal line coming out of the primary sheet surface and then roll-pressing. The process to perform.

(6) A method for producing a heat conductive sheet including the following steps (a) to (d).
(A) A step of preparing a composition by kneading a heat conductive inorganic material having a scale shape, an oval shape, a plate shape or a rod shape with an organic polymer compound.
(B) A step of applying a pressure to the composition to produce a primary sheet in which the inorganic material is oriented in a direction substantially parallel to a main surface.
(C2) A step of winding the primary sheet with the orientation direction of the inorganic material as an axis to form a laminate.
(D) (A) The laminate is sliced at an angle of 5 to 60 ° with respect to the normal line coming out of the primary sheet surface to form a sheet, and (c) the laminate is formed. Any one of the above (a) to (c), in which a sheet is obtained by slicing at a substantially perpendicular angle with respect to the normal line coming out of the primary sheet surface and then roll-pressing. The process to perform.

  The heat conductive sheet of the present invention is highly heat conductive in the film thickness direction, has both tackiness and strength to facilitate the mounting process, and the heat conductive inorganic material is also resistant to pressure applied in the mounting process. It is possible to maintain thermal conductivity without bending.

It is one Example of this invention and shows what converted the black-and-white binarization of the cross-sectional photograph of a heat conductive sheet. The graph of the tack force comparison with the heat conductive sheet which is an Example of this invention and the heat conductive sheet of a comparative example is shown. The graph of the tensile strength comparison with the heat conductive sheet which is an Example of this invention and the heat conductive sheet of a comparative example is shown. The schematic cross section of the heat conductive sheet which is a conventional example and an inorganic filler is perpendicular to a sheet surface is shown. The figure which shows the normal line which comes out from the primary sheet | seat surface in the manufacturing method of the heat conductive sheet of this invention. The figure explaining the slicing method in the manufacturing method of the heat conductive sheet of this invention is shown. The figure explaining the slicing method in the manufacturing method of the heat conductive sheet of this invention is shown.

<Heat conduction sheet>
The heat conductive sheet of the present invention includes a composition containing a heat conductive inorganic material that is scale-like, oval, plate-like, or rod-like, and an organic polymer compound, and the surface direction of the scale of the inorganic material, The major axis direction of the ellipse, the major axis direction of the plate, or the major axis direction of the rod are oriented with an inclination with respect to the thickness direction of the heat conductive sheet.

  The thermally conductive inorganic material having a scale shape, an elliptical shape, a plate shape, or a rod shape is not limited to those listed below, but examples thereof include boron nitride, graphite, and carbon fiber.

  In the present invention, the “scale-like” refers to a thin and flat shape like a fish scale. “Oval shape” indicates an ellipsoidal shape obtained by rotating an ellipse like a rugby ball.

  “Plate-like” means that the particle shape is like a plate. Specifically, a plate having a ratio (a / c) of 1.5 or more in each direction in the c-axis direction perpendicular to the a-axis direction is defined as “plate shape” in the present invention.

  The “bar shape” indicates an elongated cylindrical shape or a prismatic shape. Any shape is anisotropic.

  Specific examples of boron nitride used in the present invention include “PT-110 (trade name)” (Momentive Performance Materials Japan Godo Kaisha, average particle size 45 μm), “HP-1 CAW (trade name)” ( Made of Mizushima alloy iron, average particle size 16 μm), “PT-110 Plus (trade name)” (made by Momentive Performance Materials Japan, average grain size 45 μm), “HP-1CA (trade name)” (made by Mizushima alloy iron) And an average particle diameter of 16 μm).

  Examples of the graphite used in the present invention include scaly graphite powder, artificial graphite powder, exfoliated graphite powder, acid-treated graphite powder, expanded graphite powder, carbon fiber flakes and other scaly, oval or rod-like graphite. It is done.

  Examples of the carbon fibers used in the present invention include pitch-based carbon fibers using pitch as a raw material, PAN-based carbon fibers using polyacrylonitrile as a raw material, and the like. Commercially available products include Raheama (manufactured by Teijin Limited), Trading Card (manufactured by Toray Industries, Inc.), Tenax (manufactured by Toho Tenax Co., Ltd.), Pyrofil (manufactured by Mitsubishi Rayon Co., Ltd.), DIALEAD (Mitsubishi) Resin Co., Ltd.), GRANOC (Nippon Graphite Fiber Co., Ltd.) and the like.

The size of the inorganic material used in the present invention is preferably selected according to the slice thickness in the slicing step in the method for producing a heat conductive sheet. For example, when the slice thickness is 0.25 mm, the average particle diameter Is preferably 250 to 1000 μm. More preferably, it is 300-600 micrometers.
More preferably, an inorganic material having an average particle diameter larger than the slice thickness is preferable.
In the present invention, the average particle size of the inorganic material is measured by the value of D50 when measured by the laser diffraction / scattering method.

  Although content in particular of the inorganic material used by this invention is not restrict | limited, It is preferable that it is 10-50 volume% of the total composition volume, and it is more preferable that it is 30-45 volume%.

  Thermal conductivity can be improved as content of an inorganic material is 10 volume% or more. Moreover, since it is excellent in the cohesion force of a composition as it is 50 volume% or less, sheet formation becomes easy.

In addition, content (volume%) of the inorganic material in this specification is the value calculated | required by following Formula.
Content of inorganic material (% by volume) = (Aw / dA) / ((Aw / Ad) + (Bw / Bd) + (Cw / Cd) + (Dw / Dd) +.
Aw: mass composition of inorganic material (mass%)
Bw: mass composition of organic polymer compound (mass%)
Cw: mass composition (mass%) of other optional components
Ad: Specific gravity of the inorganic material (In the present invention, Ad is calculated as 2.1 for graphite, 2.2 for boron nitride, and 1.8 for carbon fiber.)
Bd: Specific gravity of the crosslinked cured product of the organic polymer compound Cd: Specific gravity of other optional components

The organic polymer compound in the present invention has a Tg (glass transition temperature) of 50 ° C. or lower, preferably −70 to 20 ° C., more preferably −60 to 0 ° C. If Tg is 50 ° C. or lower, the flexibility is excellent, and the adhesion to the heat generator and the heat radiator is also good.
In the present invention, the glass transition temperature is measured using thermomechanical measurement (TMA).

  Examples of the organic polymer compound used in the present invention include a poly (meth) acrylate polymer compound (so-called acrylic rubber), poly (meth) acrylate having butyl acrylate, 2-ethylhexyl acrylate and the like as main raw material components. A polymer compound having a dimethylsiloxane structure as a main structure (so-called silicone resin), a polymer compound having a polyisoprene structure as a main structure (so-called isoprene rubber, natural rubber), and a polymer compound having chloroprene as a main raw material component (so-called Examples thereof include flexible organic polymer compounds generally referred to as “rubber”, such as chloroprene rubber) and polymer compounds having a polybutadiene structure as a main structure (so-called butadiene rubber).

  Among these, a poly (meth) acrylate polymer compound, particularly butyl acrylate, 2-ethylhexyl acrylate or both are included as a copolymerization component, and they are included in the copolymer composition at 50% by mass or more. A poly (meth) acrylic acid ester polymer compound is preferable because it is easy to obtain high flexibility, excellent in chemical stability and processability, easily controls adhesiveness, and is relatively inexpensive.

  In addition, it is preferable to include a crosslinked structure within a range that does not impair flexibility, in terms of long-term adhesion retention and film strength. For example, a crosslinked structure can be included by reacting a compound having a —OH group with a compound having a plurality of isocyanate groups. Although content in particular of an organic polymer compound is not restrict | limited, Preferably it is 10-70 volume% with respect to the composition whole volume, More preferably, it is 20-50 volume%.

  Moreover, the heat conductive sheet of this invention can contain a flame retardant. It does not specifically limit as a flame retardant, For example, a red phosphorus flame retardant, a phosphate ester flame retardant, etc. can be contained.

  Examples of red phosphorus flame retardants include pure red phosphorus powder, various coatings for the purpose of improving safety and stability, and master batches. Examples include trade names: Nova Red, Nova Excel, Nova Quel, Nova Pellet, etc., manufactured by Rin Chemical Industry Co., Ltd.

Examples of the phosphate ester flame retardant include aliphatic phosphate esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate;
Triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trixylenyl phosphate, cresyl-2,6-xylenyl phosphate, tris (t-butylated phenyl) phosphate, tris (isopropylated phenyl) phosphate, phosphoric acid Aromatic phosphates such as triaryl isopropylates;
Examples thereof include aromatic condensed phosphate esters such as resorcinol bisdiphenyl phosphate, bisphenol A bis (diphenyl phosphate), and resorcinol bisdixylenyl phosphate.

  These may be used alone or in combination of two or more. In addition, it is preferable that the flame retardant is a phosphoric acid ester compound and is a liquid having a freezing point of 15 ° C. or lower and a boiling point of 120 ° C. or higher because it is easy to achieve both flame retardancy and flexibility and tackiness. Examples of liquid phosphate ester flame retardants having a freezing point of 15 ° C. or lower and a boiling point of 120 ° C. or higher include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6 -Xylenyl phosphate, resorcinol bisdiphenyl phosphate, bisphenol A bis (diphenyl phosphate) and the like.

  The content of the flame retardant is not particularly limited, but is preferably 5 to 50% by volume, more preferably 10 to 40% by volume with respect to the total volume of the composition. If the content of the flame retardant is within the above range, it is preferable because sufficient flame retardancy is exhibited and it is advantageous in terms of flexibility. If the content of the flame retardant is 5% by volume or more, sufficient flame retardancy is easily obtained, and if it is 50% by volume or less, the sheet strength is satisfactory.

  In addition, the heat conductive sheet of the present invention is further provided with a toughness improving agent such as urethane acrylate; a hygroscopic agent such as calcium oxide or magnesium oxide; an adhesive strength such as a silane coupling agent, a titanium coupling agent, or an acid anhydride. An improvement agent; a wetting improvement agent such as a nonionic surfactant or a fluorine-based surfactant; an antifoaming agent such as silicone oil; an ion trapping agent such as an inorganic ion exchanger; or the like can be appropriately added.

  In the heat conductive sheet of the present invention, the surface direction of the scale of the inorganic material, the long axis direction of the ellipsoid, the long axis direction of the plate, or the long axis direction of the rod are inclined with respect to the thickness direction of the heat conductive sheet. Yes.

  In the present invention, “orientation tilted in the thickness direction of the heat conductive sheet” means that a cross section in the thickness direction of the heat conductive sheet is observed using a metal microscope or SEM (scanning electron microscope), and any 50 inorganic materials The angle to the surface of the heat conduction sheet in the direction of the scale of the inorganic material, the long axis direction of the ellipsoid, the long axis direction of the plate, or the long axis direction of the rod (if the angle is 90 ° or more Employed) and the average value is in the range of 5 to 60 °.

Thermally conductive sheet of the present invention, the surface direction of the scale of the inorganic materials, the long axis direction of the oval sphere, the long axis direction of the long axis direction or rod of the plate, tilted with respect to the thickness direction of the thermally conductive sheet, inorganic materials The average value of the angle with respect to the surface of the heat conductive sheet in the surface direction of the scale, the long axis direction of the ellipse, the long axis direction of the plate or the long axis direction of the rod is inclined in the range of 5 to 60 °. The range is preferably 10 to 55 °, more preferably 20 to 40 °. The inclination of the inorganic material, tackiness enough large angle surface inclined with respect to the thickness direction of the thermally conductive sheet is improved, there is a tendency that the film thickness direction of the heat conduction condition becomes worse gradually.
The method for observing the alignment state is specifically described below.

The orientation of the inorganic material can be observed by the following procedure.
The heat conductive sheet is cut with a glass knife to expose a cross section in the thickness direction of the heat conductive sheet. This processing can be performed with a microtome apparatus used to produce a thin film test piece or the like. Next, the inorganic material and the organic compound are selectively etched on the cross section of the heat conductive sheet by reactive ion etching, so that the inorganic material is remarkably exposed on the cross-sectional surface layer. Furthermore, the cross section in which the inorganic material is exposed with respect to any 50 is imaged using a metal microscope or SEM (scanning electron microscope), and the orientation of the inorganic material is analyzed by the image. At that time, since the organic compound and the inorganic material are obtained as images having different contrasts, it can be divided into images of the respective materials by binarization, and the orientation state of the inorganic material is also calculated by using the pixels on the image. The angle can be calculated.

  Moreover, in the heat conductive sheet of this invention, in order to protect an adhesive surface, you may cover the adhesive surface of the heat conductive sheet before use with a protective film. Examples of the material for the protective film include resins such as polyethylene, polyester, polypropylene, polyethylene terephthalate, polyimide, polyetherimide, polyether naphthalate, and methylpentene film, and metals such as coated paper, coated cloth, and aluminum. Two or more kinds of these protective films may be combined to form a multilayer film, and the protective film whose surface is treated with a release agent such as silicone or silica is preferably used.

<The manufacturing method of a heat conductive sheet>
The manufacturing method of the heat conductive sheet of this invention is demonstrated.
The manufacturing method of the heat conductive sheet of this invention includes the following process (a) thru | or (d).
(A) A step of preparing a composition by kneading a heat conductive inorganic material having a scale shape, an elliptical shape or a rod shape with an organic polymer compound.
(B) A step of applying a pressure to the composition to produce a primary sheet in which the inorganic material is oriented in a direction substantially parallel to a main surface.
(C1) A step of laminating the primary sheets to form a laminate.
(D) (A) The laminate is sliced at an angle of 5 to 60 ° with respect to the normal line coming out of the primary sheet surface to form a sheet, and (c) the laminate is formed. Any one of the above (a) to (c), in which a sheet is obtained by slicing at a substantially perpendicular angle with respect to the normal line coming out of the primary sheet surface and then roll-pressing. The process to perform.

  Instead of the step (c1), (c2) the primary sheet may be wound around the orientation direction of the inorganic material as an axis to form a laminate.

  In the step (a), the size of the inorganic material to be used is preferably selected according to the slice thickness in the step (d), and the size of the longest portion of the scale, ellipse, plate, or rod is average. In this case, the material may be charged under conditions of 250 μm material, 500 to 1000 μm, 1500 μm to 2000 μm, and the like.

In order to further increase the thermal conductivity, it is necessary to increase the inorganic material penetrating in the cross section of the sheet after slicing. Therefore, an inorganic material larger than the slice thickness is usually selected.
The kneading means is not particularly limited, but an apparatus such as a two-roller or a kneader is used.

  In the step (b), the kneaded composition is prepared by crushing it using a flat plate press or a metal roll. The temperature condition is preferably in the range of 25 to 150 ° C. because if the temperature is too high, the resin becomes brittle and if the temperature is too low, the resin does not soften. In that case, the thinner sheet thickness is preferable, and the thickness of 0.2 mm to 1.0 mm is most preferable.

  The state in which the “inorganic material is oriented in a direction parallel to the main surface of the sheet” refers to a state in which the inorganic material is oriented so as to lie on the main surface of the sheet. The orientation of the inorganic material in the sheet surface is controlled by adjusting the direction in which the composition flows when the composition is molded. That is, the direction of the inorganic material is controlled by adjusting the direction in which the composition is passed through a rolling roll, the direction in which the composition is extruded, the direction in which the composition is applied, and the direction in which the composition is pressed. Since the inorganic material has a scale-like, oval or rod-like shape and has anisotropy, the orientation of the inorganic material is usually aligned by rolling, pressing, extrusion or coating the composition. Arranged.

  The confirmation of "the state in which the inorganic material is oriented in a direction substantially parallel to the main surface of the sheet" is the same as the confirmation method of the above-mentioned "orientation inclined in the thickness direction of the heat conductive sheet". Is observed by observing 50 arbitrary particles using SEM. Specifically, the cross section of the primary sheet is observed using a SEM, and for any 50 particles, the scale direction of the inorganic material, the long axis direction of the ellipse, the long axis direction of the plate, or the long axis direction of the rod It is confirmed whether the average value of the angle with respect to the primary sheet surface (adopting a complementary angle when it is 90 degrees or more) is in the range of 0 to 20 degrees.

  In the subsequent step (c1), the primary sheet is cut out to a predetermined size, and a plurality of sheets are laminated. Or you may fold a primary sheet and obtain a laminated body. When laminating, the orientation of the inorganic material in the sheet plane is aligned.

  The shape of the primary sheet at the time of lamination is not particularly limited. For example, when a rectangular primary sheet is laminated, a prismatic shaped body is obtained, and when a circular primary sheet is laminated, A columnar shaped body is obtained.

  When laminating, in order to increase the adhesion between the primary sheets, it is preferable to apply pressure by a press or the like. The compression amount in the press is preferably in the range of 3 to 20%. A metal roll can be used without problems in addition to the press.

  Or it is also possible to wind a primary sheet as a (c2) process instead of the (c1) process, and to obtain a laminated body. The method for winding the primary sheet is not particularly limited, and the primary sheet may be wound around the orientation direction of the inorganic material as an axis. The shape of the winding is not particularly limited, and may be, for example, a cylindrical shape or a rectangular tube shape.

In the step (d), (i) the laminated body is sliced at an angle of 5 to 60 ° with respect to the normal line coming out from the primary sheet surface to form a heat conductive sheet, and (c) the above The above-mentioned (A) to (C), wherein the laminate is formed by slicing the sheet at a substantially perpendicular angle to the normal line coming out of the primary sheet surface, and then forming a heat conductive sheet by roll pressing. Do one.
The “normal line coming out from the primary sheet surface” in the laminate refers to the arrow shown in FIG.

Since it is easy in terms of structure and process to slice the slice at an angle substantially perpendicular to the sliced surface of the laminate, it is preferable to carry out the method by the method (c) industrially.
In the method (a), as shown in FIG. 6, a primary sheet in which an inorganic material is oriented in a direction substantially parallel to the main surface is laminated, and the normal line exiting from the primary sheet surface is 5 Slice to ~ 60 °.
Further, in the above method (a), as shown in FIG. 7, a laminated body in which a primary sheet oriented in a direction substantially parallel to a main surface of an inorganic material is cut at an angle and laminated. May be produced. If this laminate is sliced substantially perpendicular to the slice plane, it is industrially preferable because it is easy in terms of process.

  Examples of the slicing means include a multi-blade method, a laser processing method, a water jet method, a knife processing method, etc., but the knife processing method is preferable in that it is easy to keep the thickness of the heat conductive sheet parallel and no chips are generated. .

  The cutting tool for slicing is not particularly limited, but is a slicing member having a flat portion having a slit and a blade portion protruding from the slit portion, and the blade portion is a heat member. If the length of the protrusion from the slit portion can be adjusted according to the desired thickness of the conductive sheet, it is difficult to disturb the orientation of the inorganic material in the vicinity of the surface of the obtained heat conductive sheet, and the desired thickness A thin sheet is also preferable because it is easy to produce.

  The roll press in the step (d) further compresses the slice sheet with a metal roll. At this time, the compression amount is preferably 0.5 to 40%. More preferably, compression is performed in the range of 10 to 30%. Depending on the amount of compression in this step, the inorganic material can be oriented with an inclination of 5 to 60 ° with respect to the thickness direction of the sheet. In the sheet thus prepared, the surface direction of the scale of the inorganic material, the long axis direction of the ellipsoid, or the long axis direction of the rod is inclined with respect to the thickness direction of the sheet (more preferably, the heat conductive sheet). It has a structure in which it is oriented (tilted in a range of 5 to 60 ° with respect to the thickness direction).

Example 1
The example which produced the heat conductive sheet of this invention according to the process mentioned above is demonstrated.

As the heat conductive inorganic material, scale-like graphite having an average particle diameter of 500 to 1000 μm was used. The graphite content was 45% by volume of the total volume of the composition. As the organic polymer compound, a poly (meth) acrylate polymer compound in which butyl acrylate was 76% by mass in the copolymer composition was used. Its content was 30% by volume with respect to the total volume of the composition.
As the flame retardant, bisphenol A bis (diphenyl phosphate), which is a phosphate ester type, was used, and the content was 25% by volume based on the total volume of the composition.

  The above materials were blended and first kneaded using a pressure kneader. The kneading was performed under the conditions that the amount of the composition substance: 3.5 kg and the temperature: 100 ° C. for 40 minutes. The kneaded product was compressed to a thickness of several tens of mm with a hydraulic press, and further passed through a metal roll at 80 ° C. several times to produce a 1.0 mm-thick primary sheet.

  The confirmation of "the state in which the inorganic material is oriented in a direction substantially parallel to the main surface of the sheet" is made by observing the cross section of the obtained primary sheet using an SEM and seeing about 50 arbitrary inorganic materials. The angle with respect to the primary sheet surface in the surface direction of the scale of the inorganic material was measured from the direction in which the inorganic material was scaled (a complementary angle was adopted when 90 degrees or more), and the average value was determined to be 2 °. It was recognized that the inorganic material (flaky graphite) was oriented in a direction substantially parallel to the main surface of the primary sheet.

  Next, the primary sheet was cut into a 50 mm × 200 mm shape and laminated until the height reached 50 mm. The laminate was further pressurized at a pressure of 0.1 MPa or less using a hydraulic press. Then, a plane parallel to the normal line of the laminate surface of the laminate was sliced at an angle substantially perpendicular to the normal line from the primary sheet surface using an apparatus having a mechanism similar to that of the plane.

  Specifically, the protrusion amount of the blade was adjusted so that the thickness of the slice sheet was 0.25 mm, the laminate temperature was 10 ° C., the processing speed was 54 mm / min, and the tip angle of the blade itself was 32 °. Processed under conditions. Finally, the slice sheet was compressed 30% using a metal roll at 80 ° C. to produce a heat conductive sheet.

  The orientation of the inorganic material of the heat conductive sheet produced on the above conditions was observed. The cross-sectional observation method was performed according to the following procedure. First, after the cross section of the heat conductive sheet was cut out with a microtome, the cross section was etched by reactive ion etching. Etching conditions were as follows: gas was injected with oxygen and argon gas at a ratio of 1: 4, the pressure was 6 Pa, and the power was 100 W for 20 minutes. After etching, the cross section was imaged with a scanning electron microscope.

  FIG. 1 is a binarized photograph, and the black portion is graphite 100. The white part is the organic polymer compound 101. FIG. 1 also illustrates an axis 201 parallel to the thickness direction of the heat conductive sheet, an axis 202 in the surface direction of the scale of the inorganic material (graphite), and an angle (inclination) 200 at which the axes 201 and 202 intersect. . The angle 200 represents the inclination orientation degree with respect to the thickness direction of the heat conductive sheet in the surface direction of the scale of the inorganic material. From this FIG. 1, it can be seen that the surface direction of the scale of the graphite 100 is inclined by 51 ° with respect to the thickness direction of the heat conductive sheet.

(Comparative Example 1)

  The heat conductive sheet of the comparative example was exactly the same as that of Example 1, and the process was performed under exactly the same conditions until the slicing process, and the procedure was performed except for the final roll press process. The heat conductive sheet of the comparative example produced under these conditions has a structure in which the surface direction of the graphite scale is not inclined with respect to the thickness direction of the heat conductive sheet but is oriented vertically.

  FIG. 2 shows the tackiness of Example 1 and Comparative Example 1.

Evaluation of tackiness was performed using a probe test apparatus, and the measurement conditions were as follows: temperature: 23 degrees, probe diameter: 5 mm, probe contact area: 19.6 mm ² , probe load: 50 g, and pressing time: 10 seconds.
As shown in FIG. 2, in Example 1, the tack force is improved more than double compared to Comparative Example 1. The sheet surface is a surface that rubs against the knife during slicing.

FIG. 3 shows a comparison of tensile strength. The strength was compared by tensile strength.
The sample shape was 10 mm wide, and the measurement conditions were a temperature of 23 degrees and a tensile speed of 50 mm / min.
As shown in FIG. 3, the tensile strength in Example 1 is doubled compared to Comparative Example 1.

  When the thermal resistances of Example 1 and Comparative Example 1 were measured, similar values could be obtained for both. The thermal resistance was measured using a transistor method. The measurement was performed according to the following procedure. A heat conductive sheet is placed on a constant controlled copper plate, the transistor is pressurized from above with a load of 1.0 MPa, and the temperature difference between the front and back of the heat conductive sheet when a power of 17 to 19 W is applied is measured with a thermocouple. The thermal resistance was calculated.

  As described above, according to the present invention, it is possible to increase tackiness and strength while maintaining high heat conduction in the film thickness direction. In addition, since the inorganic material is inclined with respect to the sheet thickness direction, it is possible to provide a heat conductive sheet that maintains thermal conductivity without the inorganic material being buckled even by a pressure load in the mounting process. .

DESCRIPTION OF SYMBOLS 1 Sheet surface 10 Inorganic filler 100 Graphite 101 Organic polymer compound 200 The angle 201 between the surface direction of the scale of an inorganic material, and the thickness direction of a heat conductive sheet 201 The axis line 202 parallel to the thickness direction of a heat conductive sheet Inorganic material (graphite) Axial surface direction axis

Claims (3)

The manufacturing method of the heat conductive sheet containing the following process (a) thru | or (d).
(A) an inorganic material containing even without less scaly graphite, and organic polymer compound, and kneaded, the composition amount of the inorganic material is 10 to 50% by volume of the total volume of the composition Preparing a product,
(B) by applying pressure to the composition, process surface Direction before Kiuroko flake graphite is to produce a primary sheet oriented in a direction substantially parallel to the main surfaces,
(C1) A step of laminating the primary sheet to form a laminate,
The (d) (i) the laminate, said sheeted by slicing at an angle of. 5 to 40 ° to the normal line emanating from the primary sheet plane, the plane Direction before Kiuroko flake graphite, heat Forming a thermally conductive sheet oriented at an angle of 5 to 40 ° with respect to the surface of the conductive sheet; and (c) the laminate being substantially perpendicular to a normal line emerging from the primary sheet surface. after a sheet by slicing at an angle, a slice sheet by roll pressing, prior to the surface direction of Kiuroko flake graphite is inclined in the range of 5 to 40 ° to the surface of the thermally conductive sheet orientation The process of performing any of said (I) and (U) of forming the heat conductive sheet which is carrying out. The manufacturing method of the heat conductive sheet containing the following process (a) thru | or (d).
(A) an inorganic material containing even without less scaly graphite, and organic polymer compound, and kneaded, the composition amount of the inorganic material is 10 to 50% by volume of the total volume of the composition Preparing a product,
(B) by applying pressure to the composition, process surface Direction before Kiuroko flake graphite is to produce a primary sheet oriented in a direction substantially parallel to the main surfaces,
(C2) a step of winding the primary sheet around the orientation direction of the scaly graphite to form a laminate,
The (d) (i) the laminate, said sheeted by slicing at an angle of. 5 to 40 ° to the normal line emanating from the primary sheet plane, the plane Direction before Kiuroko flake graphite, heat Forming a thermally conductive sheet oriented at an angle of 5 to 40 ° with respect to the surface of the conductive sheet; and (c) the laminate being substantially perpendicular to a normal line emerging from the primary sheet surface. after a sheet by slicing at an angle, a slice sheet by roll pressing, prior to the surface direction of Kiuroko flake graphite is inclined in the range of 5 to 40 ° to the surface of the thermally conductive sheet orientation The process of performing any of said (I) and (U) of forming the heat conductive sheet which is carrying out. The organic polymer compound contains a poly (meth) acrylate polymer compound containing at least one selected from the group consisting of butyl acrylate and 2-ethylhexyl acrylate as a copolymerization component. Or the manufacturing method of the heat conductive sheet of 2 .