JP2019119131A - Thermally conductive molded article and its manufacturing method - Google Patents

Abstract

To provide a new manufacturing method, etc. for manufacturing a thermally conductive molded article superior in thermal conductivity.SOLUTION: A manufacturing method of a thermally conductive molded article comprises: a step of preparing a first film which is arranged on a mold so as to follow a three-dimensional shape of the mold having the three-dimensional shape and has a shape corresponding to the three-dimensional shape; a step of arranging a curable composition containing a thermal conductive material and (meth) acrylic monomer on the first film; a step of arranging a second film on the curable composition to sandwich the curable composition with the first film and the second film; and a step of radical-polymerizing the (meth) acrylic monomer in the curable composition to form a cured product of the curable composition between the first film and the second film. Both of oxygen permeabilities of the first film and the second film are less than 1000 ml/m*24h*atm, and 50% expansion strength at the temperature 100°C of the first film is 100 N/25 mm or below.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a thermally conductive molded body and a method for producing the same.

  In order to efficiently cool the heat generation of heat-generating components (for example, battery packs for vehicles etc.) mounted on electronic devices etc., apply a thermally conductive molded object between the heat-generating components and heat-radiating components such as a heat sink It has been carried out to improve the heat dissipation of heat-generating components. Such a thermally conductive molded product is produced, for example, by forming a composition containing a resin base material and a thermally conductive filler, and forming a composition in a tray recess of a heat resistant tray having a shape corresponding to a desired shape. And a step of heat curing the composition in a state of being filled in the tray recess (see Patent Document 1).

JP, 2016-92227, A

  An object of the present invention is to provide a novel production method for producing a thermally conductive molded article excellent in thermal conductivity and a thermally conductive molded article obtained by the production method.

One aspect of the present invention is to provide a first film disposed on a mold so as to follow the three-dimensional shape of the mold having a three-dimensional shape, and having a shape corresponding to the three-dimensional shape; Placing a curable composition containing a thermally conductive material and a (meth) acrylic monomer on one film, and placing a second film on the curable composition to obtain a first film And a step of sandwiching the curable composition with the second film, and radically polymerizing the (meth) acrylic monomer in the curable composition to form the curable composition between the first film and the second film. And the step of forming a cured product thereof. In the above manufacturing method, the oxygen permeability of the first film and the second film is both less than 1000 ml / m ² · 24 h · atm, and the 50% elongation strength of the first film at a temperature of 100 ° C. is It is 100 N / 25 mm or less.

Moreover, the other one side of this invention has a 1st surface which has a three-dimensional shape, and follows the said three-dimensional shape with the resin molding which contains a thermally conductive material and a (meth) acrylic polymer. And a first film disposed on the first surface of the resin molded body, and a thermally conductive molded body. In the thermally conductive molded article, the oxygen permeability of the first film is less than 1000 ml / m ² · 24 h · atm, and the 50% tensile strength at a temperature of 100 ° C. is 100 N / 25 mm or less.

  According to the present invention, it is possible to provide a novel manufacturing method for manufacturing a thermally conductive molded body excellent in thermal conductivity and a thermally conductive molded body obtained by the manufacturing method.

FIG. 1 is a perspective view schematically showing an embodiment of a thermally conductive molded body. It is a sectional view showing one embodiment of a thermally conductive compact. It is process sectional drawing which shows one Embodiment of the manufacturing method of a heat conductive molded object.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as needed. However, the present invention is not limited to the following embodiments.

<Heat conductive molded body>
The thermally conductive molded body according to the present embodiment is a resin molded body having a first surface having a three-dimensional shape, and a first one disposed on the first surface of the resin molded body so as to follow the three-dimensional shape. And one film.

  The three-dimensional shape can be appropriately set in accordance with the shape of an adherend (for example, a heat-generating component, a heat-releasing component or the like) to which the thermally conductive molded object is applied. For example, it may be a shape along the surface shape of the adherend, and may be a shape that facilitates installation to the application site.

  Although the three-dimensional shape is not particularly limited, for example, at least a portion thereof may be hemispherical, semi-cylindrical, or the like. By having such a three-dimensional shape, it is easy to perform position alignment, while sliding, with respect to the to-be-adhered body to apply, and it is excellent in workability. Moreover, after alignment, by pressing on the adherend, the three-dimensional shape can be deformed, and the contact area can be secured.

  FIG. 1 is a perspective view schematically showing an embodiment of a heat conductive molded body. In FIG. 1 (a)-(g), a specific example of the heat conductive molded object which has a three-dimensional-shaped part is shown. As a heat conductive molded object which has a three-dimensional-shaped part, as FIG. 1 (a) and (b) show, for example, hemispherical shape, semi-cylindrical shape etc. may be sufficient. In addition, the size, number, location, etc. of the three-dimensional shaped portion in the thermally conductive molded body can be appropriately set in consideration of the shape, size, etc. of the parts to which the thermally conductive molded body is applied, For example, as shown in FIG. 1 (c) to (g), it may be a thermally conductive molded body having a plurality of, specifically two or more, three or more or five or more three-dimensional shaped parts. In addition, the hemispherical three-dimensional shape portion and the semi-cylindrical three-dimensional shape portion may coexist in the same heat conductive molded body.

  The resin molding contains a thermally conductive material and a (meth) acrylic polymer.

  The thermally conductive material is a component that imparts substantial thermal conductivity to the resin molded body. The heat conductive material is not particularly limited, and for example, known heat conductive fillers can be used.

  Examples of the heat conductive material include metal hydrate compounds, metal oxides, metal nitrides and metal carbides.

  Examples of the metal hydrate compound include aluminum hydroxide, magnesium hydroxide, barium hydroxide, calcium hydroxide, dawsonite, hydrotalcite, zinc borate, calcium aluminate, zirconium oxide hydrate and the like. Further, as the metal oxide, aluminum oxide, magnesium oxide, beryllium oxide, titanium oxide, zirconium oxide, zinc oxide and the like can be mentioned. Further, as the metal nitride, boron nitride, aluminum nitride, silicon nitride and the like can be mentioned, and as the metal carbide, boron carbide, aluminum carbide, silicon carbide and the like can be mentioned.

  These heat conductive materials are usually added in the form of particles. As the thermally conductive material, a relatively large particle size group having an average particle size of 10 to 100 μm and a relatively small particle size group having an average particle size of less than 10 μm are used in combination. The addition amount (filling amount) can be increased. In addition, an average particle diameter refers to the particle size in 50% of the integration value in the particle size distribution calculated | required by the laser diffraction scattering method.

  The thermally conductive material (thermally conductive filler) may be surface-treated with a silane coupling agent, a titanate coupling agent, a surface treatment agent such as a fatty acid, or the like. By using the thermally conductive material subjected to such surface treatment, the strength (for example, tensile strength) of the thermally conductive molded body can be improved. Moreover, since the effect of reducing the viscosity of the curable composition mentioned later is large, the said surface treatment is preferable on a manufacturing process. Although the heat conductive material may be subjected to surface treatment in advance, the effect of the surface treatment can be obtained by adding the coupling agent or the surface treatment agent together with the heat conductive material to the curable composition described later. You can also get

  The content of the thermally conductive material in the resin molding is preferably 55 to 95% by volume, and more preferably 65 to 85% by volume, based on the total amount of the resin molding. When the content of the thermally conductive material is in the above range, sufficient thermal conductivity is obtained, and the resin molded product is prevented from becoming brittle or difficult to manufacture due to too much thermally conductive material, which is sufficient. A thermally conductive molded body having strength and flexibility can be easily obtained.

  The (meth) acrylic polymer is a polymer obtained by polymerizing a monomer component containing a (meth) acrylic monomer. The polymerization can be carried out by radical polymerization as described later. Here, “(meth) acrylic monomer” means acrylic monomers such as acrylic acid and acrylic esters, and / or methacrylic monomers such as methacrylic acids and methacrylic esters. Show. That is, the (meth) acrylic polymer is a polymer obtained by polymerizing a monomer component containing at least one monomer selected from the group consisting of acrylic monomers and methacrylic monomers. You can also.

  The (meth) acrylic monomer is not particularly limited as long as it is a monomer used to form a general (meth) acrylic polymer. Moreover, a (meth) acrylic monomer may be used individually by 1 type, and may be used in combination of 2 or more types.

  It is preferable that the said monomer component contains an at least monofunctional (meth) acrylic monomer as a (meth) acrylic monomer. The monofunctional (meth) acrylic monomer is a monomer having one (meth) acryloyl group.

  Examples of the monofunctional (meth) acrylic monomer include (meth) acrylic acid, alkyl (meth) acrylate, aryl (meth) acrylate, (meth) acrylamide, epoxy acrylate, urethane acrylate and the like.

  Among these, as a monofunctional (meth) acrylic monomer, the alkyl (meth) acrylate which has a C12-C20 alkyl group is preferable. Here, the alkyl group may be linear, branched or cyclic.

  Moreover, as a monofunctional (meth) acrylic monomer, it is preferable to use 2 or more types of alkyl (meth) acrylate from which carbon number differs. In this case, by adjusting the content of each alkyl (meth) acrylate, the flexibility of the resulting resin molded product can be appropriately adjusted according to the application.

  The monomer component may further contain a polyfunctional (meth) acrylic monomer as the (meth) acrylic monomer. In addition, a polyfunctional (meth) acrylic monomer is a monomer which has two or more (meth) acryloyl groups. When the monomer component contains a polyfunctional (meth) acrylic monomer, the (meth) acrylic polymer has a crosslinked structure, so that the strength of the resin molded product is improved.

  As a polyfunctional (meth) acrylic monomer, for example, 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate ) Acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, poly (butanediol) di (meth) acrylate, 1,3-butylene glycol di (meth) 2.) Bifunctional (meth) monomers such as acrylate, triethylene glycol di (meth) acrylate, triisopropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, bisphenol A di (meth) acrylate Trimeric (meth) acrylic monomers such as ryl monomers; trimethylolpropane tri (meth) acrylate, pentaerythritol monohydroxy tri (meth) acrylate, trimethylolpropane triethoxy tri (meth) acrylate; pentaerythritol tetra (meth) acrylate Tetrafunctional (meth) acrylic monomers such as meta) acrylate and di-trimethylolpropane tetra (meth) acrylate; pentafunctional (meth) acrylic monomers such as dipentaerythritol (monohydroxy) penta (meth) acrylate; Etc.

  The content of the polyfunctional (meth) acrylic monomer in the monomer component is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the monofunctional (meth) acrylic monomer. With such a content, the strength improvement effect of the resin molded product due to the crosslinked structure is sufficiently obtained, and the decrease in flexibility due to excessive crosslinking is avoided, and a thermally conductive molded product having high flexibility is obtained. Be

  The content of the (meth) acrylic polymer in the resin molded body is preferably 0.05 to 30% by mass, and more preferably 0.5 to 15% by mass, based on the total amount of the resin molded body.

  The resin molding may contain components other than the above. For example, the resin molded product may be an antioxidant, a tackifier, a plasticizer, a flame retardant, a flame retardant auxiliary, an antisettling agent, a thickener, a thixotropy agent such as ultrafine silica, a surfactant, an antifoamer, You may contain additives, such as a coloring agent, an antistatic agent, and a metal deactivator. One of these additives may be used alone, or two or more thereof may be used in combination.

In the heat conductive molded body according to the present embodiment, the oxygen permeability of the first film needs to be less than 1000 ml / m ² · 24 h · atm. When the oxygen permeability of the first film is less than 1000 ml / m ² · 24 h · atm, the (meth) acrylic monomer is subjected to radical polymerization to produce (meth) acrylic acid in the production of a heat conductive molded body described later When manufacturing a polymer, it can prevent that radical polymerization is inhibited by oxygen. From this point of view, the oxygen permeability of the first film is preferably 200 ml / m ² · 24 h · atm or less, more preferably 150 ml / m ² · 24 h · atm or less, still more preferably 100 ml / m. m ² · 24 h · atm or less. The lower limit of the oxygen permeability of the first film is not particularly limited, and is, for example, 0.01 ml / m ² · 24 h · atm or more. In addition, in this specification, the oxygen permeability means the oxygen permeability measured using MOCON company oxygen permeability measuring apparatus OX-TRAN, Model 2/21. When the oxygen permeability exceeds 200 ml / m ² · 24 h · atm, measurement is performed by masking a part of the test cell.

  Further, the 50% tensile strength of the first film at a temperature of 100 ° C. needs to be 100 N / 25 mm or less. If the 50% tensile strength at a temperature of 100 ° C. of the first film is 100 N / 25 mm or less, the flexibility of the first film can be sufficiently secured, and in the production of a heat conductive molded body described later, Good followability can be maintained. From such a point of view, the 50% tensile strength at a temperature of 100 ° C. of the first film may be, for example, 50 N / 25 mm or less, or 25 N / 25 mm or less. In the present specification, 50% tensile strength at a temperature of 100 ° C. means tensile strength measured by a method in accordance with ISO 527-3 (JIS K 7172: 1999).

  The dynamic friction coefficient of the first film is preferably 0.7 or less from the viewpoint of giving excellent slip properties of the first film and improving the workability when applying the thermally conductive molded article to an adherend. More preferably, it is 0.5 or less, More preferably, it is 0.3 or less. The lower limit of the dynamic friction coefficient of the first film is not particularly limited, and is, for example, 0.05 or more. In addition, in this specification, a kinetic friction coefficient means the value measured as a kinetic friction coefficient with respect to copper based on the method based on ISO 8295: 1995 (JISK7125: 1999). That is, a copper foil is stuck on the bottom of the weight with a double-sided adhesive tape (ST-416 manufactured by 3M Japan), which means a value measured under a load of 200 g and a tensile speed of 100 mm / min.

  As a first film suitably used in the heat conductive molded body according to the present embodiment, for example, polyvinyl alcohol, ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene fluoride (PVDF), polyacrylonitrile, biaxial Films containing at least one selected from the group consisting of stretched polyethylene terephthalate (biaxially stretched PET), non-stretched nylon and non-stretched PET can be mentioned. Among these, at least one selected from the group consisting of EVOH, PVDF, and non-oriented nylon from the viewpoints of deep drawability, slipperiness, removability to a resin molded product, releasability to a second film described later, etc. The film is preferably a film, and the film containing EVOH is more preferably a multilayer film.

  The thickness of the first film can be appropriately set according to the application of the thermally conductive molded product and the type of the film, in the range that the effects of the present invention are not significantly impaired. The thickness of the first film may be, for example, 3 to 200 μm, 5 to 150 μm, or 10 to 130 μm. If the thickness of the first film is within the above range, the oxygen permeability and the strength can be sufficiently secured, while the thermal resistance can be suppressed and the formability can be secured.

  In addition, the first film may be composed of one layer or may be composed of two or more layers. When the first film is composed of two or more layers, at least one of the layers may have the characteristics of the first film according to the present embodiment, and all the layers according to the present embodiment It may have the characteristics of one film. When the first film is composed of two or more layers, each layer may be laminated via an adhesive layer or the like as appropriate.

  The thermally conductive molded product according to the present embodiment may further include a second film disposed on the surface opposite to the first surface of the resin molded product described above. FIG. 2 is a cross-sectional view showing an embodiment of a heat conductive molded body. As shown in FIG. 2, the heat conductive molded body 100 includes a first film 1, a second film 2, and a resin molded body 3, and the resin molded body 3 has a three-dimensional shape. It has a first surface 3a and a surface 3b opposite to the first surface. The first film 1 is disposed to follow the three-dimensional shape of the first surface 3 a of the resin molding 3, and the second film 2 is on the opposite side of the first surface of the resin molding 3. It is arranged on the surface 3b.

When the thermally conductive green body further comprises the second film 2, the oxygen permeability of the second film 2 is less than 1000 ml / m ² · 24 h · atm. When the oxygen permeability of the second film 2 is less than 1000 ml / m ² · 24 h · atm, radical polymerization of (meth) acrylic monomer is carried out in the production of a heat conductive molded body described later (meth) When manufacturing an acrylic polymer, it can prevent more effectively that radical polymerization is inhibited by oxygen. From such a viewpoint, the oxygen permeability of the second film 2 is preferably 200 ml / m ² · 24 h · atm or less, more preferably 150 ml / m ² · 24 h · atm or less, further preferably 100 ml / M ² · 24h · atm or less. The lower limit of the oxygen permeability of the second film 2 is not particularly limited, and is, for example, 0.01 ml / m ² · 24 h · atm or more.

  As such a second film, for example, polyvinyl alcohol, ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene fluoride (PVDF), polyacrylonitrile, biaxially stretched polyethylene terephthalate (biaxially stretched PET), biaxial A film containing at least one selected from the group consisting of stretched polyethylene naphthalate (biaxially stretched PEN), non-stretched nylon and non-stretched PET can be mentioned. Among these, biaxially stretched PET, biaxially stretched PEN, and non-stretched nylon are preferable from the viewpoint of sufficiently suppressing the releasability to the resin molded product, the removability to the first film, and the oxygen permeability. It is preferable that it is a film containing at least one selected from the group. In addition, when using a heat conductive molded object, as mentioned later, when using by peeling a 2nd film, the curable composition of a 2nd film contacts from a viewpoint of making peeling easy. A release agent such as silicone may be applied to the side surface.

  The thickness of the second film 2 can be appropriately set according to the application of the heat conductive molded body 100 and the type of the film, as long as the effects of the present invention are not significantly impaired. The thickness of the second film 2 may be, for example, 5 to 200 μm, 10 to 100 μm, or 20 to 75 μm.

  In addition, the second film may be composed of one layer or may be composed of two or more layers. When the second film is composed of two or more layers, at least one of the layers may have the characteristics of the second film according to the present embodiment, and all the layers may be according to the present embodiment It may have the characteristics of two films. When the second film is composed of two or more layers, each layer may be laminated via an adhesive layer or the like as appropriate.

  Further, the thermally conductive molded body 100 is provided with a reinforcing base (not shown) such as a knitted fabric, a woven fabric, a non-woven fabric or the like between the second film 2 and the resin molded body 3 or in the resin molded body 3 It is also good. By providing the reinforcing substrate, the stretchability of the heat conductive molded body 100 in the plane direction is suppressed, and the possibility of causing a defect such as a crack when peeling the heat conductive molded body from the mold is suppressed, and the handleability is improved. Can be improved. Among them, non-woven fabrics are preferable because they are excellent in the impregnation property of the curable resin composition described later. As a material of the reinforcing substrate, glass, vinylon, aramid, nylon, polyolefin, polyester, acrylic and the like can be used, but glass is preferable because it can impart flame retardancy. The thickness of the reinforcing substrate may be, for example, 20 μm or more or 40 μm or more, and may be, for example, 0.2 mm or less or 0.1 mm or less.

<Method of manufacturing thermally conductive molded body>
Then, the manufacturing method of the said heat conductive molded object is demonstrated. The method of manufacturing a thermally conductive molded body according to the present embodiment is a first film disposed on a mold so as to follow the three-dimensional shape of the mold having a three-dimensional shape, and having a shape corresponding to the three-dimensional shape. Preparing a curable composition containing a thermally conductive material and a (meth) acrylic monomer on a first film (a second step); Placing a second film on the composition, sandwiching the curable composition with the first film and the second film (third step), and (meth) acrylic monomer in the curable composition And radically polymerizing to form a cured product of the curable composition between the first film and the second film (fourth step).

  FIG. 3: is process sectional drawing which shows one Embodiment of the manufacturing method of a heat conductive molded object. The respective steps will be described below with reference to the drawings as appropriate.

(First step)
The first step is a step of preparing a first film having a shape corresponding to the three-dimensional shape, which is disposed on the mold so as to follow the three-dimensional shape of the mold having a three-dimensional shape. As a method of preparing the first film having a three-dimensional shape corresponding to the mold, for example, a vacuum heating pressure bonding method, a vacuum forming method, a film insert molding method and the like can be mentioned.

  Hereinafter, a specific method of the vacuum heating and pressing method will be exemplarily described. First, a mold 20 having a predetermined three-dimensional shape as shown in FIG. 3A is prepared. As shown in FIG. 3 (b), the exemplary vacuum heating and pressing apparatus 30 has a first vacuum chamber 31 and a second vacuum chamber 32 at the top and bottom respectively, and a mold 20 is provided between the upper and lower vacuum chambers. A jig for setting the first film 10 to be attached is provided. Further, in the lower first vacuum chamber 31, the partition plate 34 and the pedestal 33 are installed on a lift table 35 (not shown) which can move up and down vertically, and the mold 20 is mounted on the pedestal 33. Is set. As such a vacuum heating and pressure-bonding device 30, a commercially available one, for example, a double-sided vacuum forming machine (manufactured by Cloth Application Vacuum Co., Ltd.) can be used.

  As shown in FIG. 3 (b), first, with the first vacuum chamber 31 and the second vacuum chamber 32 of the vacuum heating and pressure bonding apparatus 30 open to the atmospheric pressure, the first film 10 is interposed between the upper and lower vacuum chambers. Set The mold 20 is set on the pedestal 33 in the first vacuum chamber 31.

  Next, as shown in FIG. 3C, the first vacuum chamber 31 and the second vacuum chamber 32 are closed, the pressure is reduced, and the inside of each chamber is evacuated. Thereafter, or simultaneously with the application of vacuum, the first film 10 is heated. Next, as shown in FIG. 3D, the lift table 35 is raised to push the mold 20 up to the second vacuum chamber 32. The heating can be performed, for example, by a lamp heater (not shown) incorporated in the ceiling of the second vacuum chamber 32. The heating temperature is not particularly limited, but is usually 50 ° C. or more or 130 ° C. or more, and is 180 ° C. or less or 160 ° C. or less. The degree of vacuum of the reduced pressure atmosphere can be, for example, 0.10 atm or less, 0.05 atm or less, or 0.01 atm or less, where the atmospheric pressure is 1 atm.

  The heated first film 10 is pressed against the surface of the mold 20 and stretched. Thereafter or simultaneously with the drawing, as shown in FIG. 3 (e), the inside of the second vacuum chamber 32 is pressurized to an appropriate pressure (for example, 1 atm to 3 atm). The first film 10 heated by the pressure difference is in close contact with the exposed surface of the mold 20, is drawn following the three-dimensional shape of the exposed surface, and forms a coating in a state of being peelably in contact with the surface of the mold 20 Do. After performing pressure reduction and heating in the state of FIG. 3C, the inside of the second vacuum chamber 32 can be pressurized as it is to cover the exposed surface of the mold 20 with the first film 10.

  Thereafter, the upper and lower first vacuum chambers 31 and the second vacuum chamber 32 are again opened to atmospheric pressure, and the mold 20 coated with the first film 10 is taken out. As shown in FIG. 3F, the edge of the first film 10 in close contact with the surface of the mold 20 can be trimmed to obtain an integral product 40 including the first film 10 and the mold 20. In addition, although the method to implement a 2nd process is described below using the integral product 40, in this embodiment, the type | mold 20 is peeled from the integral product 40, and the 1st shape | molded by three-dimensional shape is carried out. The second step can also be carried out using the film 10 of

(Second step)
The second step is a step of arranging a curable composition containing a thermally conductive material and a (meth) acrylic monomer on a first film. An example of the second step is described below with reference to FIG.

  As shown in FIG. 3 (g), the hollow portion 11 of the one-piece product 40 is filled with a curable composition containing a thermally conductive material and a (meth) acrylic monomer, and a blade or the like is used if necessary. Then, a flattening process is performed to form the filling portion 12 and the curable composition is disposed. There is no particular limitation on the filling of the curable composition, but it is preferable to apply a degassed one in order to prevent the mixing of air.

(Third step)
The third step is a step of disposing a second film on the curable composition and sandwiching the curable composition with the first film and the second film.

  FIG. 3G illustrates a configuration in which the second film 13 is further applied on the filling portion 12 formed in the above-described process. In this aspect, the second film 13 can be disposed so as to cover the first film 10 and the filling portion 12 to obtain the integral product 50. In the third step, in the case of arranging a reinforcing base such as a non-woven fabric between the filling portion 12 and the second film 13, for example, a reinforcing base is applied on the second film 13 It may be disposed so as to be in contact with the filling portion 12, or when the reinforcing base material is disposed in the filling portion 12, the curable composition may be previously impregnated with the reinforcing base material.

(Fourth step)
In the fourth step, the (meth) acrylic monomer in the curable composition is radically polymerized to form a cured product of the curable composition between the first film 10 and the second film 13 (resin molding) It is a process of forming 12a. Thereby, the integral product 50a which has hardened | cured material (resin molding) 12a of a curable composition is obtained.

  The radical polymerization can be performed by, for example, ultraviolet polymerization, electron beam polymerization, γ-ray irradiation polymerization, ionizing ray irradiation polymerization, and the like. The ultraviolet polymerization can be performed, for example, by filling the curable composition containing an appropriate amount of a photopolymerization initiator in the hollow portion 11 to form the filling portion 12, and then irradiating the ultraviolet portion. In the case of polymerization using particle energy rays such as electron beam polymerization, a polymerization initiator is usually unnecessary.

  Photoinitiators include benzoin ethers such as benzoin ethyl ether and benzoin isopropyl ether; anisoin ethyl ether, anisoin isopropyl ether, Michler's ketone (4,4'-tetramethyldiaminobenzophenone), 2,2-dimethoxy-2 -Phenylacetophenone (eg, trade name: KB-1 (Saltomer), trade name: Irgacure 651 (Irgacure 651 (Ciba Specialty Chemicals)), substituted acetophenones such as 2, 2-diethoxyacetophenone; 2 Substituted α-ketols such as -methyl-2-hydroxypropiophenone; aromatic sulfonyl chlorides such as 2-naphthalenesulfonyl chloride; 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) Photoactive oxime compounds such as oximes; bis (2,4,6-trimethylbenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphinocide etc Acyl phosphine oxide compounds; and the like. In addition, the said photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more types.

  The content of the photopolymerization initiator to be added to the curable composition is not particularly limited, but generally 0.05 to 2 parts by weight with respect to 100 parts by weight of the monomer component such as the (meth) acrylic monomer. .0 parts by mass.

  The one-piece product 50a obtained through the fourth step can be optionally cooled and then taken out of the mold 20 to obtain a thermally conductive compact 60 as shown in FIG. 3 (h). In addition, if necessary, the first film 10 and / or the second film 13 may be removed, and punching to an appropriate size to obtain a thermally conductive molded product having an individual three-dimensional shape is also possible. it can. When used as a product without removing the first film 10, there is an advantage that the slipperiness on the surface of the first film 10 and the strength as a product increase when the first film 10 is pushed into a gap of a battery or the like.

  The thermally conductive molded body obtained by the manufacturing method according to the present embodiment is used in vehicles, lithium ion batteries (for example, lithium ion battery packs for vehicles), home appliances, computer devices, etc., for example, IC chips etc. Are disposed so as to fill the gap between the heat-generating component and the heat-releasing component such as the heat sink, so that the heat generated from the heat-generating component can be efficiently transferred to the heat-dissipating component It can be used as a member. In particular, since the thermally conductive molded product according to the present embodiment can be designed freely in shape and size, it can be used, for example, as a substitute for a potting material of a circuit board, and can be used as a heat generating component of complex shape such as a coil. It can also be used against.

  Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to the examples.

  The abbreviations and details of each component used in the examples are described below.

<Preparation of a curable composition>
Each component shown in Table 1 is charged in a planetary mixer at a blending ratio (mass ratio) described in Table 1 and deaerated and mixed by kneading under a reduced pressure (0.01 MPa) for 30 minutes to obtain a curable composition. I got In the following curable composition, the volume ratio of the thermally conductive filler was 67.4% by volume.

  Each abbreviation shown in Table 1 means the following, respectively.

((Meth) acrylic monomer)
· LA: lauryl acrylate · ISTA: isostearyl acrylate · HDDA: 1, 6-hexanediol diacrylate

(Photopolymerization initiator)
-IRGACURE 819: manufactured by BASF, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide

(Plasticizer)
・ T10: Kao Corp., trimellitate plasticizer, trimex T-10

(Antioxidant)
-IRGANOX 1010: manufactured by BASF, pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate)
· AO 503: "ADEKA STAB AO 503" manufactured by ADEKA, ditridecylthiodipropionate

(Heat conductive filler)
・ B53: Nippon Light Metal Co., Ltd., aluminum hydroxide (average particle size 50 μm)
· BF 083: Nippon Light Metal Co., Ltd., aluminum hydroxide (average particle size 8 μm)

(Dispersant)
· BYK-145: manufactured by Big Chemie Japan Ltd., wetting and dispersing agent DISPERBYK-145

<Production of a heat conductive molded body>
Each film shown in Table 2 is prepared, and as shown in FIG. 3 (b), a double-sided vacuum forming machine (made by Fusaku Vacuum Co., Ltd.) is adopted as the vacuum heating and pressing device 30. The film was fixed on the resin mold 20 installed. The heating conditions are set such that the surface temperature of the film is 120 ° C., and the heated film is prevented from being entrained in accordance with the procedure shown in FIG. 3 (c) to FIG. 3 (e) described above. It laminated | stacked on the surface of the type | mold 20, and produced the integral product 40 as shown by FIG.3 (f). The followability of the film was visually confirmed. Here, the mold 20 has a shape such that a semicircular three-dimensional shape of 23.5 mm × 90.0 mm × 4.0 mm as shown in FIG. 3F is obtained. Each property of the used film is shown in Table 2.

The films A to I in Table 2 are as follows.
Film A: Spellen 35E-LL (manufactured by Ube Film Co., Ltd., a three-layer film of PE / EVOH / LLDPE, each layer being a film laminated via an adhesive resin)
Film B: Spellen 35E-LL (manufactured by Ube Film Co., Ltd., a three-layer film of PE / EVOH / LLDPE, each layer being a film laminated via an adhesive resin)
Film C: Hytron BX (manufactured by Tamapoly Corporation, polyacrylonitrile film)
Film D: Diamilon C (Mitsubishi Chemical Corporation, vinylidene chloride-coated non-stretched nylon-6 film)
Film E: Diamilon MF F 001 (manufactured by Mitsubishi Chemical Corporation, PP / EVOH / PP three-layer film, each layer being a film laminated via an adhesive resin)
Film F: Diamilon MF V 442 (manufactured by Mitsubishi Chemical Corporation, EVOH / Nylon / PP / LLDPH four-layer film, with some layers laminated via an adhesive resin)
Film G: UB-OB (made by Tamapoly Corporation, linear low density polyethylene film)
Film H: V-1 (manufactured by Tamapoly Co., Ltd., low density polyethylene film)
Film I: Emblet S50 (manufactured by Unitika Co., Ltd., PET film)

The second film 13 (polyester film liner, or the like) is filled with the curable composition obtained above in the cavity 11 of the one-piece product 40, and then the air is not caught on the filled curable composition. Teijin Films Solutions Co., Ltd., trade name "Purex A50", thickness 50 μm, oxygen permeability 16) was laminated. A rubber roller was applied onto the second film 13 so that the second film 13 was uniformly adhered to the mold 20, to produce an integral product 50. Using a black light lamp, UV irradiation is performed for 15 minutes from a distance of 5.5 cm on the second film 13 side of the integrated product 50 to polymerize the acrylic monomer contained in the curable composition (irradiation conditions: UV- A (wavelength 315 to 380 nm), 7.46 mW / cm ² ), and subsequently the heat conductive molded body 60 was removed from the mold 20.

Cured state of thermally conductive molded body
The first film was peeled off from the obtained heat conductive molded product, and the cured state of the curable composition was confirmed visually and with a finger. If polymerization inhibition occurred, the uncured curable composition slightly remained on the top of the thermally conductive molded product and on the film surface and was cloudy, but if polymerization inhibition did not occur, the film was transparent. It remained as it was. Moreover, the surface of the heat conductive molded object when superposition | polymerization inhibition did not occur was able to confirm presence of tack | tuck by finger touch.

  DESCRIPTION OF SYMBOLS 1 ... 1st film, 2 ... 2nd film, 3 ... Resin molded object, 3a ... 1st surface, 3b ... surface on the opposite side to 1st surface, 100 ... heat conductive molded object.

Claims (7)

Providing a first film disposed on the mold so as to follow the three-dimensional shape of the mold having a three-dimensional shape, and having a shape corresponding to the three-dimensional shape;
Placing on the first film a curable composition comprising a thermally conductive material and a (meth) acrylic monomer;
Placing a second film on the curable composition and sandwiching the curable composition with the first film and the second film;
Radically polymerizing a (meth) acrylic monomer in the curable composition to form a cured product of the curable composition between the first film and the second film;
Equipped with
The oxygen permeability of each of the first film and the second film is less than 1000 ml / m ² · 24 h · atm, and the 50% tensile strength at a temperature of 100 ° C. of the first film is 100 N / 25 mm or less A method for producing a thermally conductive molded article.   The manufacturing method of the thermally conductive molded object of Claim 1 whose thickness of said 1st film is 3-200 micrometers.   The manufacturing method of the thermally conductive molded object of Claim 1 or 2 whose dynamic friction coefficient of said 1st film is 0.7 or less. A resin molded product having a first surface having a three-dimensional shape and containing a thermally conductive material and a (meth) acrylic polymer;
A first film disposed on the first surface of the resin molding so as to follow the three-dimensional shape;
Equipped with
The thermally conductive molded article, wherein the oxygen permeability of the first film is less than 1000 ml / m ² · 24 h · atm, and the 50% tensile strength at a temperature of 100 ° C. is 100 N / 25 mm or less.   The heat conductive compact according to claim 4, wherein the thickness of the first film is 3 to 200 m.   The thermally conductive molded body according to claim 4, wherein a dynamic friction coefficient of the first film is 0.7 or less. And a second film disposed on the surface of the resin molding opposite to the first surface,
The heat conductive molded object according to any one of claims 4 to 6, wherein the oxygen permeability of the second film is less than 1000 ml / m ² · 24 h · atm.

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