TWI608071B - Thermal-radiative film and thermal adhesive tape - Google Patents

Description

Thermal radiation film and thermal radioactive adhesive tape

The present invention relates to thermal radiation films and thermal radioactive adhesive tapes. More specifically, the present invention relates to a thermal radiation film and a thermal radioactive adhesive tape which are suitable for use in heat dissipation from a member which is expected to generate heat due to power consumption such as an electric machine or an electronic device.

The components constituting the electric machine, the electronic device, etc., increase the consumption power as the degree of integration increases and the operation speed increases, and as a result, the amount of heat generation increases. If the amount of heat is increased, the temperature of the component itself will rise. When the temperature of the component rises, the life of the component is reduced due to malfunction or malfunction of the component, and the user is burnt. Therefore, it is desirable to suppress an increase in temperature.

A means for suppressing the rise in temperature is known as a technique for bringing a heat sink into contact with a member. By bringing the heat sink into contact with the member, the heat generated by the member is conducted to the heat sink, and as a result, the temperature rise of the member can be suppressed.

A material having a high thermal conductivity such as metal is used in the heat dissipation plate. However, if the difference between the temperature of the heat sink and the temperature of the outside air is small, the heat accumulated in the heat sink is not discharged, but is still accumulated in the heat sink. Therefore, there is still room for improvement in the heat dissipation plate system as a means for suppressing the temperature rise.

It has been proposed in Japanese Patent No. 2807198 (Patent Document 1) The technology of the subject of the heat sink. In Patent Document 1, it is proposed to use a laminate including a sheet of a thermally radioactive material having a large thermal emissivity and a sheet comprising a sheet of a thermally conductive material having a large thermal conductivity as a heat dissipating body. In the patent document 1, the thermal conductive material may, for example, be cordierite, aluminum titanate, β-spodumene, ceramics, carbon black, or carbon fiber, and the thermal conductive material may be ferrite. Further, in Patent Document 1, the above two types of sheets are maintained in shape by a polyfluorene oxygen addition body, and the individual thicknesses are formed to be 1 mm.

[Advanced technical literature]

Patent Document 1: Japanese Patent No. 2807198

The heat sink of the above Patent Document 1 cannot sufficiently suppress the temperature rise of the member, and it is desired to be more improved. Further, since the electric device or the electronic device is made thinner, the heat sink is also thinned. From this point of view, the heat sink of Patent Document 1 has its limit in thinning in its usable range.

Thus, according to the present invention, a thermal radioactive film comprising a urethane resin and a thermally conductive filler and having a thickness of 0.5 W/m can be provided. The thermal conductivity of K or more, the thermal emissivity of 0.85 or more, the tensile strength of 5N/20 mm or more, and the film thickness of 10 to 30 μm.

Further, according to the present invention, there can be provided a thermal radioactive adhesive tape comprising the above-mentioned thermal radiation film and an adhesive layer in the thickness direction.

According to the present invention, it is possible to provide a device that can more inhibit the formation of electrical equipment and electricity. A thermal radiation film of a film whose temperature rises as a component of a child machine, and a thermal radioactive adhesive tape.

Moreover, in the case of any of the following, it is possible to provide a thermal radiation film of a film which can further suppress the temperature rise of the member, and a thermal radioactive adhesive tape.

(1) The thermally conductive filler is composed of alumina, titania, zirconia, ferrite, cerium oxide, zinc oxide, magnesium oxide, aluminum carbide, lanthanum carbide, aluminum nitride, boron nitride, carbon black, graphite, carbon fiber. And one of the selected ones of melamine cyanurate.

(2) Thermally conductive filler selected from alumina, titania, zirconia, ferrite, cerium oxide, zinc oxide, magnesium oxide, aluminum carbide, tantalum carbide, aluminum nitride, boron nitride and melamine cyanurate a combination of filler A and filler B selected from carbon black, graphite and carbon fibers, or alumina, titania, zirconia, ferrite, cerium oxide, zinc oxide, magnesium oxide, aluminum carbide, tantalum carbide, Combination of filler C selected from aluminum nitride and boron nitride with filler D of melamine cyanurate.

(3) The thermally conductive filler is contained in an amount of 100 to 600 parts by weight based on 100 parts by weight of the urethane resin.

(4) The filler B contains 0.5 to 30 parts by weight based on 100 parts by weight of the filler A, and the filler D contains 1 to 200 parts by weight based on 100 parts by weight of the filler C.

(5) The thermally conductive filler is any combination of the following: ‧ a combination of a filler selected from alumina, tantalum carbide, aluminum nitride and melamine cyanurate and a filler of carbon black; ‧ a filler of alumina and melamine cyanurate a combination of fillers.

(6) When the thickness of the urethane-based resin is 25 μm, the tensile strength is 5 N/20 mm or more.

1‧‧‧Thermal radioactive film

2, 4‧‧‧ adhesive layer

3‧‧‧Hot conductive materials (flakes)

a‧‧‧Hot radioactive adhesive tape

B‧‧‧copper foil

C‧‧‧heater

D‧‧‧ thermocouple

e‧‧‧Insulation

Figure 1 is a schematic cross-sectional view of a thermal radioactive adhesive tape of the present invention.

Figure 2 is a schematic cross-sectional view of a thermal radioactive adhesive tape of the present invention.

Figure 3 is a schematic cross-sectional view of a thermal radioactive adhesive tape of the present invention.

Fig. 4 (a) and (b) are schematic explanatory views of the heat dissipation effect test of the embodiment.

Fig. 5 is a graph showing changes in temperature over time in the heat radiation effect test of the thermal radiation adhesive tapes of Example 1 and Comparative Example 1.

(thermal radiation film)

The thermal radiation film is represented by a film containing an urethane resin and a thermally conductive filler and having a film thickness of 10 to 30 μm. Further, the thermal radioactive film has a thickness of 0.5 W/m. The thermal conductivity of K or more, the thermal emissivity of 0.85 or more, and the tensile strength of 5N/20 mm or more.

The thermal radiation film has the thermal conductivity, the thermal emissivity, the tensile strength, and the film thickness in the above range, and can suppress the temperature rise of the member, and can be thinned within a usable range. Here, the usable range refers to the usability in which the film does not easily cause work obstacles when attached to the member.

The thermal conductivity is preferably 0.5 W/m. K or more, more preferably 1.0 W/m. K or more. The heat emissivity is preferably 0.85 or more, more preferably 0.88 or more. In the range of such preferable thermal conductivity and thermal emissivity, a film which can further suppress the temperature rise of the member can be provided. The thermal conductivity can be 0.5W/m. K, 1.0W/m. K, 1.5W/m. K, 2.0W/m. K, 2.5W/m. K, 3.0W/m. The value of K, etc. The heat emissivity may be 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.95.

The tensile strength is preferably 5 N/20 mm or more, more preferably 10 N/20 mm or more. membrane The thickness is preferably from 10 to 30 μm, more preferably from 10 to 25 μm. If such a preferred range of tensile strength and film thickness is present, a film that is easier and more film-friendly can be provided. The tensile strength may be 10 N/20 mm, 15 N/20 mm, 20 N/20 mm, 25 N/20 mm, 30 N/20 mm, 35 N/20 mm, 40 N/20 mm. The film thickness may be 10 μm, 15 μm, 20 μm, or 25 μm.

(a) Amino acid ester resin

The urethane-based resin may have a film shape having a thickness of 30 μm, and is not particularly limited as long as it is a resin capable of imparting a tensile strength of 5 N/20 mm or more. Among these urethane-based resins, a resin having a tensile strength of 5 N/20 mm or more at a thickness of 25 μm is more preferable. The tensile strength at a thickness of 30 μm and/or 25 μm may be 5 N/20 mm, 10 N/20 mm, 15 N/20 mm, 20 N/20 mm, 25 N/20 mm, 30 N/20 mm, 35 N/20 mm, 40 N/20 mm.

Examples of the urethane-based resin include (1) a polylactone ester polyol obtained by ring-opening polymerization of caprolactone and a diisocyanate (for example, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, and hexa a methyl diisocyanate or the like) a caprolactone type polyurethane elastomer synthesized by a polymerization addition reaction; (2) a dicarboxylic acid (for example, adipic acid, citric acid, etc.) and a diol (for example, poly a dicarboxylate polyol of propylene glycol), a dicarboxylate type polyurethane elastomer synthesized by a polymerization addition reaction with a diisocyanate; (3) a polybutanediol, a polyalkylene glycol to be polymerized A polyether polyol such as polypropylene glycol (polypropylene glycol), a polyether polyurethane elastomer synthesized by a polymerization addition reaction with a diisocyanate; and (4) a polycarbonate polyol.

The urethane resin may be a mixture of the above (1) to (4).

The urethane-based resin may have a functional group such as a carboxyl group or an amine group. In particular, by having a carboxyl group, the dispersibility of the thermally conductive filler can be improved.

The urethane elastomer preferably has a weight average molecular weight of 10,000 to 200,000. If the molecular weight is in this range, a film which is easier to use and more thin can be obtained.

The commercially available product of the urethane-based resin may be a DAIFERAMINE MAU series (models 5022, 4308HV, 9022, etc.) or a RESAMINE ME series (models ME-44ELP, ME-8105LP, etc.) derived from Dairi Seiki Co., Ltd. Elastomer of a reaction of a polyurethane elastomer precursor with an isocyanate crosslinking agent such as CORONATE L-55E of Japan Polyurethane Co., Ltd., Takenate D-160N of Mitsui Chemicals Co., Ltd., KURAMIRON U1000 of Kuraray Co., Ltd. Elastomers of the series (models 1180, 1190, etc.) or 9000 series (models 9180, 9185, etc.).

(b) Thermally conductive filler

As a thermally conductive filler, as long as it can be applied to the film 0.5W / m. The filler having a thermal conductivity of K or more and a thermal emissivity of 0.85 or more is not particularly limited. Specifically, it is composed of alumina, titania, zirconia, ferrite, cerium oxide, zinc oxide, magnesium oxide, aluminum carbide, cerium carbide, aluminum nitride, boron nitride, carbon black, graphite, carbon fiber, and cyanuric acid. One or more selected from the group consisting of melamine. The thermal conductivity can be 0.5W/m. K, 1.0W/m. K, 1.5W/m. K, 2.0W/m. K, 2.5W/m. K, 3.0W/m. The value of K, etc. The heat emissivity may be 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.95.

In order to improve heat transfer and heat radiation efficiency, the thermally conductive filler is preferably: alumina, titania, zirconia, ferrite, yttria, zinc oxide, magnesium oxide, aluminum carbide, tantalum carbide, aluminum nitride, nitride a combination of boron and melamine cyanurate selected filler A, and filler B selected from carbon black, graphite and carbon fibers; Or filler C selected from alumina, titania, zirconia, ferrite, cerium oxide, zinc oxide, magnesium oxide, aluminum carbide, tantalum carbide, aluminum nitride and boron nitride, and filler D of melamine cyanurate The combination.

For example, the combination of the filler A and the filler B may be exemplified by alumina/carbon black, titanium oxide/carbon black, zirconia/carbon black, ferrite/carbon black, cerium oxide/carbon black, zinc oxide/carbon black, oxidation. Magnesium/carbon black, aluminum carbide/carbon black, tantalum carbide/carbon black, aluminum nitride/carbon black, boron nitride/carbon black and melamine cyanurate/carbon black; alumina/graphite, titanium oxide/graphite, zirconia /graphite, ferrite/graphite, yttria/graphite, zinc oxide/graphite, magnesia/graphite, aluminum carbide/graphite, tantalum carbide/graphite, aluminum nitride/graphite, boron nitride/graphite and melamine cyanurate/ Graphite; alumina/carbon fiber, titanium oxide/carbon fiber, zirconia/carbon fiber, ferrite/carbon fiber, cerium oxide/carbon fiber, zinc oxide/carbon fiber, magnesium oxide/carbon fiber, aluminum carbide/carbon fiber, tantalum carbide/carbon fiber, nitriding Aluminum/carbon fiber, boron nitride/carbon fiber and melamine cyanurate/carbon fiber.

For example, the combination of the filler C and the filler D may be exemplified by alumina/melamine cyanurate, titanium oxide/melamine cyanurate, zirconia/melamine cyanurate, ferrite/melamine cyanurate, cerium oxide/melamine cyanurate, zinc oxide. / Melamine cyanurate, magnesium oxide / melamine cyanurate, aluminum carbonate / melamine cyanurate, lanthanum carbide / melamine cyanurate, aluminum nitride / melamine cyanurate and boron nitride / melamine cyanurate.

A better combination is: ‧ a filler selected from alumina, tantalum carbide, aluminum nitride and melamine cyanurate, in combination with a filler of carbon black; ‧ Combination of alumina filler and melamine cyanurate filler.

In order to increase the efficiency of heat conduction, the thermally conductive filler preferably has a small particle diameter. For example, the particle diameter is preferably 20 μm or less, more preferably 10 μm or less. The lower limit of the particle diameter is preferably 0.1 μm from the viewpoint of ease of work and ease of availability. The particle diameter may be 0.1 μm, 1 μm, 5 μm, 10 μm, 15 μm, or 20 μm.

The particle size can be determined by laser diffraction scattering.

(c) urethane resin and thermally conductive filler

The content ratio of the urethane-based resin and the thermally conductive filler is not particularly limited as long as it can impart specific thermal conductivity, thermal activity, tensile strength, and film thickness to the film. For example, the thermally conductive filler preferably contains 100 to 600 parts by weight, more preferably 200 to 500 parts by weight, based on 100 parts by weight of the urethane resin.

Thermal Conductive Filler When the combination of the above filler A and filler B is used, the filler B preferably contains 0.5 to 30 parts by weight based on 100 parts by weight of the filler A. The content of the filler B may be 0.5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, or 30 parts by weight. Further, when the combination of the above filler C and the filler D is used, the filler D preferably contains from 1 to 200 parts by weight based on 100 parts by weight of the filler C. The content of the filler D may be 1 part by weight, 50 parts by weight, 100 parts by weight, or 200 parts by weight.

(d) Other ingredients

The film system may contain other components within a range that does not impair the effects of the present invention. Other components include a coloring agent, an antistatic agent, and an antioxidant.

(e) Planar shape of the thermal radiation film

The thermal radiation film is not particularly limited, and may be a planar shape required for a machine that requires heat radiation.

(thermal radioactive adhesive tape) (a) Adhesive layer

The thermal radiation adhesive tape is, for example, a schematic cross-sectional view of Fig. 1 and refers to the thermal radiation film 1 and the adhesive layer 2 in the thickness direction. The thickness of the adhesive layer can be, for example, in the range of 3 to 50 μm. The adhesive layer can be formed entirely in the thermal radiation film or partially formed in a specific pattern. The film thickness may be 3 μm, 10 μm, 20 μm, 30 μm, 40 μm, or 50 μm.

The adhesive layer is not particularly limited, and a layer composed of a known adhesive can be used. For example, an acrylic adhesive can be mentioned.

As the acrylic pressure-sensitive adhesive, for example, an adhesive obtained by polymerizing an acrylic monomer in the presence of any polymerization initiator or a commercially available adhesive can be used.

(a-1) Acrylic monomer

Among the acrylic monomers, an alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms is preferably contained as a main component (50% by weight or more). Further, (meth) acrylate means methacrylate or acrylate.

The alkyl (meth)acrylate having an alkyl group having 1 to 14 carbon atoms may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate or n-propyl (meth)acrylate, or (methyl). Isopropyl acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, n-octyl (meth)acrylate, (meth)acrylic acid Octyl ester, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, and the like. These alkyl (meth)acrylates may be used alone or in combination of two or more. Among the alkyl (meth)acrylates, preferred are alkyl (meth)acrylates having an alkyl group having 1 to 8 carbon atoms, more preferably (meth)acrylic groups having an alkyl group having 1 to 4 carbon atoms. The alkyl ester is more preferably n-butyl (meth)acrylate, particularly preferably n-butyl acrylate.

Examples of the other acrylic monomer include a carboxyl group-containing monomer such as acrylic acid, methacrylic acid or carboxyethyl acrylate; 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate; a hydroxyl group-containing monomer such as 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth)acrylate or (4-hydroxymethylcyclohexyl)-methyl acrylate. These other (meth) acrylates may be used alone or in combination of two or more. The (meth) acrylate preferably contains both a carboxyl group-containing monomer and a hydroxyl group-containing monomer.

The acrylic monomer contains, as a main component, an alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms. Therefore, the acrylic single system does not require the use of other acrylic monomers, and may be formed only of alkyl (meth)acrylate. Further, from the viewpoint of easily obtaining an adhesive composition having desired properties, the other acrylic monomer preferably contains less than 50% by weight and 1% by weight or more, more preferably 5 to 30% by weight, and still more It is preferably 5 to 15% by weight. The content of the acrylic monomer may be 1% by weight, 5% by weight, 10% by weight, 30% by weight, 40% by weight, or 49% by weight.

Further, a vinyl monomer may be added to the (meth) acrylate as needed. Examples of the vinyl monomer include itaconic acid, maleic acid, crotonic acid, maleic anhydride, itaconic anhydride, vinyl acetate, N-vinylpyrrolidone, N-vinylcarboxylic acid decylamine, styrene, and the like. N-ethylene caprolactam and the like. These vinyl monomers may be used alone or in combination of two or more.

(a-2) polymerization initiator

Examples of the polymerization initiator to be used arbitrarily include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylpropionamidine) disulfide, and 2,2'-couple. Nitrogen bis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis (2) -methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4,4-trimethyl) Pentane), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis[2-methyl-N-(phenylmethyl)-propane脒] hydrochloride, 2,2'-azobis[2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane] hydrochloride, 2,2'-azobis[2 An azo polymerization initiator such as -(2-imidazolin-2-yl)propane; a persulfate polymerization initiator such as potassium persulfate or ammonium persulfate; benzamidine peroxide, hydrogen peroxide, hydrogen Tert-butyl peroxide, di(tert-butyl peroxide), tert-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis(t-butylperoxy-3)-3, 3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 3,3,5-trimethylcyclohexanyl peroxide, peroxylated valeric acid A peroxide-based polymerization initiator such as t-butyl peroxypivalate; a reducing oxidation polymerization initiator composed of persulfate and sodium hydrogen sulfite. These polymerization initiators may be used alone or in combination of two or more.

The polymerization initiator is preferably used in an amount of from 0.005 to 1 part by weight based on 100 parts by weight of the acrylic monomer. By using a polymerization initiator in this range, an acrylic adhesive having improved adhesion characteristics can be formed. Further, the polymerization initiator is preferably used in an amount of from 0.1 to 0.5 parts by weight. The polymerization initiator may be used in an amount of 0.005 parts by weight, 0.01 parts by weight, 0.1 parts by weight, 0.5 parts by weight, or 1 part by weight.

(a-3) organic solvent

The organic solvent may be contained from the viewpoint of easiness of formation of the adhesive layer. The organic solvent is not particularly limited, and examples thereof include known organic solvents which can be used for the adhesive composition. Examples thereof include aliphatic hydrocarbons such as hexane and heptane; esters such as methyl acetate, ethyl acetate, and propyl acetate; and aromatic hydrocarbons such as toluene, xylene, and ethylbenzene. These organic solvents may be used alone or in combination of two or more.

Further, when an organic solvent is used, it is preferred to adjust the ratio of use to make acrylic The solid content of the adhesive is 10% by weight or more. Further, it is more preferable to adjust the use ratio so that the solid content is 20 to 50% by weight.

(a-4) Other ingredients

In order to improve the shape stability of the adhesive layer, the acrylic adhesive may have a crosslinked structure. In order to provide the crosslinked structure, for example, the isocyanate crosslinking agent or the aluminum chelate crosslinking agent may be used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the acrylic pressure-sensitive adhesive. The crosslinking agent may be used in an amount of 0.01 parts by weight, 0.1 parts by weight, 1.0 part by weight, 5.0 parts by weight, or 10 parts by weight.

Further, in order to improve the thermal conductivity of the adhesive layer, the acrylic adhesive may contain a thermally conductive filler. As the filler, any of the thermally conductive fillers exemplified in the above description of the thermal radiation film can be used. The thermally conductive filler may be used in an amount of 50 to 500 parts by weight based on 100 parts by weight of the acrylic adhesive. The heat conductive filler may be used in an amount of 50 parts by weight, 100 parts by weight, 200 parts by weight, 350 parts by weight, or 500 parts by weight.

(b) a sheet containing a thermally conductive material

In order to improve the thermal conductivity of the tape, the thermal radioactive adhesive tape may further have a sheet containing a thermally conductive material selected from copper, aluminum and graphite between the thermal radiation film and the adhesive layer. The specific configuration is a configuration in which the sheet 3 is directly adhered to the thermal radiation film 1 as shown in Fig. 2, or the sheet 3 is adhered to the thermal radiation film 1 through the adhesive layer 4 as shown in Fig. 3. Composition.

For example, when a thermally conductive material such as a copper foil can be individually held in a sheet-like shape, the sheet can be used as it is. Moreover, when a particulate heat conductive material is used, it can be formed into a sheet shape by mixing with a resin binder.

The thickness of the sheet is not particularly limited insofar as it does not inhibit thermal conductivity, and for example, 10 to 5000 μm.

(Use of thermal radiation film and thermal radioactive adhesive tape)

The thermal radiation film and the thermal radioactive adhesive tape can be used for any of the applications as long as it is desired to dissipate the generated heat to the outside. For example, electrical equipment such as motors and illuminations, and heat dissipation applications of electronic devices such as LSIs, ICs, and resistors can be cited. In particular, it is possible to use a mobile phone or a display such as a liquid crystal or an organic EL which has been significantly thinned in recent years, and the film and the tape system of the present invention can be sufficiently exhibited as a film.

Example

The present invention will be further illustrated by the following examples, but the present invention is not limited to the following examples. Further, the thermal conductivity of the thermal radiation film, the measurement of the thermal emissivity and the tensile strength, and the heat radiation effect test method of the thermal radiation adhesive tape are as follows.

(Thermal conductivity)

The measurement of the thermal conductivity was carried out using a steady-state thermal conductivity measuring device GH-1 manufactured by ULVAC Corporation. The thermal radiation film was sandwiched between aluminum plates having a diameter of 50 mm, and the holder was placed in a measuring device, and the thermal conductivity was measured in accordance with ASTM E1530.

(thermal emissivity)

The measurement of the heat emissivity was carried out using a thermal emissivity meter D&S AERD manufactured by Kyoto Electronics Manufacturing Co., Ltd. The sample was measured by cutting the thermal radiation film into a width of 60 mm in length. After the thermal emissivity meter was calibrated to the standard sample, the measurement sample was placed on a thermal emissivity meter and the thermal emissivity was measured.

(Tensile Strength)

The sample was measured by cutting the thermal radiation film to a size of 20 mm in width and 100 mm in length. To fix both sides of the test sample to Shimadzu Corporation The sample was set in the manner of AUTOGRAPH AGS-H, and the sample was stretched at a stretching speed of 300 mm/min. The force at which the sample was broken was measured, and the obtained value was tensile strength (N/20 mm).

(heat dissipation test)

A heater (output 10 W, width 25 mm, length 50 mm) was placed at a center below the 70 μm thick copper foil (width and length 150 mm) using an adhesive having a thickness of 10 μm. After the thermocouple is placed in the center of the heater and the thermocouple is placed on the insulation, the heater is heated at a constant output (10W). The temperature after heating for 15 minutes was measured. The resulting temperature is the reference temperature.

Next, after bonding the thermal radiation adhesive tape to the said copper foil, the temperature after heating for 15 minutes was measured by the method similar to the measurement of a reference temperature. Fig. 4 (a) and (b) are schematic views showing the state of installation at the time of measurement. Fig. 4(a) is a plan view and Fig. 4(b) is a side view. In the figure, a represents a thermal radioactive adhesive tape, b represents a copper foil, c represents a heater, d represents a thermocouple, and e represents a heat insulating material.

The reference temperature is subtracted from the measured temperature, and the obtained value is used to evaluate the heat dissipation effect. When the reduction value is below -10 °C, the heat dissipation effect is large and evaluated as ○. When the temperature is higher than -10 °C, the heat dissipation effect is insufficient and evaluated as ×.

Example 1 (thermal radiation film)

An isocyanate-based crosslinking agent (Japan Polyamine A) was added to 286 parts by weight of a urethane resin precursor (DAIFERAMINE MAU-5022, manufactured by Dairi Seiki Co., Ltd., solid content: 35 wt%, weight average molecular weight: 6 to 70,000). CORONATE L-55E manufactured by Oleate Co., Ltd., 55 parts by weight of solid content) 57 parts by weight, 400 parts by weight of alumina (AL-47H manufactured by Showa Denko Co., Ltd., particle size: 2 μm), and carbon black (CB4873, manufactured by Taiping Chemical Co., Ltd.) Parts by weight and stirred. After stirring, the composition for producing a thermal radiation film is obtained by defoaming.

The obtained composition was applied to the release film at a specific thickness. The obtained coating film was dried at 100 ° C for 2 minutes, and then aged at 40 ° C for 3 days, whereby a thermal radiation film having a thickness of 25 μm was obtained.

(thermal radioactive adhesive tape)

91 parts by weight of n-butyl acrylate, 8 parts by weight of acrylic acid, 1 part by weight of 2-hydroxyethyl methacrylate, 0.2 parts by weight of azobisisobutyronitrile (AIBN, polymerization initiator), and a solvent (ethyl acetate: Toluene = 9:1 (weight ratio)) 150 parts by weight of the mixture. The obtained mixture was reacted at 85 ° C for 5 hours in a nitrogen stream, thereby obtaining a solid content of 40% by weight and a viscosity of 7000 mP. s acrylic adhesive.

1 part by weight of an isocyanate-based crosslinking agent (CORONATE L-55E manufactured by Nippon Polyurethane Co., Ltd.) and 120 parts by weight of alumina (AL-47H manufactured by Showa Denko Co., Ltd.) were added to 100 parts by weight of the acrylic pressure-sensitive adhesive. Stir. After stirring, the composition for producing an adhesive layer was obtained by defoaming.

The obtained composition was applied to the release film at a specific thickness. The obtained coating film was dried at 100 ° C for 2 minutes, thereby forming an adhesive layer having a thickness of 25 μm. The adhesive layer was transferred to a thermal radioactive film and aged at 40 ° C for 3 days, thereby obtaining a thermal radioactive adhesive tape.

Example 2

A thermal radioactive adhesive tape was obtained in the same manner as in Example 1 except that the amount of alumina contained in the composition for producing a thermal radiation film was 200 parts by weight.

Example 3

A thermal radioactive adhesive tape was obtained in the same manner as in Example 1 except that the amount of alumina contained in the composition for producing a thermal radiation film was 500 parts by weight.

Example 4

In addition, the addition amount of the alumina contained in the composition for the production of the thermal radiation film was 180 parts by weight, and 80 parts by weight of the substituted carbon black of melamine cyanurate (manufactured by Nissan Chemical Industries, Ltd., particle size: 2 μm) was added. A thermal radioactive adhesive tape was obtained in the same manner as in Example 1.

Example 5

A thermal radioactive adhesive was obtained in the same manner as in Example 1 except that 170 parts by weight of melamine cyanurate (MC-6000 manufactured by Nissan Chemical Industries, Inc., particle size: 2 μm) was added instead of the alumina contained in the composition for producing a thermal radiation film. band.

Example 6

A thermal radioactive adhesive tape was obtained in the same manner as in Example 1 except that aluminum nitride (having a particle size of 1 μm manufactured by Tokuyama Co., Ltd.) was added instead of the alumina contained in the composition for producing a thermal radiation film.

Example 7

A thermal radioactive adhesive tape was obtained in the same manner as in Example 1 except that cerium carbide (H3000 manufactured by Shin-Etsu Chemical Co., Ltd., particle size: 4 μm) was added instead of the alumina contained in the composition for producing a thermal radiation film.

Example 8

131 parts by weight of a urethane-based thermoplastic resin (KURAMIRON U1190, manufactured by Kuraray Co., Ltd., solid content: 100% by weight) was dissolved in 131 parts by weight of N,N'-dimethylformamide at 60 °C. To the solution obtained, 400 parts by weight of alumina (AL-47H, manufactured by Showa Denko Co., Ltd., particle size: 2 μm) and 12 parts by weight of carbon black (CB4873 manufactured by Taiping Chemical Co., Ltd.) were added and stirred. After stirring, the composition for producing a thermal radiation film is obtained by defoaming.

The obtained composition was applied to the release film at a specific thickness. The obtained coating film was dried at 150 ° C for 3 minutes, and then aged at 40 ° C for 3 days, thereby obtaining a thickness of 25 μm. Thermal radioactive film.

A thermal radioactive adhesive tape was obtained in the same manner as in Example 1 except that the above film was used.

Example 9

A thermal radioactive adhesive tape was obtained in the same manner as in Example 8 except that KURAMIRON U9185 (solid content: 100% by weight) manufactured by Kuraray Co., Ltd. was used as the urethane-based thermoplastic resin.

Comparative example 1

A thermal radioactive adhesive tape was obtained in the same manner as in Example 1 except that alumina was not added to the composition for producing a thermal radiation film.

Comparative example 2

The thermal radiation film was produced in the same manner as in Example 1 except that the amount of alumina contained in the composition for producing a thermal radiation film was 700 parts by weight, but the film could not be formed as a film.

Comparative example 3

A thermal radioactive adhesive tape was obtained in the same manner as in Example 1 except that carbon black was not added to the composition for producing a thermal radiation film.

Comparative example 4

In the same manner as in Example 1, except that alumina and carbon black were not added to the composition for producing a thermal radiation film, and 150 parts by weight of melamine cyanurate (MC-6000 manufactured by Nissan Chemical Industries, Ltd., particle size: 2 μm) was added. Get a radioactive adhesive tape.

Comparative Example 5

In addition to the addition of aluminum oxide and carbon black to the composition for producing a thermal radiation film, and adding 200 parts by weight of aluminum (11-0018, manufactured by Toyo Aluminum Co., Ltd.), it was the same as Example 1. In the same way, a thermal radioactive adhesive tape is obtained.

Comparative Example 6

Alumina (AL-47H, manufactured by Showa Denko Co., Ltd., particle size 2 μm) was added to 286 parts by weight of epoxy resin (YP-50EK35, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., solid content: 35 wt%, weight average molecular weight: about 70,000). 200 parts by weight and carbon black (CB4873 manufactured by Taiping Chemical Co., Ltd.) 12 parts by weight and stirred. After stirring, the composition for producing a thermal radiation film was obtained by defoaming.

A thermal radiation film was obtained in the same manner as in Example 1 except that the above composition for film production was used. The resulting film did not have sufficient tensile strength.

Comparative Example 7

The thermal radiation film was produced in the same manner as in Comparative Example 6, except that the amount of alumina contained in the composition for producing a thermal radiation film was 400 parts by weight, but the film could not be formed as a film.

Comparative Example 8

An isocyanate-based crosslinking agent (CORONATE L-55E, manufactured by Nippon Polyurethane Co., Ltd., solid content: 55 wt%) was added to 200 parts by weight of an acrylic resin (ACRYDIC A-804, manufactured by DIC Co., Ltd., 50% by weight). 2 parts by weight, 200 parts by weight of alumina (AL-47H manufactured by Showa Denko Co., Ltd., particle size: 2 μm), and 12 parts by weight of carbon black (CB4873 manufactured by Taiping Chemical Co., Ltd.) were stirred and stirred. After stirring, a composition for producing a thermal radiation film was obtained by defoaming.

A thermal radiation film was obtained in the same manner as in Example 1 except that the above composition for film production was used. The resulting film did not have sufficient tensile strength.

Comparative Example 9

In addition to setting the amount of alumina contained in the composition for producing a thermal radiation film to A thermal radioactive film was produced in the same manner as in Comparative Example 8 except for 400 parts by weight, but a film could not be formed as a film.

Comparative Example 10

100 parts by weight of a polyester-based thermoplastic resin (ER-1082, manufactured by Mitsubishi Rayon Co., Ltd., 100% by weight solids, and a weight average molecular weight of about 30,000) was dissolved in 100 parts by weight of ethyl acetate at 50 °C. To the obtained solution, 200 parts by weight of alumina (AL-47H, manufactured by Showa Denko Co., Ltd., particle size: 2 μm) and 12 parts by weight of carbon black (CB4873 manufactured by Taiping Chemical Co., Ltd.) were added and stirred. After stirring, the composition for producing a thermal radiation film was obtained by defoaming.

The obtained composition was applied to the release film at a specific thickness. The obtained coating film was dried at 100 ° C for 3 minutes, and then aged at 40 ° C for 3 days, whereby a thermal radiation film having a thickness of 25 μm was obtained. The resulting film did not have sufficient tensile strength.

Comparative Example 11

The thermal radiation film was produced in the same manner as in Comparative Example 10 except that the amount of alumina contained in the composition for producing a thermal radiation film was 400 parts by weight, but the film could not be formed as a film.

The various test results of the obtained thermal radiation film and the thermal radioactive adhesive tape, the types of materials used, and the amounts used are shown in Table 1.

Fig. 5 is a graph showing changes in the measured temperature over time in the heat radiation effect test of the thermal radiation adhesive tapes of Example 1 and Comparative Example 1. Figure 5 shows a diagram of a thermal radioactive adhesive tape without a thermal radiation film.

It can be confirmed from Table 1 and Figure 5 that it has 0.5 W/m. The thermal radiation film of the embodiment having a thermal conductivity of K or more, a thermal emissivity of 0.85 or more, a tensile strength of 5 N/20 mm or more, and a film thickness of 10 to 30 μm is high in heat dissipation.

1‧‧‧Thermal radioactive film

2‧‧‧Adhesive layer

Claims (8)

A thermal radioactive film comprising an urethane resin and a thermally conductive filler and having a thickness of 0.5 W/m. Thermal conductivity above K, thermal emissivity of 0.85 or more, tensile strength of 5N/20 mm or more, and film thickness of 10 to 30 μm; the above thermally conductive filler: by alumina, titania, zirconia, ferrite, oxidation Combination of filler A selected from cerium, zinc oxide, magnesium oxide, aluminum carbide, cerium carbide, aluminum nitride, boron nitride and melamine cyanurate, and filler B selected from carbon black, graphite and carbon fibers; a combination of filler C selected from titanium oxide, zirconium oxide, ferrite, lanthanum oxide, zinc oxide, magnesium oxide, aluminum carbide, tantalum carbide, aluminum nitride and boron nitride, and filler D of melamine cyanurate; or It contains at least a filler selected from aluminum carbide, aluminum nitride and boron nitride. The thermally conductive film according to the above aspect of the invention, wherein the thermally conductive filler is contained in an amount of 100 to 600 parts by weight based on 100 parts by weight of the urethane resin. The thermal radiation film according to claim 1, wherein the filler B contains 0.5 to 30 parts by weight based on 100 parts by weight of the filler A, and the filler D is contained in 100 parts by weight of the filler C. 1 to 200 parts by weight. The thermal radiation film according to claim 1, wherein the thermally conductive filler is a combination of a filler selected from alumina, tantalum carbide, aluminum nitride, and melamine cyanurate and a filler of carbon black; or A combination of a filler of alumina and a filler of melamine cyanurate. The thermal radiation film according to the first aspect of the invention, wherein the urethane resin has a tensile strength of 5 N/20 mm or more when the thickness of the urethane resin is 25 μm. A thermal radioactive adhesive tape having a thermal radiation film and an adhesive layer as described in claim 1 in the thickness direction. The thermal radioactive adhesive tape according to claim 6, which is provided between the thermal radiation film and the adhesive layer, and further comprises a sheet containing a thermally conductive material selected from copper, aluminum and graphite. The thermal radioactive adhesive tape according to claim 7, wherein the thermal radiation film and the heat conductive material-containing sheet further have an adhesive layer.