TW201617218A - Laminated sheet and manufacturing method of the laminated sheet - Google Patents

Abstract

The present invention provides a laminate sheet which is available to adhere to a heating element easily and is usable as a heat spreader which has high emission properties, and a manufacturing method of the laminated sheet. The present invention provides a laminated sheet (10), which includes a metal sheet layer (1) and an adhesive layer (2), wherein the metal sheet layer includes a metal layer (12) and a heat radiation layer (11) which comprises a heat radiation filler (C) and a binder component (D), and wherein the adhesive layer (2) includes an adhesive resin composition (A) and a heat conductive filler (B), and the adhesive layer (2) is provided on the surface of the metal sheet layer (1) at the side where the metal layer is provided.

Description

Laminated sheet and method for manufacturing laminated sheet

The present invention relates to a method of manufacturing an electronic component such as a semiconductor wafer, a transistor, or a condenser, and a laminated sheet and a laminated sheet provided by radiation from a battery.

In recent years, in electronic components such as semiconductor wafers, transistors, and condensers, and electric components such as batteries have been developed to have higher performance. Along with this, the amount of heat generated by the electronic component or the electrical component gradually increases. If the electronic component or the electrical component is at a high temperature, the life may be shortened or the reliability may be lowered.

Therefore, conventionally, a heat sink or a heat spreader that dissipates heat generated by such heat is attached to an electronic component or an electrical component. As the heat sink system, an adhesive tape or the like is bonded to a metal foil having thermal conductivity such as aluminum foil or copper foil.

For example, Patent Document 1 discloses a heat-dissipating heat-dissipating sheet obtained by laminating an adhesive layer and a heat-radiating sheet, and the heat-radiating sheet is provided with a heat radiation layer on a layer made of aluminum or an aluminum alloy. .

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2005-101025

However, the heat radiation layer disclosed in Patent Document 1 is not coated with alumina, and thus is not sufficient in heat radiation.

The present invention has been made in view of the above circumstances, and provides a laminated body which can be easily joined to a heat generating body such as an electronic component, and which efficiently diffuses and dissipates heat generated, and which is small and lightweight in accordance with various electronic components. A thinned laminated sheet and a method of producing the laminated sheet.

The present invention has the following (1) to (13) as its gist.

(1) A laminated sheet comprising: a metal foil layer composed of a heat radiation layer containing a heat radiation filler (C) and a binder component (D) and a metal layer, and laminated to the metal foil An adhesive layer on the side of the metal layer side of the layer, the adhesive layer comprising an adhesive resin composition (A) and a thermally conductive filler (B).

(2) The laminated thin film of (1), wherein the heat radiation filler (C) is a carbonaceous material.

(3) The laminated sheet according to (2), wherein the carbonaceous material is One or two or more selected from the group consisting of carbon black, graphite, and gas phase carbon fiber.

(4) The laminated sheet according to any one of (1) to (3), wherein the binder component (D) contains a polymer polysaccharide and an acid crosslinking agent.

(5) The laminated thin film according to (4), wherein the polymer polysaccharide is one or more selected from the group consisting of chitin, chitosan and derivatives thereof, and the acid crosslinking agent is One or two or more selected from the group consisting of pyromellitic acid, trimellitic acid, maleic acid, phthalic acid, and the like.

(6) The laminated sheet according to any one of (1) to (5) wherein the heat radiation layer has an average thickness of 0.1 to 4 μm.

(7) The laminated sheet according to any one of (1) to (6) wherein the metal foil layer has an average thickness of 0.02 to 0.5 mm.

The laminated sheet according to any one of (1) to (7), wherein the adhesive layer comprises: an adhesive resin composition (A), the aforementioned thermally conductive filler (B), and a polymerization initiator (E) The cured resin composition (A) contains a (meth)acryl fluorenyl group-containing polyurethane (a) and a polymerizable monomer (b).

(9) The laminated sheet according to any one of (1) to (8), wherein the thermally conductive filler (B) is contained in an amount of from 250 to 900 parts by mass based on 100 parts by mass of the adhesive resin composition (A). ).

The laminated thin film of any one of (1) to (9), wherein the heat conductive filler (B) contains one or more selected from the group consisting of metal oxides and metal hydrates.

(11) The laminated sheet according to any one of (1) to (10), wherein the adhesive layer is laminated on the opposite side of the metal foil layer There are peeling sheets.

(12) A heat sink comprising the laminated sheet according to any one of (1) to (11).

(13) An electronic machine in which a heat sink such as (12) is incorporated.

(14) A method of producing a laminated sheet, characterized in that an adhesive sheet and a metal foil are laminated on the release sheet in this order, and laminated in such a manner that the heat radiation layer is located at the outermost side, the adhesive sheet It is composed of an adhesive layer containing an adhesive resin composition (A) and a heat conductive filler (B); the metal foil is composed of a metal layer and a heat radiation layer containing the heat radiation filler (C) and the binder component (D). Composition.

In the laminated sheet of the present invention, the laminated sheet can be easily joined to the heat generating body by closely adhering the adhesive layer to the heat generating body, and the heat can be efficiently diffused and radiated.

Further, in the laminated sheet of the present invention, since the adhesive layer contains the adhesive resin and the thermally conductive filler, the heat of the heat generating body can be efficiently dissipated.

1‧‧‧metal foil layer

1a‧‧‧ Surface of the thermal radiation layer on the metal foil layer 1

1b‧‧‧Metal layer side of metal foil layer 1

11‧‧‧thermal radiation layer

12‧‧‧metal layer

2‧‧‧Adhesive layer

2b‧‧‧ The opposite side of the adhesive layer to the metal foil

3‧‧‧ peeling sheet

10‧‧‧Laminated sheets

[Fig. 1] Fig. 1 is a cross-sectional view showing an example of a laminated sheet of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments. The present invention can be variously modified without departing from the spirit and scope of the invention, and can be easily understood as long as it has ordinary knowledge in the field of the invention. Therefore, the present invention is not limited to the description of the description of the embodiments shown below. Additions, omissions, changes, substitutions, and other modifications may be made without departing from the scope of the invention.

Fig. 1 is a schematic view showing an example of a laminated sheet of the present invention, and showing a cross-sectional view. The laminated sheet 10 shown in Fig. 1 comprises a metal foil layer 1 and an adhesive layer 2, which is composed of a heat radiation layer 11 and a metal layer 12; the adhesive layer 2 is laminated on the metal layer 12 side face 1b. Further, the release sheet 3 may be further laminated on the exposed surface 2b of the adhesive layer 2 before use of the laminated sheet 10, if necessary.

The total thickness of the metal foil layer 1 and the adhesive layer 2 described above can be selected as needed. It is preferably 0.05 to 3 mm, more preferably 0.1 mm to 2.5 mm, and still more preferably 0.15 mm to 2 mm. Other examples of the preferred range of the average thickness may be 0.05 to 1.5 mm, or 0.05 to 1 mm, or 0.05 to 0.8 mm. When the average thickness is 0.05 mm or more, the laminated sheet 10 having high heat dissipation property due to the metal foil layer 1 and sufficient adhesion due to the adhesive layer 2 can be easily obtained. Further, the laminated sheet 10 having a shape that is stable and easily follows the shape of the joined heat generating body. Therefore, it is possible to efficiently transfer the heat of the heating element to the layer. The sheet 10 is bonded to heat the heat of the heat generating body efficiently.

The average thickness of the above-mentioned metal foil layer 1 and the above-mentioned adhesive layer 2 in the present specification means that the above-mentioned metal foil layer 1 of 10 randomly selected and the aforementioned adhesion are observed by the cross section of the laminated foil 10 of the present invention. The total thickness of the layer 2 was measured and used as the value obtained by the arithmetic mean.

<metal foil layer>

The metal foil layer will be described by taking Fig. 1 as an example. The metal foil layer is composed of the heat radiation layer 11 and the metal layer 12 as shown in Fig. 1 . The heat radiation layer 11 contains a heat radiation filler (C) and a binder component (D). The thickness of the heat radiation layer 11 can be selected as needed, but is preferably 0.1 to 4 μm, more preferably 0.5 to 3 μm. When it is 0.1 μm or more, the amount of the heat radiation filler in the heat radiation layer can be sufficiently ensured, and sufficient heat dissipation can be obtained. Since heat radiation does not rise even if it exceeds 4 μm, it is disadvantageous for the cost side.

The heat radiation filler (C) used as the heat radiation layer 11 is not particularly limited as long as it is a metal or a nonmetal. From the viewpoint of high heat emissivity and low cost, a carbonaceous material is preferred. Examples of the carbonaceous material include carbon black such as acetylene black and ketjen black, graphite, and gas-phase carbon fiber. One or two or more of them may be used. The particle size of the heat radiation filler (C) is preferably 0.1 to 2.0 μm in terms of cumulative mass 50% particle diameter (D50), more preferably 0.2 to 1 μm. When the cumulative mass 50% particle diameter (D50) is 0.1 to 2.0 μm, a heat radiation layer having high smoothness can be obtained. The amount of the heat radiation filler (C) in the heat radiation layer 11 can be arbitrarily selected, but is preferably 20 to 80% by mass, more preferably 30 to 60% by mass, still more preferably 30 to 60% by mass.

The binder component (D) used as the heat radiation layer 11 is not particularly limited as long as it can adhere the heat radiation filler (C). The applicability of the heat-radiating filler (C) or the composition of the heat-radiating filler (C) and the binder component (D) as the heat radiation layer 11 to be laminated on the metal layer 12 From the viewpoint of the film properties of the heat radiation layer 11, the binder component (D) preferably contains a polymer polysaccharide and an acid crosslinking agent. The polymer polysaccharides may be one or more selected from the group consisting of chitosan, chitin and derivatives thereof. The acid crosslinking agent may be one or more selected from the group consisting of pyromellitic acid, trimellitic acid, maleic acid, phthalic acid, and the like.

Although the average thickness of the above-mentioned metal foil layer 1 can be selected as needed, it is preferably 0.02 to 0.5 mm. When the average thickness of the metal foil layer 1 is 0.02 mm or more, the laminated sheet 10 excellent in heat radiation property can be obtained, and the deformation or deformation of the metal foil layer 1 in the step of producing the laminated sheet 10 can be minimized. When the average thickness of the foil layer 1 is 0.5 mm or less, the shape followability of the heat generating body for the laminated sheet 10 when the laminated sheet 10 is joined to the heat generating body can be sufficiently ensured. Therefore, even when the surface of the heat generating body is a curved surface, the contact area between the heat generating body and the laminated sheet 10 can be sufficiently ensured, so that heat of the heat generating body can be efficiently radiated. The average thickness of the metal foil layer 1 is more preferably 0.05 to 0.4 mm, still more preferably 0.05 to 0.35 mm. As other preferred thicknesses Examples may also be listed in the range of 0.05 to 0.25 mm, or 0.05 to 0.15 mm.

As the metal layer 12, gold, silver, copper, aluminum, an alloy containing the metal, or the like can be used. A metal having a high thermal conductivity is preferable, and from the viewpoint of low cost or ease of processing, copper, aluminum, and an alloy containing the metal are preferably used as the metal layer 12.

The method of forming the foil layer 1 composed of the heat radiation layer 11 and the metal layer 12 is not particularly limited, and may be selected as needed. For example, a method of forming a composition for forming the heat radiation layer 11 by gravure coating on the metal layer 12, and forming the heat radiation layer 11 by heating in a drying furnace may be mentioned.

The coating method by gravure coating is preferred as a coating method for forming a uniform film. Further, the binder component is reacted by heating to form a stronger film. Therefore, by forming the metal foil layer 1 by the above-described method, excellent productivity can be obtained, and the metal foil layer 1 having the heat radiation layer 11 having a uniform thickness can be obtained.

<adhesive layer>

The thickness of the adhesive layer 2 used in the present invention may be selected according to needs, but is preferably 0.1 to 1 mm on average, more preferably 0.1 to 0.7 mm, still more preferably 0.2 to 0.5 mm. When the thickness of the adhesive layer 2 is 0.1 mm or more on average, the laminated sheet 10 in which the bonding strength between the adhesive layer 2 and the heat generating body and the metal foil layer 1 is sufficiently high is obtained. When the thickness of the adhesive layer 2 is 1 mm or less on average, the heat of the heat generating body can be efficiently conducted to the metal foil layer 1 via the adhesive layer 2.

In addition, in the present invention, the average thickness of the adhesive layer 2 means From the cross section of the laminated sheet 10 of the present invention, the thickness of the randomly selected adhesive layer 2 at 30 points was measured as a value obtained by the arithmetic mean.

The adhesive layer 2 preferably has an adhesive force to SUS304 of 1 N/25 mm or more, more preferably 5 N/25 mm or more, and still more preferably 10 N/25 mm or more, measured by a measuring method described later. When the above-mentioned adhesive force is 1 N/25 mm or more, the laminated sheet 10 in which the bonding strength between the adhesive layer 2 and the heat generating body and the metal foil layer 1 is sufficiently high is obtained.

"Test Method for Adhesion"

The adhesive force of the adhesive layer 2 was obtained by the method shown below.

A PET film ("LUMIRROR (trademark) S-10" manufactured by Toray Co., Ltd.) having a thickness of 50 μm was used as a substrate, and an adhesive layer was formed on the substrate to prepare a laminated sheet for testing. Next, the test laminated sheet was cut into a size of 25 mm in length and 100 mm in width to obtain a long sheet. Then, on the test plate composed of SUS304, the adhesive layer was laminated to the test plate to laminate the elongated sheet. Thereafter, a 2 kg rubber roller (width: about 50 mm) was placed one time on the long sheet to join the test sheet to the long sheet.

The joined test panels and long strips were allowed to stand in an environment of 23 ° C and a humidity of 50% RH for 24 hours. Thereafter, a tensile test in a 180° direction was carried out at a peeling speed of 300 mm/min in accordance with JIS Z0237, and the adhesion (N/25 mm) of the test piece to the elongated sheet was measured.

"The composition of the adhesive layer"

The adhesive layer 2 is composed of an adhesive composition containing an adhesive resin composition (A) and a heat conductive filler (B). The heat conductive filler (B) may be one or two or more kinds selected from the group consisting of metal oxides, metal nitrides, and metal hydrates, as long as it has heat conductivity. Examples of the metal oxides include alumina, magnesia, zinc oxide, and titania. Examples of the metal nitride system include aluminum nitride, boron nitride, and tantalum nitride. The metal hydrate system may, for example, be magnesium hydroxide or aluminum hydroxide, and preferably contains aluminum hydroxide from the viewpoint of excellent thermal conductivity or flame retardancy.

Further, as the thermally conductive filler (B), metal powder such as aluminum or tantalum carbide can be used.

As the thermally conductive filler (B), among the above materials, a metal hydrate is particularly preferable. The adhesive layer 2 having excellent thermal conductivity and flame retardancy can be formed by using a metal hydrate as a heat conductive filler. Further, from the viewpoint of ease of handling, it is preferred to use a metal hydrate.

It is preferable that the thermally conductive filler (B) is a powder, and the adhesive layer 2 is uniformly dispersed. The particle diameter of the thermally conductive filler (B) is preferably 50 to 50 μm in terms of cumulative mass 50% (D50), more preferably 3 to 30 μm. When the cumulative mass 50% particle diameter (D50) is 1 to 50 μm, the contact area between the heat conductive filler (B) contained in the adhesive layer 2 and the heat generating body and the metal foil layer 1 can be sufficiently obtained, and the heat generating body can be obtained. The heat is efficiently conducted to the foil layer 1 through the adhesive layer 2.

"Cumulative mass 50% particle size (D50)", for example, by using shares It is obtained by laser diffraction type particle size distribution measurement of a laser diffraction type particle size distribution measuring device of the product name "SALD-200V ER" manufactured by Shimadzu Corporation.

The adhesive resin composition (A) used as the adhesive layer 2 is sufficient as long as the adhesiveness can be sufficiently obtained. The adhesive resin composition (A) may be only a resin component, or may be a reactive component as a resin component, and may include a polymerizable monomer or a polymerization initiator. Examples of the resin component include a (meth)acrylic resin and an anthrone-based resin.

As the anthrone-based resin used as the adhesive resin component, for example, a general structural formula -[(CH ₃ ) ₂ SiO] _m -[(CH ₃ )SiO _3/2 ] _n -[(CH ₃ ) ₃ SiO can be used. _1/2 ] _p - (in the above structural formula, m, n, and p are integers).

In the case where a (meth)acrylic resin is contained as the adhesive resin component, the adhesive layer 2 is provided to contain the adhesive resin composition (A), the above-mentioned thermally conductive filler (B), and a photopolymerization initiator (E). It is preferable that the adhesive composition is cured, and the adhesive resin composition (A) contains a (meth)acryl oxime group-containing polyurethane (a) and a polymerizable monomer (b).

In the scope of the present specification, "(meth)acrylonitrile" means a group represented by the chemical formula "CH ₂ =CH-CO-" or a chemical formula "CH ₂ =C(CH ₃ )-CO-" The "isocyanate group" means a group represented by the chemical formula "-N=C=O".

"Adhesive resin composition (A)"

The case where the polyaminoformate (a) having a (meth)acryl fluorenyl group and the polymerizable monomer (b) are used as the adhesive resin composition (A) will be described below.

(polyurethane (a))

The polyhydric alcohol used in the production of the polyurethane (a) is not particularly limited, but is preferably a polyoxyalkylene polyol, and further has an alkylene chain having a carbon number of 2 to 4. Polyoxyalkylene polyols are preferred.

Preferable examples of the polyoxyalkylene polyol include polyoxyethylene polyol, polyoxypropylene polyol, polyoxybutylene polyol, and polytetramethylene ether glycol. These polyoxyalkylene polyols are obtained by addition polymerization of an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide. The polyoxyalkylene polyol used in the present invention may be a polymer obtained by addition polymerization of one type of alkylene oxide or the like, or two or more kinds of alkylene oxides may be used. The resulting copolymer is copolymerized.

The polyoxyalkylene polyol has a number average molecular weight of usually 500 to 5,000, preferably 800 to 4,000, more preferably 1,000 to 3,000. Since the number average molecular weight of the polyoxyalkylene polyol is 500 to 5,000, the adhesion of the adhesive layer 2 can be sufficiently obtained, and the urethane in the polyurethane can be ensured in a desired amount. The key, so the cohesive force of the adhesive layer 2 is sufficiently high.

The polyisocyanate used in the production of the polyurethane (a) is not particularly limited, but preferably contains two isocyanate groups. Compound. Examples of the polyisocyanate include tolylene diisocyanate and its hydride, xylene diisocyanate and its hydride, diphenylmethane diisocyanate and its hydride, 1,5-anthranyl Isocyanate and its hydride, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, tetramethyl xylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexyl diisocyanate, 1, A diisocyanate such as 3-bis(methyl isocyanate) cyclohexane or a decane diisocyanate may be used in combination of two or more kinds. Among them, isophorone diisocyanate or diphenylmethane diisocyanate and a hydrogenated product thereof are preferred from the viewpoint of excellent control of reactivity.

[First Synthesis Method of Polyurethane (a)]

Next, a method for synthesizing the first synthesis method of the polyurethane (a), that is, the polyurethane (a1) will be described.

First, a polyoxoalkylene polyol and a polyisocyanate are reacted in a ratio of an amount of isocyanate groups more than a hydroxyl group to synthesize a "polyurethane having an isocyanate group".

At this time, the molecular weight of the polyaminocarbamate having an isocyanate group can be adjusted by adjusting the ratio of the amount of isocyanate groups to the amount of hydroxyl groups. Specifically, the smaller the ratio of the amount of the isocyanate group to the amount of the hydroxyl group, the larger the molecular weight of the polyaminocarbamate having an isocyanate group, and the larger the ratio of the amount of the isocyanate group to the amount of the hydroxyl group. The smaller the molecular weight of the polyaminocarbamate having an isocyanate group. Preferably, for the hydroxyl group 1 mole of the polyoxyalkylene polyol, the isocyanate group of the polyisocyanate is 1.03 to 1.35 moles, more preferably 1.05 to 1.1 moles. ear.

Next, the polyurethane having an isocyanate group is reacted with a compound having a hydroxyl group and a (meth)acrylonium group to synthesize a polyurethane (a1).

The compound having a hydroxyl group and a (meth)acrylinyl group is not particularly limited, and examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyrate. Hydroxyalkyl (meth) acrylate such as benzyl (meth) acrylate; 1,3-butylene glycol mono (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 1 A monohydric alcohol having a (meth)acrylonyl group derived from various polyols, such as 6-hexanediol mono(meth)acrylate or 3-methylpentanediol mono(meth)acrylate. They may be used alone or in combination of two or more. Among them, 2-hydroxyethyl acrylate is preferably used from the viewpoint of excellent reactivity with an isocyanate group and photocurability.

When a polyaminocarbamate having an isocyanate group is reacted with a compound having a hydroxyl group and a (meth)acryloyl group, a polyamine group having an isocyanate group is added by adding an alkyl alcohol. The acid ester is reacted, and the amount of introduction of the (meth) acrylonitrile group of the polyurethane (a1) can be adjusted.

The amount of introduction of the (meth)acryl fluorenyl group of the polyurethane (a) is usually 50 to 100 mol%, preferably 70 to 100 mol%, more preferably 90 to the isocyanate group. 100 mol%. When the amount of introduction of the (meth) acrylonitrile group is 50 to 100 mol% with respect to the isocyanate group, the cohesive force of the adhesive layer 2 is sufficiently high.

The alkyl alcohol is not particularly limited, and examples thereof include a linear type, a branched type, and an alicyclic alkyl alcohol. Specific examples thereof include ethanol, propanol, and butanol.

[Second Synthesis Method of Polyurethane (a)]

Next, a second synthesis method of the polyurethane (a), that is, a method of synthesizing the polyurethane (a2) will be described.

First, a polyoxyalkylene polyol and a polyisocyanate are reacted in a ratio of a hydroxyl group amount to an isocyanate group to synthesize a "hydroxyl-containing polyurethane".

Next, a polyurethane having a hydroxyl group is reacted with a compound having an isocyanato group and a (meth)acryloyl group to synthesize a polyurethane (a2).

The compound having an isocyanato group and a (meth)acryl fluorenyl group is not particularly limited, and examples thereof include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis(acryloxymethyl). Ethyl isocyanate and the like. They may be used alone or in combination of two or more. Among them, from the viewpoint of excellent reactivity with a hydroxyl group and excellent photocurability, 2-(meth)acryloyloxyethyl isocyanate is preferably used.

In the synthesis of the polyurethane (a), the reaction of a hydroxyl group with an isocyanate group is carried out in the presence of an organic solvent inert to the isocyanate group, using dibutyltin dilaurate or diethylhexylate. A urethane catalyst such as dibutyltin acid or dioctyltin dilaurate is usually carried out at 30 to 100 ° C for about 1 to 5 hours.

The amount of the urethane catalyst used is usually 50 to 500 ppm by mass based on the total mass of the reactants.

The weight average molecular weight of the polyurethane (a) may be arbitrarily selected, but is preferably 10,000 to 300,000, more preferably 20,000 to 200,000, still more preferably 30,000 to 100,000. When the weight average molecular weight of the polyurethane (a) is 10,000 to 300,000, the adhesive force of the adhesive layer 2 can be sufficiently obtained, and handling is easy and workability is also improved.

"weight average molecular weight"

The weight average molecular weight is a polystyrene-equivalent molecular weight measured by gel permeation chromatography: trade name "Shodex GPC-101" (manufactured by Showa Denko Co., Ltd., "Shodex" is a registered trademark).

Pipe column: LF-804 (made by Showa Denko Co., Ltd.)

Column temperature: 40 ° C

Sample: 0.2% by mass tetrahydrofuran solution

Flow rate: 1ml/min

Dissolution: tetrahydrofuran

Detector: RI detector

The content of the polyurethane (a) in the adhesive resin composition (A) is preferably from 10 to 40% by mass, more preferably from 15 to 35% by mass. When the content of the polyurethane (a) in the adhesive resin composition (A) is 10% by mass or more and 40% by mass or less, the adhesive force of the adhesive layer 2 can be sufficiently obtained, and the adhesive layer 2 can be obtained. Cohesion is fully high By.

"Polymerizable monomer (b)"

The polymerizable monomer (b) used in the adhesive resin composition (A) is not particularly limited, but (meth) acrylate is preferably used. Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and n-butyl (meth) acrylate. Ester, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-hexyl (A Alkyl esters of acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, etc. Acryl ester; a cyclic alkyl (meth) acrylate such as cyclohexyl (meth) acrylate or norbornyl (meth) acrylate; or an alkyl group such as ethoxyethyl (meth) acrylate An alkoxy (poly)alkylene glycol such as oxyalkyl (meth) acrylate; methoxy diethylene glycol (meth) acrylate or ethoxy diethylene glycol (meth) acrylate ( a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl (meth) acrylate; a carboxyl group such as (meth)acrylic acid or β-carboxyethyl (meth) acrylate; (meth) acrylate; 2-sulfoethyl (methyl) a sulfonic acid group (meth) acrylate such as an enoate; a fluorinated alkyl (meth) acrylate such as octafluoropentyl (meth) acrylate; N,N-dimethylaminoethyl ( N,N-dialkylamine alkyl (meth) acrylate such as methyl) acrylate; polyethylene glycol di(meth) acrylate, a polyfunctional (meth) acrylate such as dipentaerythritol hexa(meth) acrylate or pentaerythritol tetra(meth) acrylate; (meth) acrylamide, dimethyl (meth) acrylamide or the like ( Methyl) acrylamide; (meth) acrylate having an epoxy group such as a glycidyl (meth) acrylate. They may be used alone or in combination of two or more. Among the above, an alkyl (meth) acrylate, a carboxyl group-containing (meth) acrylate, and a hydroxyl group-containing (meth) acrylate are preferable.

The polymerizable monomer (b) preferably contains a (meth) acrylate having a carboxyl group and/or a hydroxyl group from the viewpoint of the viscosity of the adhesive composition and the adhesion, strength, and heat resistance of the adhesive layer 2. A (meth) acrylate having a polar group such as (meth) acrylate.

The content of the (meth) acrylate having a polar group is preferably from 1 to 40% by mass in the adhesive resin composition (A). When the content of the (meth) acrylate having a hydroxyl group is from 1 to 40% by mass in the adhesive resin composition (A), the adhesive force of the adhesive layer 2 can be sufficiently obtained, and the water resistance of the adhesive layer 2 can be made good.

The polymerizable monomer (b) preferably contains n-butyl acrylate, 2-ethylhexyl acrylate or isooctyl acrylate from the viewpoint of imparting adhesion to the adhesive layer 2, and the like. The glass transition point of the cured product of the adhesive resin composition (A). The composition of the polymerizable monomer (b) is preferably a glass transition caused by the following FOX formula when only the polymerizable monomer (b) contained in the adhesive resin composition (A) is polymerized. The theoretical value of the temperature is a composition of -80 ° C to -10 ° C, and more preferably a composition of -70 ° C to -20 ° C.

"glass transition temperature"

1/(Tg+273)=Σ[Wi/(Tgi+273)]:Fox

Tg (°C): Calculate the glass transition temperature

Wi: the weight fraction of each monomer

Tgi (°C): glass transition temperature of homopolymer of each monomer component

The content of the polymerizable monomer (b) used in the adhesive resin composition (A) of the present invention is preferably 60 to 90% by mass, more preferably 65 to 85% by mass. When the content of the polymerizable monomer (b) in the adhesive composition is from 60 to 90% by mass, the adhesive force of the adhesive layer 2 can be sufficiently obtained, and the cohesive force of the adhesive layer 2 is sufficiently high.

The adhesive resin composition (A) may also have a degree of influence on the function of the adhesive layer 2 such as adhesion, strength, heat resistance, etc., except for the poly(meth) acrylate having a (meth) acrylonitrile group (a) Other polymers are also included in addition to the polymerizable monomer (b).

As another example of the polymer, for example, a conjugated diene polymer such as natural rubber or polybutadiene rubber; butyl rubber; styrene-butadiene random copolymer, styrene-isoprene can be used. An aromatic vinyl-conjugated diene copolymer such as an olefin random copolymer; a hydride of an aromatic vinyl-conjugated diene copolymer; a vinyl cyanide compound such as an acrylonitrile-butadiene copolymer rubber Conjugated diene copolymer; ethylene cyanide-aromatic vinyl-conjugated diene copolymer; mixture of vinyl cyanide compound-conjugated diene copolymer and poly(vinyl halide); polyepichlorohydrin rubber, etc. Polyepianol rubber; polyalkylene oxide of polyethylene oxide, polypropylene oxide, etc.; Ethylene-propylene-diene copolymer (EPDM); anthrone rubber; fluororubber; polyethylene; ethylene-α-olefin copolymer such as ethylene-propylene copolymer; α-olefin polymer such as polypropylene; polyvinyl chloride Polyvinyl halide resin such as resin; polyvinyl halide resin such as polyvinylidene chloride resin; epoxy resin; phenol resin; polyphenylene ether resin; polyamine which is resistant to uranium-6; ; polyester; polyvinyl acetate; poly(ethylene vinyl alcohol) and the like. They may be used alone or in combination of two or more.

The total content of the (meth)acrylonitrile-based polyurethane (a) and the polymerizable monomer (b) is preferably 80% by mass based on 100 parts by mass of the adhesive resin composition (A). The amount is more than 90 parts by mass, more preferably 100 parts by mass. By setting the total content of the (meth)acrylonitrile group-containing polyurethane (a) and the polymerizable monomer (b) to 80 parts by mass or more, the adhesion of the adhesive layer 2 can be sufficiently obtained. , and the cohesive force of the adhesive layer 2 is sufficiently high.

"Polymerization initiator (E)"

A thermal polymerization initiator, a photopolymerization initiator, and the like can be used as the polymerization initiator (E). However, from the viewpoint of easiness of production, a photopolymerization initiator is preferably used.

Examples of the photopolymerization initiator include carbonyl photopolymerization initiators such as diphenyl ketone and diphenyl ethane diketone; and sulfides such as diphenyl disulfide and tetramethylammonium monosulfide; a photopolymerization initiator; a mercaptophosphine oxide such as 2,4,6-trimethylbenzhydryldiphenylphosphine oxide; an oxime photopolymerization initiator of benzoquinone or anthracene; Azobisisobutyronitrile, 2,2'-azodipropane, etc. An azo-based photopolymerization initiator; a sulfonium chloride-based photopolymerization initiator; a thioxanthone-based photopolymerization initiator such as thioxanthone or 2-chlorothioxanthone; An oxide photopolymerization initiator or the like may be used in combination of two or more kinds.

Among the above, from the viewpoint of solubility in the adhesive composition, the photopolymerization initiator is preferably a mercaptophosphine oxide, more preferably 2,4,6-trimethylbenzylidene. Diphenylphosphine oxide.

In the adhesive composition for the adhesive layer 2, it is preferable to contain 0.1 to 5.0 parts by mass of the photopolymerization initiator (E) per 100 parts by mass of the adhesive resin composition (A). In the adhesive composition for the adhesive layer 2, it is preferable to contain 250 to 900 parts by mass of the thermally conductive filler (B) for 100 parts by mass of the adhesive resin composition (A). It is particularly preferable to contain 250 to 900 parts by mass of the thermally conductive filler (B) and 0.1 to 5.0 parts by mass of the photopolymerization initiator (E) per 100 parts by mass of the adhesive resin composition (A).

When the content of the thermally conductive filler (B) is 250 parts by mass or more for 100 parts by mass of the adhesive resin composition (A), the heat of the heating element can be efficiently conducted to the foil layer 1 via the adhesive layer 2 .

When the content of the heat conductive filler (B) is 900 parts by mass or less based on 100 parts by mass of the adhesive resin composition (A), the adhesive layer 2 having a sufficiently high bonding strength between the heat generating body and the metal foil layer 1 is obtained. The content of the heat conductive filler (B) is preferably 700 parts by mass or less based on 100 parts by mass of the adhesive resin composition (A). The upper limit of the content of the thermally conductive filler (B) may be arbitrarily selected as needed, and may be 600 parts by mass or less, or 400 parts by mass, per 100 parts by mass of the adhesive resin composition (A). under.

When a metal hydrate is used as the thermally conductive filler (B), if the content of the metal hydrate is 250 parts by mass or more based on 100 parts by mass of the adhesive resin composition (A), a laminate sheet having high flame retardancy can be obtained. 10. In order to further improve the flame retardancy of the laminated sheet 10, the content of the metal hydrate is more preferably 290 parts by mass or more based on 100 parts by mass of the adhesive resin composition (A).

The content of the polymerization initiator (E) in the adhesive composition is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, even more preferably 100 parts by mass of the adhesive resin composition (A). It is 0.5 to 2 parts by mass. When the content of the polymerization initiator (E) is 0.1 to 5 parts by mass based on 100 parts by mass of the adhesive resin composition (A), the photocurability of the adhesive composition can be sufficiently obtained, and the adhesive layer 2 can be sufficiently obtained. Adhesion.

The adhesive composition used for the adhesive layer 2 may further contain a resin different from the polyurethane (a) in order to enhance the adhesion of the adhesive layer 2.

The resin is not particularly limited, and examples thereof include rosin-based resins such as rosin and rosin esterified compounds; terpene-based resins such as diterpene polymers and α-pinene-phenol copolymers; and aliphatic systems (C5-based systems). A petroleum resin such as an aromatic system (C9 series); a styrene resin, a phenol resin, a xylene resin, or the like may be used in combination of two or more kinds.

The adhesive composition used for the adhesive layer 2 may further contain an additive as needed.

The additive is not particularly limited, but examples thereof include a dispersing agent and a plasticizer. Agents, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, UV absorbers, polymerization inhibitors, benzotriazole-based light stabilizers, phosphate esters and other flame retardants, interfaces An antistatic agent such as an active agent.

"stripping sheet"

The example of the release sheet 3 is not particularly limited, and examples thereof include a plastic film which has been surface-treated by a release treatment agent.

As the release treatment agent, an anthrone type, a long-chain alkyl type, a fluorine type or the like can be used. Examples of the plastic film include a polyethylene terephthalate (PET) film and the like.

"Method for manufacturing laminated sheets"

Next, as an example of the method for producing a laminated sheet of the present invention, a method of producing the laminated sheet 10 shown in Fig. 1 will be described as an example.

First, the adhesive layer 2 is formed by peeling off one side of the sheet 3 to form an adhesive sheet.

The method of forming the pressure-sensitive adhesive layer 2 is, for example, a method in which the above-described pressure-sensitive adhesive composition is applied to one surface of the release sheet 3, and is cured by irradiation with ultraviolet rays.

The coating method of the adhesive composition is not particularly limited, and examples thereof include a gravure roll coater, a reverse roll coater, a contact roll coater, a dip roll coater, and a bar coating. A method such as a cloth machine, a knife coater, a spray coater, a spot coater, or a direct coater.

When the ultraviolet ray is irradiated to cure the adhesive composition, the ultraviolet ray irradiation amount is preferably 500 to 5,000 mJ/cm ² .

In the adhesive sheet obtained in this manner, in order to protect the adhesive layer 2 during the use of the adhesive sheet, the protective release sheet is placed on the adhesive layer 2, and the adhesive layer 2 is held in two sheets. The shape between the sheets is peeled off. Further, the latter may be treated as a release sheet 3 by using a release treatment agent on both sides, and the adhesive sheet may be wound into a roll shape to be in a state in which the adhesive layer 2 is held between the release sheets until the adhesive sheet is adhered. When used.

Further, when the release sheet for protection is disposed on the adhesive layer 2, the adhesive composition to be the adhesive layer 2 may be cured before the release sheet for protection is disposed, or after the release sheet for protection may be disposed. The adhesive composition that becomes the adhesive layer 2 hardens. In the case where the adhesive sheet for the adhesive layer 2 is cured after the release sheet for protection is disposed, the release sheet 3 and/or the release sheet for protection are used to have light transparency.

Next, the adhesive sheet is laminated with the metal foil composed of the heat radiation layer 11 and the metal layer 12 to form a laminated sheet 10. In the case where the release sheet for protection is disposed on the adhesive layer 2 of the adhesive sheet, the release sheet for protection is removed, and then laminated with the metal sheet. The adhesive sheet and the metal foil are such that the adhesive layer 2 of the adhesive sheet faces the metal layer 12 side of the metal foil layer 1.

In the laminating step, a vacuum laminating device, an autoclave, a press machine, or the like may be used to avoid the adhesion between the adhesive sheet and the foil layer 1 Biting into the bubble, that is, avoiding bubble generation.

When the laminated sheet 10 is joined to the heat generating body, the peeling sheet 3 is removed to bond the exposed surface of the adhesive layer 2 to the heat generating body.

The laminated sheet 10 of the present embodiment has the metal foil layer 1 and an adhesive layer 2 laminated on the surface of the metal foil layer 1 on the metal layer 12 side. Therefore, the laminated sheet 10 can be joined to the heat generating body by closely adhering the adhesive layer 2 to the heat generating body. Therefore, in the laminated sheet 10 of the present embodiment, the laminated sheet can be easily joined to the heat generating body.

Since the laminated sheet 10 of the present embodiment is an adhesive layer 2 containing an adhesive resin and a thermally conductive filler, for example, the heat of the heat generating body can be efficiently conducted to the adhesive layer as compared with the case where only the adhesive resin is used. Laminated sheet 10. Therefore, the laminated sheet 10 of the present embodiment can efficiently dissipate heat of the heat generating body.

The adhesive layer 2 of the laminated sheet 10 shown in Fig. 1 is cured by an adhesive composition containing the adhesive resin composition (A), the thermally conductive filler (B), and the polymerization initiator (E). In the case of the case, the bonding strength between the heating element and the laminated sheet 10 is excellent, and the adhesive resin composition (A) contains a (meth) acrylonitrile-based polyurethane (a) and Polymerizable monomer (b).

Since the laminated sheet 10 shown in FIG. 1 is formed by laminating the release sheet 3 on the surface of the adhesive layer 2 opposite to the metal foil layer 1, the laminate sheet 10 can be bonded to the heating element until the laminated sheet 10 is bonded thereto. The adhesive layer 2 is protected by peeling off the sheet 3.

In the method of manufacturing the laminated sheet 10 of the present embodiment, The adhesive sheet and the metal foil are laminated by facing the adhesive layer 2 of the adhesive sheet and the metal layer 12 side of the metal foil layer 1, thereby obtaining a laminated sheet 10 which is attached to one side of the peeling sheet 3. There is an adhesive layer 2; the metal foil has a heat radiation layer 11 on one side.

In addition, as an example of a method of forming an adhesive layer on the surface 1b of the metal foil layer 1 on the metal layer side, for example, it is also possible to apply the adhesive resin composition (A) to the surface 1b on the metal layer side of the metal foil layer 1. A method of hardening a composition with an adhesive of a thermally conductive filler (B).

The laminated sheet 10 shown in Fig. 1 can be easily joined to the heat generating body, and can be easily reattached after being joined to the heat generating body, and further, the heat of the heat generating body can be efficiently radiated. Therefore, the laminated sheet 10 can be suitably used as a diffusion sheet for dissipating heat generated in the heat generating body. Examples of the heat generating system include electrical components such as a semiconductor wafer, a transistor, a condenser, and the like, and an electric component such as a battery. Other examples of the heating element include an electronic circuit board, a solar cell panel, a lighting fixture, a display backlight, a liquid crystal projector, an LED lamp, a signal, a mobile phone, a smart phone, a personal computer, a tablet computer, a server, Small game consoles, solar panel memory modules, amplifiers, various batteries, and camera modules.

The laminated sheet of the present invention is not limited to the laminated sheet 10 shown in Fig. 1 described above.

For example, in the laminated sheet 10 shown in Fig. 1, the release sheet 3 is laminated on the surface of the adhesive layer 2 opposite to the metal foil layer 1. The case will be described as an example, but there may be no peeling sheet.

[Examples]

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

(Example A-1) <Synthesis of Polyurethane (a)>

The product name "D-2000" (manufactured by Mitsui Fine Chemicals Co., Ltd., number average molecular weight: 2000) of isophorone diisocyanate and polypropylene glycol having a hydroxyl group having a hydroxyl group of 56 mgKOH/g at the end is 15 mol. The ear, which was 14 moles, was placed in a four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with a drying tube. Thereafter, 100 wt% of dioctyltin dilaurate was added to the above isophorone diisocyanate and polypropylene glycol, and the temperature was raised to 70 ° C to carry out a reaction for 4 hours to obtain a polyaminocarboxylic acid having an isocyanate group at the terminal. ester.

Next, 2 mol of 2-hydroxyethyl acrylate was added to the obtained polyurethane, and the temperature was raised to 70 ° C, and the reaction was carried out for 2 hours to obtain an acrylonitrile having a weight average molecular weight of 70,000 at the terminal. The base of the polyurethane (a). At this time, it was confirmed by the IR spectrum that the absorption peak derived from the isocyanate group disappeared, and the reaction was terminated.

<Manufacture of Adhesive Resin Composition (A)>

100 parts by mass of the polyurethane (a) obtained in this manner, and 252 parts by mass of 2-ethylhexyl acrylate as the polymerizable monomer (b) and 196 parts by mass of isostearyl acrylate 18 parts by mass of acrylic acid and 10 parts by mass of 2-hydroxyethyl acrylate were mixed in a flask to obtain an adhesive resin composition (A).

<Manufacture of Adhesive Composition>

300 parts by mass of aluminum hydroxide (manufactured by Showa Denko KK, trade name HIGILITE (trademark) H-31) having a D50 of 40 μm as a heat conductive filler (B), as a heat conductive filler (B), 100 parts by mass of the adhesive resin composition (A). And 0.8 parts by mass of 2,4,6-trimethylbenzimidyl diphenylphosphine oxide (manufactured by BASF Corporation, trade name: LUCIRIN TPO) as a photopolymerization initiator (E) at room temperature The diaper is used for mixing, and the uniform adhesive composition is adjusted.

<Manufacture of laminated sheets>

Using the adhesive composition adjusted in this manner, the laminated sheet shown in Fig. 1 was formed by the method shown below.

The adhesive composition was applied to a peeled PET film (200 mm × 200 mm) having a thickness of 75 μm which was surface-treated by a release treatment agent so that the film thickness (average thickness after hardening) was 0.4 mm thick using an applicator. Thereafter, the same peeled PET film was placed on the coating film composed of the adhesive composition. Next, on one of the peeling PET films, an ultraviolet irradiation device (manufactured by Nippon Battery Co., Ltd., UV irradiation device 4 kw × 1, output: 160 W/cm, metal halide lamp) was used, and the irradiation distance was 12 cm, and the lamp moving speed was 20 m. /min, and the irradiation amount of about 1000 mJ/cm ² is irradiated with ultraviolet rays to harden the adhesive composition.

By the above procedure, an adhesive sheet in which an adhesive layer having a thickness of 0.4 mm was held between two peeling PET films was obtained.

Then, the adhesive sheet after peeling off one of the PET films and the aluminum foil formed of the heat radiation layer 11 and the metal layer 12 shown in Fig. 1 (made by Showa Denko: carbon coated foil SDX (trademark)) , thickness: 0.05 mm) was laminated to form a laminate. The heat radiation layer used herein contains carbon black as a heat radiation filler, and as a binder component, a chitosan derivative is crosslinked by an acid. The thickness of the heat radiation layer was 1 μm. The adhesive sheet and the metal foil are laminated such that the adhesive layer of the adhesive sheet is opposed to the metal layer side of the metal foil.

The thickness of the metal foil shown in Table 1 is the average thickness.

Next, the obtained laminate of the adhesive sheet and the metal foil was subjected to curing in an autoclave at 40 ° C and 0.5 MPa for 10 minutes. Thereby, the adhesive layer and the metal foil can be sufficiently bonded, and the air bubbles between the adhesive layer and the metal foil can be removed to obtain the laminated foil (A-1) shown in Fig. 1.

(Example A-2)

In the same manner as the laminated sheet of Example A-1, except that the thermally conductive filler (B) was used as 390 parts by mass of alumina having a D50 of 9 μm (trade name: AS-50, manufactured by Showa Denko Co., Ltd.). Example Laminate sheet of A-2.

(Example A-3)

Example A was obtained in the same manner as the laminated sheet of Example A-1 except that the thickness of the aluminum metal foil composed of the heat radiation layer 11 and the metal layer 12 of Example A-1 was changed to 0.1 mm. 3 laminated sheets. In addition, the conditions of the heat radiation layer are the same.

(Example A-4)

In addition to the aluminum foil of the heat radiation layer 11 and the metal layer 12 shown in the first embodiment of the embodiment A-1, it is changed to a copper foil (manufactured by Showa Denko: carbon coated copper foil CDX) of 0.01 mm thick. The laminated sheet of Example A-4 was obtained in the same manner as the laminated sheet of Example A-1. In addition, the conditions of the heat radiation layer are the same.

(Comparative Example B-1)

A laminated sheet of Comparative Example B-1 was obtained in the same manner as in the laminated sheet of Example A-1 except that the metal foil was set to an aluminum foil of 50 μm.

(Comparative Example B-2)

In addition to using a foil as a surface-treated heat radiation sheet, in particular, "KOBEHONETSU (trademark) ‧ aluminum KS750" manufactured by Kobe Steel Co., Ltd. (single-sided heat radiation coating material (0.1 mm) A laminate sheet of Comparative Example B-2 was obtained in the same manner as in the laminated sheet of Example A-1 except for the thickness). In the heat radiating sheet, the metal layer is an aluminum layer, and the heat radiating layer is not included in the range of the heat radiating layer of the present invention.

(Comparative Example B-3)

In the production of the adhesive composition, Comparative Example B-3 was obtained in the same manner as in the laminated sheet of Example A-1 except that the thermally conductive filler (B) was not added and the thickness of the adhesive layer was set to 0.05 mm. Laminated sheets.

(Comparative Example B-4)

A laminated sheet of Comparative Example B-4 was obtained in the same manner as in the laminated sheet of Example A-1 except that the metal foil was a copper foil of 10 μm and the thickness of the adhesive layer was 0.1 mm.

For each of the laminated sheets of Examples A-1 and A-2 and Comparative Examples B-1 and B-2, the adhesion of the adhesive layer was determined by the above method. Further, for each of the laminated sheets of Examples A-1 and A-2 and Comparative Examples B-1 and B-2, the heat dissipation property was evaluated by the following method. The results of these are shown in Table 2.

(Evaluation of heat dissipation)

A laminated sheet of 60 mm in length and 60 mm in width after peeling off the PET film was peeled off on both sides of a square ceramic heater (WALN-1 manufactured by Koukou Electric Co., Ltd.) of 60 mm in length and 60 mm in width to make the adhesive layer of the adhesive sheet and The ceramic heater is laminated to the original. Next, the heater temperature (after 60 minutes) when the ceramic heater was heated at 5 W was measured, and the heat dissipation property was evaluated. The evaluation was carried out in an environment of room temperature 25 ° C and a humidity of 50%.

Further, the heater temperature in the case where the ceramic heater in the state in which the laminated sheet was not attached was cooled at 5 W was 150 °C.

From the above results, it was confirmed that the laminated sheet of the present invention has excellent heat dissipation properties. On the other hand, it can be confirmed that there is no heat radiation layer (Comparative Examples 1 and 4), no filler (Comparative Example 3), and heat radiation layer in the adhesive layer. In the comparative example of the layer (Comparative Example 2) which is not in the range of the present invention, heat dissipation was poor.

1‧‧‧metal foil layer

1a‧‧‧ Surface of the thermal radiation layer on the metal foil layer 1

1b‧‧‧Metal layer side of metal foil layer 1

2‧‧‧Adhesive layer

2b‧‧‧ The opposite side of the adhesive layer to the metal foil

3‧‧‧ peeling sheet

10‧‧‧Laminated sheets

11‧‧‧thermal radiation layer

12‧‧‧metal layer

Claims (14)

A laminated sheet comprising: a metal foil layer composed of a heat radiation layer and a metal layer containing a heat radiation filler (C) and a binder component (D), and a metal layer laminated to the metal foil layer An adhesive layer on the side of the layer side, the adhesive layer comprising an adhesive resin composition (A) and a thermally conductive filler (B). The laminated sheet of claim 1, wherein the heat radiation filler (C) is a carbonaceous material. The laminated sheet according to claim 2, wherein the carbonaceous material is one or more selected from the group consisting of carbon black, graphite, and fumed carbon fibers. The laminated sheet according to claim 1, wherein the binder component (D) contains a polymer polysaccharide and an acid crosslinking agent. The laminated sheet according to claim 4, wherein the polymer polysaccharide is one or more selected from the group consisting of chitin, chitosan and derivatives thereof, and the acid crosslinking agent is derived from benzene. One or two or more selected from the group consisting of tetracarboxylic acid, trimellitic acid, maleic acid, phthalic acid, and the like. The laminated sheet of claim 1, wherein the heat radiation layer has an average thickness of 0.1 to 4 μm. The laminated sheet of claim 1, wherein the metal foil layer has an average thickness of 0.02 to 0.5 mm. The laminated sheet according to claim 1, wherein the adhesive layer comprises a cured product of the adhesive composition (A), the thermally conductive filler (B), and the polymerization initiator (E), which is a cured product. The adhesive resin composition (A) contains a poly (meth) acrylate group having a (meth) acrylonitrile group. (a) and a polymerizable monomer (b). The laminated thin film of claim 1 which contains 250 to 900 parts by mass of the above-mentioned thermally conductive filler (B) to 100 parts by mass of the above-mentioned adhesive resin composition (A). The laminated sheet according to claim 1, wherein the thermally conductive filler (B) contains one or more selected from the group consisting of metal oxides and metal hydrates. The laminated sheet according to claim 1, wherein a release sheet is laminated on the opposite side of the adhesive layer from the metal foil layer. A heat spreader consisting of the laminated sheet of claim 1. An electronic machine incorporating a heat sink as claimed in claim 12. A method for producing a laminated sheet, characterized in that an adhesive sheet and a metal foil are laminated on the release sheet in this order, and the heat radiation layer is laminated on the outermost side, and the adhesive sheet is contained The adhesive layer of the adhesive resin composition (A) and the heat conductive filler (B) is composed of a metal layer and a heat radiation layer containing the heat radiation filler (C) and the binder component (D).