JP2006213845A - Heat-conductive pressure-sensitive adhesive sheet-like foamed shaped article and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-conductive pressure-sensitive adhesive composition which has hardness and pressure-sensitive adhesiveness in an excellent balance, and has excellent shape followability and pressure-sensitive adhesion retainability, and to provide a heat-conductive pressure-sensitive adhesive sheet. <P>SOLUTION: This heat-conductive pressure-sensitive adhesive sheet-like foamed shaped article (F) having an average foam cell diameter of 50 to 550 μm is obtained by heating and molding a heat-conductive pressure-sensitive adhesive composition (E) comprising 100 pts.wt. of a (meth)acrylate polymer (A1), 20 to 55 pts.wt. of a (meth)acrylate monomer mixture (A2m), 50 to 500 pts.wt. of a heat-conductive inorganic compound (B), and 0.1 to 5 pts.wt. of an organic peroxide thermal polymerization initiator (C2), and 0.01 to 0.8 pt.wt. of a thermally decomposable organic foaming agent (D) into a sheet-like article, thereby sheet molding the heat-conductive pressure-sensitive adhesive composition (E), polymerizing the (meth)acrylate monomer mixture (A2m), and thermally decomposing the thermally decomposable organic foaming agent (D). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a heat conductive pressure-sensitive adhesive sheet-like foamed molded article and a method for producing the same.

In recent years, electronic components such as plasma display panels (PDP), integrated circuit (IC) chips, and the like have increased in heat generation as their performance has increased. As a result, there is a need to take measures against functional failures due to temperature rise. In general, a method of diffusing heat by attaching a heat sink such as a heat sink, a heat radiating metal plate, or a heat radiating fin to a heat generating body such as an electronic component is employed. Various types of heat conductive sheets are used to efficiently conduct heat from the heat generating element to the heat radiating element. In general, a pressure-sensitive adhesive sheet is required for fixing the heat generating element and the heat radiating element. .
Patent Document 1 discloses a thermally conductive electrical insulation containing a polymer from a monomer containing a polar monomer copolymerizable with (meth) acrylic acid alkyl ester and thermally conductive electrically insulating particles (thermally conductive filler). A pressure sensitive adhesive is disclosed. Specifically, a pressure sensitive adhesive is obtained by photopolymerization by adding a crosslinking agent such as acrylic acid, alumina and tripropylene glycol diacrylate to polyisooctyl acrylate syrup.
In Patent Document 2, a monomer mixture containing (meth) acrylic acid alkyl ester as a main component and not containing a polar group-containing monomer, a photopolymerization initiator, a polyfunctional (meth) acrylate as a cross-linking agent, and A thermally conductive pressure sensitive adhesive comprising a photopolymer of a mixture of thermally conductive fillers is disclosed.
The pressure-sensitive adhesives disclosed in these documents are difficult to balance between hardness and pressure-sensitive adhesiveness, and in reality, because photopolymerization is required, equipment for that is necessary, It is hard to say that it is economically advantageous.

Patent Document 3 discloses a heat conductive pressure-sensitive adhesive obtained by blending heat conductive particles with a copolymer of an alkyl (meth) acrylate and a vinyl monomer that satisfies a specific formula. The specific vinyl monomer used here is preferably a special one such as (meth) acrylate having a phosphoric acid group or 2-hydroxy-3-phenoxypropyl acrylate.
In this method, in order to obtain a suitable effect, a large amount of special monomers must be used, which is not economically advantageous, and it is necessary to balance hardness and pressure-sensitive adhesiveness. There is a problem that it is difficult.
The present applicant has proposed a pressure-sensitive adhesive composition containing a (meth) acrylate polymer having a specific solvent solubility as a solution to these problems of the prior art (Patent Document 4). After all, it has been found that it is difficult to keep a good balance between hardness and pressure-sensitive adhesiveness, and that shape conformity to uneven heating elements is not sufficient.
Patent Document 5 proposes a pressure-sensitive adhesive composition foamed at a specific magnification. As a result, the shape followability to uneven heating elements and the like was improved, but this sheet was inferior in pressure-sensitive adhesive holding performance with a glass surface or the like in the vicinity of 100 ° C., which is a normal temperature, and the glass over time. There were problems such as natural peeling and floating from the surface.

Japanese Patent Laid-Open No. 6-080861 Japanese Patent Laid-Open No. 10-324853 JP 2002-322449 A JP 2002-285121 A JP 2002-128931 A

  As described above, a great deal of research has been conducted on heat-conductive pressure-sensitive adhesives, but it has an excellent balance between hardness and pressure-sensitive adhesive properties, as well as excellent shape following properties and pressure-sensitive adhesive retention. Nothing is available at present.

  Accordingly, an object of the present invention is to provide a heat conductive pressure-sensitive adhesive composition and a heat conductive pressure-sensitive adhesive sheet that have an excellent balance between hardness and pressure-sensitive adhesiveness, and are excellent in shape following and pressure-sensitive adhesive retention. It is to be.

  The inventors of the present invention have made extensive studies on the heat-conductive pressure-sensitive adhesive sheet. In synthesizing the (meth) acrylic acid ester polymer, a specific polymerization method is employed to synthesize the (meth) acrylic acid ester polymer. While obtaining a sheet of a heat conductive pressure-sensitive adhesive composition comprising a (meth) acrylic acid ester monomer mixture, a heat conductive inorganic compound, a specific polymerization initiator, and a specific foaming agent. It is possible to achieve the above object by using a pressure-sensitive adhesive sheet obtained by heating, polymerizing a (meth) acrylic acid ester monomer mixture, decomposing a specific foaming agent, and forming a sheet. Based on this finding, the present invention has been completed.

Thus, according to the present invention,
1. (Meth) acrylic acid ester polymer (A1) 100 parts by weight, (Meth) acrylic acid ester monomer mixture (A2m) 20 to 55 parts by weight, thermally conductive inorganic compound (B) 50 to 500 parts by weight, A thermally conductive pressure-sensitive adhesive composition (E) comprising 0.1 to 5 parts by weight of an oxide thermal polymerization initiator (C2) and 0.01 to 0.8 parts by weight of a thermally decomposable organic foaming agent (D) The sheet is formed into a sheet and heated to form a sheet of the heat conductive pressure-sensitive adhesive composition (E), the polymerization of the (meth) acrylate monomer mixture (A2m), and the thermally decomposable organic foaming agent. (D) The thermal conductive pressure-sensitive adhesive sheet-like foamed molded article (F) having an average diameter of foamed cells of 50 μm to 550 μm, which is obtained by performing thermal decomposition of (D);
2. (Meth) acrylic acid ester polymer (A1) 100 parts by weight, (Meth) acrylic acid ester monomer mixture (A2m) 20 to 55 parts by weight, thermally conductive inorganic compound (B) 50 to 500 parts by weight, A thermally conductive pressure-sensitive adhesive composition (E) comprising 0.1 to 5 parts by weight of an oxide thermal polymerization initiator (C2) and 0.01 to 0.8 parts by weight of a thermally decomposable organic foaming agent (D) The sheet is formed into a sheet and heated to form a sheet of the heat conductive pressure-sensitive adhesive composition (E), the polymerization of the (meth) acrylate monomer mixture (A2m), and the thermally decomposable organic foaming agent. (D) thermal decomposition, and a method for producing a thermally conductive pressure-sensitive adhesive sheet-like foamed molded article (F) having an average diameter of foamed cells of 50 to 550 μm;
Is provided.

  The heat conductive pressure-sensitive adhesive sheet-like foamed molded article of the present invention is excellent in the balance between hardness and pressure-sensitive adhesiveness, and is excellent in shape followability and pressure-sensitive adhesive retention. Therefore, this heat conductive pressure-sensitive adhesive sheet-like foam molded article is useful as a heat conductive sheet for efficiently conducting heat conduction from a heat generating body such as an electronic component such as a plasma display panel (PDP) to a heat radiating body. is there.

Hereinafter, the present invention will be described in detail.
According to the present invention,
1. (Meth) acrylic acid ester polymer (A1) 100 parts by weight, (Meth) acrylic acid ester monomer mixture (A2m) 20 to 55 parts by weight, thermally conductive inorganic compound (B) 50 to 500 parts by weight, A thermally conductive pressure-sensitive adhesive composition (E) comprising 0.1 to 5 parts by weight of an oxide thermal polymerization initiator (C2) and 0.01 to 0.8 parts by weight of a thermally decomposable organic foaming agent (D) The sheet is formed into a sheet and heated to form a sheet of the heat conductive pressure-sensitive adhesive composition (E), the polymerization of the (meth) acrylate monomer mixture (A2m), and the thermally decomposable organic foaming agent. (D) The thermal conductive pressure-sensitive adhesive sheet-like foamed molded article (F) having an average diameter of foamed cells of 50 μm to 550 μm, which is obtained by performing thermal decomposition of (D);
2. (Meth) acrylic acid ester polymer (A1) 100 parts by weight, (Meth) acrylic acid ester monomer mixture (A2m) 20 to 55 parts by weight, thermally conductive inorganic compound (B) 50 to 500 parts by weight, A thermally conductive pressure-sensitive adhesive composition (E) comprising 0.1 to 5 parts by weight of an oxide thermal polymerization initiator (C2) and 0.01 to 0.8 parts by weight of a thermally decomposable organic foaming agent (D) The sheet is formed into a sheet and heated to form a sheet of the heat conductive pressure-sensitive adhesive composition (E), the polymerization of the (meth) acrylate monomer mixture (A2m), and the thermally decomposable organic foaming agent. (D) thermal decomposition, and a method for producing a thermally conductive pressure-sensitive adhesive sheet-like foamed molded article (F) having an average diameter of foamed cells of 50 to 550 μm;
Is provided.

  In the above, “the heat conductive pressure-sensitive adhesive composition (E) is formed into a sheet and heated to form a sheet of the heat conductive pressure-sensitive adhesive composition (E), and (meth) acrylic acid ester alone. “Performing polymerization of the monomer mixture (A2m) and thermal decomposition of the thermally decomposable organic foaming agent (D)” means that the thermally conductive pressure-sensitive adhesive composition (E) is molded into a sheet and heated. The (meth) acryl is one of the constituents of the heat conductive pressure sensitive adhesive composition (E) and the heat conductive pressure sensitive adhesive composition (E). Three operations: polymerization of the acid ester monomer mixture (A2m) and thermal decomposition of the thermally decomposable organic foaming agent (D) which is one of the constituents of the thermally conductive pressure-sensitive adhesive composition (E) Or it means that the phenomenon occurs or occurs incidentally .

The heat conductive pressure-sensitive-adhesive sheet-like foam molded article (F) of the present invention contains a (meth) acrylic acid ester polymer (A1) as a first essential component. The (meth) acrylic acid ester polymer (A1) is not particularly limited, but the unit (a1) 80 to (meth) acrylic acid ester monomer forming a homopolymer having a glass transition temperature of -20 ° C. or lower. It preferably contains 99.9% by weight and 20 to 0.1% by weight of the monomer unit (a2) having an organic acid group.
In the present invention, (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester.

There is no particular limitation on the (meth) acrylate monomer (a1m) that gives the (meth) acrylate monomer unit (a1) that forms a homopolymer having a glass transition temperature of −20 ° C. or less. However, for example, ethyl acrylate (the glass transition temperature of the homopolymer is −24 ° C.), propyl acrylate (-37 ° C.), butyl acrylate (-54 ° C.), sec-butyl acrylate (the same − 22 ° C), heptyl acrylate (-60 ° C), hexyl acrylate (-61 ° C), octyl acrylate (-65 ° C), 2-ethylhexyl acrylate (-50 ° C), 2-acrylic acid 2- Methoxyethyl (-50 ° C), 3-methoxypropyl acrylate (-75 ° C), 3-methoxybutyl acrylate (-56 ° C), 2-ethoxymethyl acrylate (-50 ° C) , Octyl methacrylate (same -25 ° C.), it can be mentioned decyl methacrylate (same -49 ° C.).
These (meth) acrylic acid ester monomers (a1m) may be used alone or in combination of two or more.
These (meth) acrylic acid ester monomers (a1m) are preferably 80 to 99.9% by weight of the monomer unit (a1) derived from the (meth) acrylic acid ester copolymer (A1). More preferably, it is used for the polymerization in an amount of 85 to 99.5% by weight. If the amount of the (meth) acrylic acid ester monomer (a1m) is within the above range, the heat-sensitive pressure-sensitive adhesive sheet-like foamed molded product (F) obtained from the pressure-sensitive adhesive property near room temperature. Excellent.

The monomer (a2m) that gives the monomer unit (a2) having an organic acid group is not particularly limited, and representative examples thereof include organic acid groups such as a carboxyl group, an acid anhydride group, and a sulfonic acid group. In addition to these, monomers containing sulfenic acid groups, sulfinic acid groups, phosphoric acid groups, and the like can also be used. Specific examples of the monomer having a carboxyl group include α, β-ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; α, β- such as itaconic acid, maleic acid, and fumaric acid. And ethylenically unsaturated polyvalent carboxylic acids; α, β-ethylenically unsaturated polyvalent carboxylic acid partial esters such as methyl itaconate, butyl maleate and propyl fumarate; Moreover, what has group which can be induced | guided | derived to a carboxyl group by hydrolysis etc., such as maleic anhydride and itaconic anhydride, can be used similarly.
Specific examples of the monomer having a sulfonic acid group include allyl sulfonic acid, methallyl sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, α, β-unsaturated sulfonic acid such as acrylamide-2-methylpropane sulfonic acid, and the like. These salts can be mentioned.
Among these monomers having an organic acid group, monomers having a carboxyl group are more preferable, and among these, acrylic acid and methacrylic acid are particularly preferable. These are industrially inexpensive and can be easily obtained, have good copolymerizability with other monomer components, and are preferable in terms of productivity.

These monomers (a2m) having an organic acid group may be used alone or in combination of two or more.
In the monomer (a2m) having these organic acid groups, the monomer unit (a2) derived therefrom is 20 to 0.1% by weight, preferably 15 in the (meth) acrylic acid ester polymer (A1). It is desirable to be used for the polymerization in an amount of ˜0.5% by weight. In use within the above range, the viscosity of the polymerization system at the time of polymerization can be maintained in an appropriate range.
The monomer unit (a2) having an organic acid group is introduced into the (meth) acrylic acid ester polymer by polymerization of the monomer (a2m) having an organic acid group as described above. Although simple and preferable, an organic acid group may be introduced by a known polymer reaction after the (meth) acrylic acid ester polymer is formed.

The (meth) acrylic acid ester polymer (A1) may contain 10% by weight or less of a polymer unit (a3) derived from a monomer (a3m) containing a functional group other than an organic acid group. .
Examples of functional groups other than organic acid groups include hydroxyl groups, amino groups, amide groups, epoxy groups, mercapto groups, and the like.
Examples of the monomer having a hydroxyl group include (meth) acrylic acid hydroxyalkyl esters such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
Examples of the monomer containing an amino group include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and aminostyrene.
Examples of monomers having an amide group include α, β-ethylenically unsaturated carboxylic acid amide monomers such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and N, N-dimethylacrylamide. Can be mentioned.
Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and allyl glycidyl ether.
As the monomer (a3m) containing a functional group other than an organic acid group, one type may be used alone, or two or more types may be used in combination.
The monomer (a3m) having a functional group other than these organic acid groups is such that the monomer unit (a3) derived therefrom is 10% by weight or less in the (meth) acrylate polymer (A1). It is preferred to be used in the polymerization in an appropriate amount. By using 10% by weight or less of the monomer (a3m), the viscosity at the time of polymerization can be properly maintained.

The (meth) acrylic acid ester polymer (A1) is a (meth) acrylic acid ester monomer unit (a1) that forms a homopolymer of −20 ° C. or lower, a monomer unit having an organic acid group ( In addition to a monomer unit (a3) containing a functional group other than a2) and an organic acid group, a monomer unit (a4) derived from a monomer copolymerizable with these monomers (a4m) May be contained.
A monomer (a4m) may be used individually by 1 type, and may use 2 or more types together.
The amount of the monomer unit (a4) derived from the monomer (a4m) is preferably 10% by weight or less, more preferably 5% by weight or less of the acrylate polymer (A1). It is.
Although a monomer (a4m) is not specifically limited, (meth) acrylic acid ester other than the (meth) acrylic acid ester monomer (a1m) which forms the homopolymer which will be -20 degrees C or less as the specific example. Monomer, α, β-ethylenically unsaturated polyvalent carboxylic acid complete ester, alkenyl aromatic monomer, conjugated diene monomer, non-conjugated diene monomer, vinyl cyanide monomer, carboxylic acid Examples include unsaturated alcohol esters and olefinic monomers.

Specific examples of (meth) acrylic acid ester monomers other than the (meth) acrylic acid ester monomer (a1m) forming a homopolymer of −20 ° C. or lower include methyl acrylate (homopolymer glass) Examples of the transition temperature include 10 ° C., methyl methacrylate (105 ° C.), ethyl methacrylate (63 ° C.), propyl methacrylate (25 ° C.), butyl methacrylate (20 ° C.), and the like.
Specific examples of α, β-ethylenically unsaturated polyvalent carboxylic acid complete esters such as methyl itaconate, butyl maleate and propyl fumarate include dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, itacon Examples thereof include dimethyl acid.
Specific examples of the alkenyl aromatic monomer include styrene, α-methylstyrene, methyl α-methylstyrene, vinyl toluene and divinylbenzene.

Specific examples of the conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 2-chloro- Examples thereof include 1,3-butadiene and cyclopentadiene.
Specific examples of the non-conjugated diene monomer include 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene and the like.
Specific examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile and the like.
Specific examples of the carboxylic acid unsaturated alcohol ester monomer include vinyl acetate.
Specific examples of the olefin monomer include ethylene, propylene, butene, pentene and the like.

The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1) is preferably in the range of 100,000 to 400,000 as measured by gel permeation chromatography (GPC method). It is more preferable that it is in the range of 300 to 300,000.
The (meth) acrylic acid ester polymer (A1) is a (meth) acrylic acid ester monomer (a1m), a monomer having an organic acid group (a2m) that forms a homopolymer of −20 ° C. or lower, A monomer (a3m) containing a functional group other than an organic acid group, which is used as necessary, and a monomer copolymerizable with these monomers (a4m), which are used as needed, are copolymerized. Can be obtained particularly suitably.
The polymerization method is not particularly limited, and may be any of solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and the like, and may be other methods. Solution polymerization is preferred, and among these, solution polymerization using a carboxylic acid ester such as ethyl acetate or ethyl lactate or an aromatic solvent such as benzene, toluene or xylene is more preferred.
In the polymerization, the monomer may be added in portions to the polymerization reaction vessel, but it is preferable to add the whole amount at once.

The polymerization initiation method is not particularly limited, but it is preferable to use a thermal polymerization initiator as the polymerization initiator (C1). The thermal polymerization initiator is not particularly limited, and may be either a peroxide or an azo compound.
Examples of peroxide polymerization initiators include hydroperoxides such as t-butyl hydroperoxide; peroxides such as benzoyl peroxide and cyclohexanone peroxide; persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate; Can do.
These peroxides can also be used as a redox catalyst in appropriate combination with a reducing agent.
As the azo compound polymerization initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile) Etc.
Although the usage-amount of a polymerization initiator (C1) is not specifically limited, It is preferable that it is the range of 0.01-50 weight part with respect to 100 weight part of monomers.
There are no particular restrictions on the other polymerization conditions (polymerization temperature, pressure, stirring conditions, etc.) of these monomers.

  After completion of the polymerization reaction, the obtained polymer is separated from the polymerization medium as necessary. The separation method is not particularly limited, but in the case of solution polymerization, the (meth) acrylic acid ester polymer (A1) can be obtained by placing the polymerization solution under reduced pressure and distilling off the polymerization solvent.

  The (meth) acrylic acid ester monomer mixture (A2m) is not particularly limited as long as it is a mixture of a (meth) acrylic acid ester monomer and a monomer copolymerizable therewith, but the glass transition temperature is − (Meth) acrylic acid ester monomer (a5m) 70 to 99.9% by weight and a monomer having an organic acid group (a6m) 30 to 0.1% by weight forming a homopolymer of 20 ° C. or less Preferably it consists of.

  The (meth) acrylic acid ester monomer mixture (A2m) is 70 to 99.9% by weight of the (meth) acrylic acid ester monomer (a5m), the monomer having an organic acid group (a6m) 30 to 0 In addition to 0.1% by weight, it is preferable to contain a monomer (a7m) copolymerizable with these in an amount of 20% by weight or less.

As an example of the (meth) acrylic acid ester monomer (a5m) that forms a homopolymer having a glass transition temperature of −20 ° C. or lower, it is used for the synthesis of a (meth) acrylic acid ester polymer (A1) (meta ) The same (meth) acrylate monomer as the acrylate monomer (a1m) can be mentioned.
The (meth) acrylic acid ester monomer (a5m) may be used alone or in combination of two or more.
The ratio of the (meth) acrylic acid ester monomer (a5m) in the (meth) acrylic acid ester monomer mixture (A2m) is preferably 70 to 99.9% by weight, more preferably 75 to 99% by weight. is there.
When the ratio of the (meth) acrylic acid ester monomer (a5m) is in the above range, the heat-sensitive pressure-sensitive adhesive sheet-like foamed molded article (F) is excellent in pressure-sensitive adhesiveness and flexibility.

As an example of the monomer (a6m) having an organic acid group, a monomer having the same organic acid group as exemplified as the monomer (a2m) used for the synthesis of the (meth) acrylic acid ester polymer (A1) The body can be mentioned.
As the monomer having an organic acid group (a6m), one type may be used alone, or two or more types may be used in combination.
The ratio of the monomer (a6m) having an organic acid group in the (meth) acrylic acid ester monomer mixture (A2m) is preferably 30 to 0.1% by weight, more preferably 25 to 1% by weight. .
When the ratio of the monomer (a6m) having an organic acid group is within the above range, the hardness of the thermally conductive pressure-sensitive adhesive sheet-like foamed molded product (F) becomes appropriate, and the sensitivity at a high temperature (100 ° C.). The pressure adhesion is good.
Monomer (a7m) copolymerizable with (meth) acrylate monomer (a5m) and monomer having organic acid group (a6m) to form a homopolymer having a glass transition temperature of -20 ° C. or lower Examples of () are the same as those exemplified as the monomer (a3m), monomer (a4m), or polyfunctional monomer shown below for use in the synthesis of the (meth) acrylic acid ester polymer (A1). Can be mentioned.

As (a7m), as described above, a polyfunctional monomer having two or more polymerizable unsaturated bonds can also be used. By copolymerizing the polyfunctional monomer, intramolecular and / or intermolecular crosslinking can be introduced into the copolymer to increase the cohesive force as a pressure-sensitive adhesive.
Polyfunctional monomers include 1,6-hexanediol di (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, polyethylene glycol di (meth) ) Acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane triacrylate Polyfunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate; 2,4-bis (trichloromethyl) -6-p-me Monoethylenically unsaturated aromatic ketones such as 4-acryloxy benzophenone; substituted triazines such Kishisuchiren 5-triazine and the like can be used.

  The amount of the (meth) acrylic acid ester monomer mixture (A2m) is 20 to 55 parts by weight, preferably 25 to 50 parts by weight, more preferably 100 parts by weight of the (meth) acrylic acid ester polymer (A1). Is 30 to 45 parts by weight. When the amount of the (meth) acrylic acid ester monomer mixture (A2m) is less than the lower limit or exceeds the upper limit of the above range, the heat-sensitive pressure-sensitive adhesive sheet-like foamed molded product (F) is inferior in pressure-sensitive adhesiveness retention.

In the presence of the (meth) acrylic acid ester polymer (A1), the thermally conductive inorganic compound (B), the organic peroxide thermal polymerization initiator (C2), and the thermally decomposable organic foaming agent (D), ) The conditions for polymerizing the acrylate monomer mixture (A2m) are not particularly limited in addition to the polymerization initiation method described later.
In the present invention, the method for initiating polymerization for polymerizing the (meth) acrylic acid ester monomer mixture (A2m) in the presence of the (meth) acrylic acid ester polymer (A1) or the like includes organic peroxide heat. It is essential to use a polymerization initiator (C2). When a photopolymerization initiator is used instead of the organic peroxide thermal polymerization initiator, the adhesive strength of the resulting heat conductive pressure-sensitive adhesive sheet-like foamed molded article (F) is poor. In addition, when an azo thermal polymerization initiator is used instead of the organic peroxide thermal polymerization initiator, nitrogen gas is released during decomposition, and the average diameter of the foamed cell may deviate from the target range of the present invention. This is not preferable.
Examples of the organic peroxide thermal polymerization initiator (C2) include hydroperoxides such as t-butyl hydroperoxide; benzoyl peroxide, cyclohexanone peroxide, 1,6-bis (t-butylperoxycarbonyloxy) hexane (hereinafter referred to as “tBCH”). And a peroxide such as 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexanone (hereinafter sometimes abbreviated as “TMCH”); However, it is preferable not to release volatile substances that cause odor during thermal decomposition. Among the peroxide thermal polymerization initiators (C2), those having a one-minute half-life temperature of 120 ° C. or more and 170 ° C. or less are preferable.
The usage-amount of a peroxide thermal-polymerization initiator (C2) is the range of 0.1-5 weight part with respect to 100 weight part of (meth) acrylic acid ester polymers (A1). Preferably, it is 0.5-3 weight part. More preferably, it is 0.7-2 weight part.
The polymerization conversion rate of the (meth) acrylic acid ester monomer mixture (A2m) is preferably 95% by weight or more. If the polymerization conversion rate is too low, a monomer odor remains in the obtained heat conductive pressure-sensitive adhesive sheet-like foamed molded product (F), which is not preferable.

It is essential that the heat conductive pressure-sensitive adhesive sheet-like foamed molded article (F) of the present invention contains a heat conductive inorganic compound (B).
Examples of the thermally conductive inorganic compound (B) include metal oxides such as alumina, magnesium oxide, beryllium oxide and titanium oxide; metal nitrides such as boron nitride, silicon nitride and aluminum nitride; carbides such as silicon carbide; copper and silver Metals such as iron, aluminum and nickel; Carbon compounds such as diamond and carbon; Silica powder such as quartz and quartz glass, and the like. Preferably, the metal hydroxide of Group 2 or Group 13 of the Periodic Table is used. Oxide, oxide or nitride.
Examples of the Group 2 metal include magnesium, calcium, strontium, barium, and the like. Examples of the Group 13 metal include aluminum, gallium, and indium.
These heat conductive inorganic compounds (B) may be used individually by 1 type, and may use 2 or more types together.
The shape of the heat conductive inorganic compound (B) is not particularly limited, and may be any of a spherical shape, a needle shape, a fiber shape, a scale shape, a dendritic shape, a flat plate shape, and an indefinite shape.
Among the thermally conductive inorganic compounds (B), metal hydroxides are preferable, and aluminum hydroxide is particularly preferable. By using aluminum hydroxide, excellent flame retardancy can be imparted to the heat conductive pressure-sensitive adhesive composition of the present invention.

As the aluminum hydroxide, one having a particle size of 0.2 to 150 μm, preferably 0.7 to 100 μm is usually used. Moreover, it is preferable to have an average particle diameter of 1 to 80 μm. When the average particle size is less than 1 μm, the viscosity of the pressure-sensitive adhesive composition is increased, and at the same time, the hardness is increased, and the shape following property of the heat conductive pressure-sensitive adhesive sheet-like foamed molded product (F) is lowered. There is a fear.
On the other hand, when the average particle size exceeds 80 μm, the heat conductive pressure-sensitive adhesive sheet-like foamed molded article (F) becomes too soft and excessively pressure-sensitively bonded, the adhesive strength decreases at high temperatures, There is a risk of thermal deformation.

In this invention, the usage-amount of a heat conductive inorganic compound (B) is 50-500 weight part normally with respect to 100 weight part of (meth) acrylic acid ester polymer (A1), Preferably it is 100-300 weight part. More preferably, it is in the range of 150 to 250 parts by weight.
If the amount used is less than 50 parts by weight, there are problems such as high-temperature adhesive strength and thermal conductivity reduction of the heat conductive pressure-sensitive adhesive sheet-like foamed molded product (F). The hardness of the pressure-adhesive sheet-like foamed molded product (F) is increased, resulting in a problem of a decrease in shape followability.

  The average diameter of the foamed cells of the heat conductive pressure-sensitive adhesive sheet-like foamed molded product (F) of the present invention needs to be 50 μm to 550 μm. When the average diameter of the foamed cells is out of the range, the pressure-sensitive adhesive retention is inferior. The preferred average diameter of the foamed cells of the heat conductive pressure-sensitive adhesive sheet-like foamed molded article (F) is 100 μm to 500 μm, and more preferably 150 to 450 μm.

  The expansion ratio of the heat conductive pressure-sensitive adhesive sheet-like foamed molded article (F) of the present invention is usually 1.01 to 1.4 times. If it is out of the range of the expansion ratio, the pressure-sensitive adhesiveness is poor. A preferable expansion ratio of the heat conductive pressure-sensitive adhesive sheet-like foamed molded article (F) is 1.03 to 1.3 times, and a more preferable expansion ratio is 1.05 to 1.2 times.

As a foaming method, the thermal decomposable organic foaming agent (D) may be heated to a temperature equal to or higher than the thermal decomposition temperature to cause thermal decomposition. If desired, a foaming aid can be introduced. Examples of the foaming aid include zinc stearate, a mixture of stearic acid and zinc white, zinc laurate, a mixture of lauric acid and zinc white, and the like.
Examples of the thermally decomposable organic foaming agent (D) include p, p′-oxybis (benzenesulfonylhydrazide) (hereinafter sometimes referred to as “OBSH”), azodicarboxamide, and the like. The amount of the thermally decomposable organic foaming agent (D) used is 0.01 to 0.8 parts by weight, preferably 0.05 to 0.6 parts per 100 parts by weight of the (meth) acrylic acid ester polymer (A1). Parts by weight, more preferably 0.1 to 0.4 parts by weight, still more preferably 0.1 to 0.3 parts by weight. Thus, as the amount of the foaming agent used is within the above-mentioned preferable range, the average diameter of the foamed cells can be adjusted to the preferable range, and the balance between hardness and pressure-sensitive adhesiveness is excellent, and the shape followability and feeling are excellent. The heat conductive pressure-sensitive-adhesive sheet-like foaming molding (F) excellent in pressure-bonding retention property can be obtained.

The heat conductive pressure-sensitive adhesive composition (E), which is a precursor of the heat conductive pressure-sensitive adhesive sheet-like foamed molded article (F) of the present invention, is a (meth) acrylic acid ester polymer (A1) or (meth). In addition to the acrylic ester monomer mixture (A2m), the thermally conductive inorganic compound (B), the organic peroxide thermal polymerization initiator (C2), and the thermally decomposable organic foaming agent (D) in the above proportions, If necessary, various known additives such as pigments, other fillers, other thermal conductivity-imparting materials, flame retardants, anti-aging agents, thickeners, tackifiers, and the like within a range that does not impair the effects of the present invention. Can be contained.
The pigment can be used regardless of organic type or inorganic type such as carbon black and titanium dioxide.
Examples of other fillers include inorganic compounds such as clay. You may add nanoparticles, such as fullerene and a carbon nanotube.
Examples of other thermal conductivity imparting materials include inorganic compounds such as boron nitride, aluminum nitride, silicon nitride, aluminum oxide, and magnesium oxide as thermal conductivity imparting materials other than metal hydroxides.
Examples of the flame retardant include ammonium polyphosphate, zinc borate, tin compound, organic phosphorus compound, red phosphorus compound, and silicone flame retardant.
Antioxidants such as polyphenols, hydroquinones, and hindered amines can be used as the anti-aging agent, although they are not usually used because they are likely to inhibit radical polymerization.
As the thickener, inorganic polymer fine particles such as acrylic polymer particles and fine silica, and reactive inorganic compounds such as magnesium oxide can be used.
Examples of tackifiers include terpene resins, terpene phenol resins, rosin resins, petroleum resins, coumarone-indene resins, phenol resins, hydrogenated rosin esters, disproportionated rosin esters, xylene resins, and the like. it can.

Furthermore, in order to increase the cohesive force as a pressure-sensitive adhesive and improve heat resistance, etc. to the heat conductive pressure-sensitive adhesive sheet-like foamed molded article (F) of the present invention, an external crosslinking agent is added, A crosslinked structure can be introduced into the polymer mixture of the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer mixture (A2m).
As an external crosslinking agent, polyfunctional isocyanate type crosslinking agents such as tolylene diisocyanate, trimethylolpropane diisocyanate, diphenylmethane triisocyanate; epoxy crosslinking agents such as diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether; Examples thereof include melamine resin crosslinking agent; amino resin crosslinking agent; metal salt crosslinking agent; metal chelate crosslinking agent; peroxide crosslinking agent;
The external cross-linking agent was added to the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer mixture (A2m) polymer mixture, and then added to the heat treatment or radiation. By performing the irradiation treatment, a cross-link is formed within and / or between the molecules of the copolymer.

  The manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like foaming molding (F) of this invention is the (meth) acrylic acid ester polymer (A1) 100 weight part, (meth) acrylic acid ester monomer mixture (A2m). 20 to 55 parts by weight, thermally conductive inorganic compound (B) 50 to 500 parts by weight, organic peroxide thermal polymerization initiator (C2) 0.1 to 5 parts by weight, and thermally decomposable organic foaming agent (D) 0 The heat conductive pressure sensitive adhesive composition (E) composed of .01 to 0.8 parts by weight is formed into a sheet and heated to form a sheet of the heat conductive pressure sensitive adhesive composition (E). Polymerization of the (meth) acrylic acid ester monomer mixture (A2m) and thermal decomposition of the thermally decomposable organic foaming agent (D) are performed.

  The heat conductive pressure-sensitive adhesive composition (E), which is a precursor of the heat conductive pressure-sensitive adhesive sheet-like foamed molded article (F), comprises (meth) acrylic acid ester polymer (A1) 100 parts by weight, (meth). 20 to 55 parts by weight of acrylic acid ester monomer mixture (A2m), 50 to 500 parts by weight of thermally conductive inorganic compound (B), 0.1 to 5 parts by weight of organic peroxide thermal polymerization initiator (C2), and It is preferable to obtain 0.01 to 0.8 parts by weight of the thermally decomposable organic foaming agent (D) using a roll, a Henschel mixer, a kneader or the like. The mixing order of each component is not particularly limited. The mixing is preferably performed at a temperature at which the polymerization of the monomer mixture (A2m) and the decomposition of the thermally decomposable organic foaming agent (D) do not proceed.

The heat conductive pressure-sensitive adhesive sheet-like foamed molded article (F) of the present invention may be composed only of the heat conductive pressure-sensitive adhesive composition (E), and is formed on a substrate and one or both surfaces thereof. Further, it may be a composite comprising a layer of the heat conductive pressure-sensitive adhesive composition (E).
The thickness of the layer of the heat conductive pressure-sensitive adhesive composition (E) in the heat conductive pressure-sensitive adhesive sheet-like foamed molded product (F) of the present invention is not particularly limited, but is usually 50 μm to 3 mm. If it is thinner than 50 μm, air is likely to be involved when affixing to the heating element and the radiator, and as a result, sufficient thermal conductivity may not be obtained. On the other hand, when it is thicker than 3 mm, the heat resistance of the heat conductive pressure-sensitive adhesive sheet-like foamed molded product (F) increases, and the heat dissipation may be impaired.

When the layer of the heat conductive pressure-sensitive adhesive composition is formed on one side or both sides of the base material, the base material is not particularly limited.
Specific examples thereof include foils of metals and alloys having excellent thermal conductivity such as aluminum, copper, stainless steel, and beryllium copper; sheet-like materials made of a polymer having excellent thermal conductivity such as thermal conductive silicone; A heat conductive plastic film containing a heat conductive filler; various nonwoven fabrics; glass cloth; honeycomb structure; and the like can be used. Plastic films include polyimide, polyethylene terephthalate, polyethylene naphthalate, polytetrafluoroethylene, polyether ketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfone, polyphenylene sulfide, polyamideimide, polyesterimide, aromatic polyamide, etc. A film made of a heat-resistant polymer can be used.

Of the methods for producing a heat conductive pressure-sensitive adhesive sheet-like foamed molded article (F) from the heat conductive pressure-sensitive adhesive composition (E), the sheet forming method is, for example, a heat conductive pressure-sensitive adhesive composition ( E) is applied onto process paper such as a peeled polyester film, or a heat conductive pressure sensitive adhesive composition (E) is sandwiched between two exfoliated process papers if necessary, It is possible to control the thickness through a die when extruding between rolls or using an extruder.
In forming the sheet, it is desirable to apply pressure in order to make the thickness uniform. The pressure condition is usually 10 MPa or less, preferably 1 MPa or less. Pressurization exceeding 10 MPa is not preferable because the foamed cell may be crushed. The pressurization time may be selected in accordance with the temperature conditions and the type / amount of the polymerization initiator to be used, but is preferably within 1 hour in view of productivity.
While forming into a sheet or after forming into a sheet, for example, by heating the heat conductive pressure-sensitive adhesive composition (E) with hot air, an electric heater, infrared rays, or the like, the heat conductive feeling formed on the substrate and one or both sides thereof is formed. A heat conductive pressure-sensitive adhesive sheet-like foamed molded article (F) comprising a pressure adhesive composition layer can be obtained. The heating temperature at this time is such that the organic peroxide thermal polymerization initiator (C2) and the thermally decomposable organic foaming agent (D) are efficiently decomposed, and the polymerization of the (meth) acrylic acid ester monomer mixture (A2m) Conditions under which the thermal decomposition of the thermally decomposable organic foaming agent (D) proceeds almost simultaneously are preferred. The temperature range varies depending on the types of the organic peroxide thermal polymerization initiator (C2) and the thermally decomposable organic foaming agent (D) to be used, but is preferably 120 ° C to 160 ° C.

  The heat conductive pressure-sensitive adhesive composition of the present invention can be directly formed on a substrate such as a heat radiator and provided as a part of an electronic component.

Hereinafter, the present invention will be described in more detail with reference to examples. Parts and percentages in the examples are by weight unless otherwise specified.
In addition, the evaluation method of each characteristic of a (meth) acrylic acid ester copolymer, a heat conductive pressure sensitive adhesive composition, and a heat conductive foam sheet is as follows.
(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of (meth) acrylic acid ester copolymer
It is determined in terms of standard polystyrene by gel permeation chromatography using tetrahydrofuran as a developing solvent.
(2) Average diameter of foam cell of thermally conductive pressure-sensitive adhesive sheet-like foamed molded article (F) The surface of thermally conductive pressure-sensitive adhesive sheet-like foamed molded article (F) was observed with a laser microscope. The diameter of the foam cell is measured and the average diameter is obtained.
(3) Foaming ratio of heat-conductive pressure-sensitive adhesive sheet-like foamed molded article (F) The volume per unit weight of heat-conductive pressure-sensitive adhesive sheet-like foamed molded article (F) is unfoamed heat conduction having the same composition. It is obtained by dividing by the volume per unit weight of the pressure-sensitive adhesive sheet-like molded product.
(4) Hardness of heat conductive pressure-sensitive adhesive sheet-like foamed molded product (F) Measured by the Japan Rubber Association Standard (SRIS) Asker C method.
(5) Thermal conductivity of heat conductive pressure-sensitive adhesive sheet-like foamed molded article (F) Measured at room temperature using a rapid thermal conductivity meter (QTM-500, manufactured by Kyoto Electronics Industry Co., Ltd.).

(6) Room temperature adhesive force of heat conductive pressure-sensitive adhesive sheet-like foamed molded article (F) A 25 mm × 125 mm test piece is placed on an aluminum plate, pressed with a 2 kg roller, and left for 1 hour. This sample is set in a thermostatic chamber set at room temperature, and the maximum adhesive strength in the 90-degree direction is measured at a tensile speed of 50 mm / min.
(7) High-temperature adhesive strength of heat conductive pressure-sensitive adhesive sheet-like foamed molded article (F) The same as the room temperature adhesive strength test, except that the temperature of the thermostatic bath is 100 ° C.
(8) Shape followability of heat conductive pressure-sensitive adhesive sheet-like foamed molded article (F) A glass plate is placed on a 50 mm × 100 mm test piece, and a stress of 20 g / cm ² is applied to the glass plate for 30 seconds. After removing the stress and adjusting the state for 3 days, the ratio of the area in close contact with the glass surface is measured.
(9) Pressure-sensitive adhesive retention of thermally conductive pressure-sensitive adhesive sheet-like foamed molded article (F) A 25 mm × 25 mm test piece is placed on an aluminum plate and pressed with a 2 kg roller, and then glass is applied to the other surface. Crimp the plate. After leaving for 1 hour, with this test piece in a vertical state, an aluminum plate is fixed to the wall, and a 500 g weight is suspended from the glass plate and placed in a constant temperature layer at 100 ° C. atmosphere. The time (holding time) until the weight falls in this state is measured. The longer the time, the better the pressure-sensitive adhesive retention.

A reactor was charged with 100 parts of a monomer mixture composed of 94% 2-ethylhexyl acrylate and 6% acrylic acid, 0.03 parts 2,2′-azobisisobutyronitrile and 700 parts ethyl acetate. Then, after substitution with nitrogen, a polymerization reaction was carried out at 80 ° C. for 6 hours. The polymerization conversion rate was 97%. The obtained polymer was dried under reduced pressure to evaporate ethyl acetate to obtain a viscous solid (meth) acrylic acid ester polymer (A1) (1). Mw of the (meth) acrylic acid ester polymer (A1) (1) was 270,000, and Mw / Mn was 3.1.
In a mortar for crusher, 100 parts of (meth) acrylic acid ester polymer (A1) (1), 2-ethylhexyl acrylate 91.3%, methacrylic acid 6.1%, and pentaerythritol triacrylate (light acrylate PE) -3A: manufactured by Kyoeisha Chemical Co., Ltd.) (hereinafter abbreviated as “PETA”) 2.6% (meth) acrylic acid ester monomer mixture (A2m) (1) 32.85 parts, organic 1,6-bis (t-butylperoxycarbonyloxy) hexane (hereinafter abbreviated as “tBCH”) which is a peroxide thermal polymerization initiator (C2) [1 minute half-life temperature is 150 ° C. 0.9 parts, 0.2 parts of p, p′-oxybis (benzenesulfonylhydrazide) (hereinafter abbreviated as “OBSH”) which is a thermally decomposable organic foaming agent (D), and a thermally conductive inorganic compound 200 parts of aluminum hydroxide (B) was added all at once, and sufficiently mixed at room temperature with a crusher. Thereafter, the mixture was defoamed with stirring under reduced pressure to obtain a viscous liquid sample. A polyester film with a release agent was laid on the bottom surface of a mold having a length of 400 mm, a width of 400 mm, and a depth of 2 mm, and then the sample was poured into the mold and covered with a polyester film with a release agent. This was taken out from the mold, polymerized and foamed for 30 minutes in a hot air oven at 155 ° C., and heat-conductive pressure-sensitive adhesive sheet-like foamed molding (F) (F) (both sides covered with a polyester film with a release agent) 1) was obtained.
The polymerization conversion rate of the (meth) acrylic acid ester monomer mixture (A2m) was calculated from the amount of residual monomers in the sheet and found to be 99.9%.
Each characteristic was evaluated about this heat conductive pressure-sensitive-adhesive sheet-like foaming molding (F) (1). The results are shown in Table 1.

[Comparative Example 1]
A polyester film with a release agent on both sides, except that 1.0 part of OBSH was used instead of 0.2 part of p, p'-oxybis (benzenesulfonylhydrazide) (OBSH). A heat-conductive pressure-sensitive adhesive sheet-like foamed molded product (F) (2) covered with a coating was obtained.
Each characteristic was evaluated about this heat conductive pressure-sensitive-adhesive sheet-like foaming molding (F) (2). The results are shown in Table 1.

[Comparative Example 2]
As a (meth) acrylic acid ester monomer mixture (A2m), n-butyl acrylate 50.6%, 2-ethylhexyl acrylate 33.7%, methacrylic acid 11.2%, and pentaerythritol triacrylate (PETA) 44.5 parts of 4.5% are used, 1.6 parts of tBCH are used instead of 0.9 parts of 1,6-bis (t-butylperoxycarbonyloxy) hexane (tBCH), and p, p ′ -Oxybis (benzenesulfonyl hydrazide) (OBSH) The heat which covered both surfaces with the polyester film with a mold release agent by performing the same operation as Example 1 except having used 1.0 part of OBSH instead of 0.2 part. A conductive pressure-sensitive adhesive sheet-like foamed molded article (F) (3) was obtained.
Each characteristic was evaluated about this heat conductive pressure-sensitive-adhesive sheet-like foaming molding (F) (3). The results are shown in Table 1.

(Note to Table 1)
1: Pentaerythritol triacrylate 2: 1,6-bis (t-butylperoxycarbonyloxy) hexane 3: p, p'-oxybis (benzenesulfonylhydrazide)

From the results in Table 1, the following can be understood.
(Meth) acrylic acid ester polymer (A1) 100 parts, (meth) acrylic acid ester monomer mixture (A2m) 32.85 parts, thermally conductive inorganic compound (B) 200 parts, organic peroxide thermal polymerization start The heat conductive pressure-sensitive adhesive composition (E) comprising 0.9 part of the agent (C2) and 0.2 part of the thermally decomposable organic foaming agent (D) is molded into a sheet and heated. The conductive pressure-sensitive adhesive composition (E) is formed into a sheet, the (meth) acrylic acid ester monomer mixture (A2m) is polymerized, and the thermally decomposable organic foaming agent (D) is thermally decomposed, In Example 1 where the heat-conductive pressure-sensitive adhesive sheet-like foamed molded article (F) (1) having an average diameter of 340 μm was prepared, the hardness was good, the adhesive force, the shape following property, and the pressure-sensitive adhesive retention. A heat-conductive pressure-sensitive adhesive sheet-like foamed molded article excellent in the above was obtained.
On the other hand, in the case where 1.0 part of OBSH which is the thermally decomposable organic foaming agent (D) is used and the average diameter of the foamed cell is larger than the range described in the present invention (Comparative Example 1 and Comparative Example 2), The result was inferior in pressure-sensitive adhesion retention.

Claims (2)

(Meth) acrylic acid ester polymer (A1) 100 parts by weight, (Meth) acrylic acid ester monomer mixture (A2m) 20 to 55 parts by weight, thermally conductive inorganic compound (B) 50 to 500 parts by weight, A thermally conductive pressure-sensitive adhesive composition (E) comprising 0.1 to 5 parts by weight of an oxide thermal polymerization initiator (C2) and 0.01 to 0.8 parts by weight of a thermally decomposable organic foaming agent (D) The sheet is formed into a sheet and heated to form a sheet of the heat conductive pressure-sensitive adhesive composition (E), the polymerization of the (meth) acrylate monomer mixture (A2m), and the thermally decomposable organic foaming agent. A thermally conductive pressure-sensitive adhesive sheet-like foamed molded article (F) having an average diameter of foamed cells of 50 μm to 550 μm, which is obtained by performing thermal decomposition of (D). (Meth) acrylic acid ester polymer (A1) 100 parts by weight, (Meth) acrylic acid ester monomer mixture (A2m) 20 to 55 parts by weight, thermally conductive inorganic compound (B) 50 to 500 parts by weight, A thermally conductive pressure-sensitive adhesive composition (E) comprising 0.1 to 5 parts by weight of an oxide thermal polymerization initiator (C2) and 0.01 to 0.8 parts by weight of a thermally decomposable organic foaming agent (D) The sheet is formed into a sheet and heated to form a sheet of the heat conductive pressure-sensitive adhesive composition (E), the polymerization of the (meth) acrylate monomer mixture (A2m), and the thermally decomposable organic foaming agent. A method for producing a thermally conductive and pressure-sensitive adhesive sheet-like foamed molded article (F) having an average diameter of foamed cells of 50 μm to 550 μm, wherein the thermal decomposition of (D) is performed.