TW201522556A - Method for manufacturing thermally conductive pressure-sensitive adhesive composition, method for manufacturing thermally conductive pressure-sensitive adhesive sheet-like molded body, and electronic device - Google Patents

Abstract

Provided is a method for manufacturing a thermally conductive pressure-sensitive adhesive composition (F) including: a first mixing step of producing a first mixture composition including 0.3 part by mass or more and 3.5 parts by mass or less of a polar group modified halogenated hydrocarbon fiber (C) and 2 parts by mass or more and 13 parts by mass or less of a fatty acid ester of polyhydric alcohol polymer (D); a second mixing step of producing a second mixture composition including 100 parts by mass of a (meth)acrylic resin composition (A) including a (meth)acrylic acid ester polymer (A1) and a (meth)acrylic acid ester monomer ([alpha]1), 50 parts by mass or more and 1000 parts by mass or less of a thermally conductive filler (B), and the first mixture composition; and a polymerization step of carrying out at least polymerization reaction of the (meth)acrylic acid ester monomer ([alpha]1) in the second mixture composition.

Description

Method for producing heat-conductive sexy pressure-sensitive adhesive composition, method for producing heat-conductive elastic pressure-sensitive sheet-like molded body, and electronic device

The present invention relates to a method for producing a thermally conductive and sexy pressure-sensitive adhesive composition, a method for producing a thermally conductive and elastic pressure-sensitive sheet-like molded article, and a thermally conductive and elastic pressure-sensitive adhesive composition or the heat-conductive and elastic pressure-sensitive sheet-like formed body. Electronic machine.

In recent years, electronic components such as plasma display panels (PDPs) and integrated circuit (IC) wafers have increased heat generation due to their high performance. As a result, there is a need to take countermeasures against dysfunction caused by an increase in temperature. In general, a method in which a heat sink such as a metal heat sink, a heat sink, or a heat sink is attached to a heat generating body provided in an electronic component or the like is used. In order to efficiently perform heat conduction from the heat generating body to the heat radiating body, a sheet-like member (thermal conductive sheet) having high thermal conductivity is used. In general, in applications in which a heat generating body and a heat sink are fixed, a composition having pressure-sensitive adhesive properties in addition to thermal conductivity is required ( Hereinafter, it is called a "heat-conducting pressure-sensitive adhesive composition" or a sheet-shaped member (hereinafter referred to as "heat-conducting pressure-sensitive sheet-like molded body").

The heat-conducting elastic pressure-sensitive adhesive composition and the heat-conductive elastic pressure-sensitive sheet-like molded body are mainly intended to conduct heat to the heat radiating body by the heat generating body, and therefore it is preferable to improve the heat conductivity. In addition, the heat-conductive elastic pressure-sensitive adhesive composition and the heat-conductive elastic pressure-sensitive sheet-like molded body are provided with a filler corresponding to the intended function in order to have other functions than thermal conductivity in accordance with the use. For example, Patent Document 1 listed below discloses a thermally conductive and pressure-sensitive sheet-like formed body in which an expanded graphite powder or a polar-based denatured halogenated hydrocarbon fiber is added.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2011-246590

According to the technique disclosed in Patent Document 1, a thermally conductive and pressure-sensitive sheet-like formed body having thermal conductivity, flame retardancy, insulation, and flexibility in a well-balanced manner can be obtained. According to the technique disclosed in Patent Document 1, by adding a polar group-denatured halogenated hydrocarbon fiber, the function of flame retardancy of the heat-conductive elastic pressure-sensitive sheet-like formed body can be improved.

However, in consideration of increasing the addition amount of the polar group-denatured halogenated hydrocarbon fiber in order to further improve the flame retardancy of the heat-conductive pressure-sensitive sheet-like formed body, the viscosity of the composition before molding is excessively increased, and the productivity is deteriorated. Or a problem that cannot be formed.

In view of the above, it is an object of the present invention to provide a heat conductive and sexy pressure-sensitive adhesive composition which is improved in flame retardancy and has good productivity, and a method for producing a heat-conductive elastic pressure-sensitive sheet-like molded body. Moreover, the present invention provides an electronic device including a thermally conductive and sexy pressure-sensitive adhesive composition obtained by the above-described production methods or a thermally conductive and elastic pressure-sensitive sheet-like molded body.

According to a first aspect of the invention, there is provided a method of producing a thermally conductive and sexy pressure-sensitive adhesive composition (F), comprising the steps of: preparing a polar-containing modified halogenated hydrocarbon fiber (C) in an amount of 0.3 parts by mass or more in a first mixing step: 3.5 a first mixed composition of 2 parts by mass or more and 13 parts by mass or less of the fatty acid ester (D) of the polyol polymer or less; and a second mixing step to prepare the (meth)acrylate-containing polymer (A1) and 100 parts by mass of the (meth)acrylic resin composition (A) of the (meth) acrylate monomer (α1), 50 parts by mass or more and 1000 parts by mass or less of the thermally conductive filler (B), and the first mixed composition And a second mixing composition; and a polymerization step of performing at least a polymerization reaction of the (meth) acrylate monomer (α1) in the second mixed composition.

In the present specification, "a polar group-modified halogenated hydrocarbon fiber" means a halogenated hydrocarbon having a polar group in the structure. Specific examples of the polar group-modified halogenated hydrocarbon fiber (C) will be described below. Further, "(meth)acrylic" means "acrylic acid and/or methacrylic acid". In addition, the "thermally conductive filler" means the thermal conductivity of the heat-conductive elastic pressure-sensitive adhesive composition (F) or the heat-conductive elastic pressure-sensitive sheet-like molded body (G) which can be improved by the addition, and the thermal conductivity itself. It is 0.3W/m. Filler above K. Further, the "polymerization reaction of the (meth) acrylate monomer (?1)" means a polymerization reaction for obtaining a polymer containing a structural unit derived from the (meth) acrylate monomer (?1).

A second aspect of the present invention provides a method for producing a thermally conductive, pressure-sensitive, pressure-sensitive sheet-like molded article (G) comprising the steps of: preparing a polar component-containing denatured halogenated hydrocarbon fiber (C) by 0.3 parts by mass in a first mixing step 3.5 parts by mass or less of the first mixed composition of 2 parts by mass or more and 13 parts by mass or less of the fatty acid ester (D) of the polyol polymer; and a second mixing step to prepare a polymer containing (meth) acrylate (A1) And 100 parts by mass of the (meth)acrylic resin composition (A) of the (meth) acrylate monomer (α1), 50 parts by mass or more and 1000 parts by mass or less of the thermally conductive filler (B), and the first mixture a second mixed composition of the composition; and a molding step and a polymerization step, wherein the second mixed composition is formed into a sheet shape, or at least the methyl mixed composition is formed into a sheet shape, and the methyl group is at least Polymerization of acrylate monomer (α1).

According to a third aspect of the invention, there is provided an electronic device comprising: a heating element; and a method of manufacturing the thermally conductive and sexy pressure-sensitive adhesive composition (F) according to the first aspect of the invention, which is bonded to the heating element. The heat-conducting pressure-sensitive adhesive composition (F), or a heat generating body, and the heat-conductive elastic pressure-sensitive sheet-like molded body (G) according to the second aspect of the present invention The heat-conductive elastic pressure-sensitive sheet-like formed body (G) obtained by the method.

According to the present invention, it is possible to obtain a heat-conductive and sexy pressure-sensitive adhesive composition which is improved in flame retardancy and has good productivity, and a heat-conducting elastic pressure A sheet-like formed body.

1‧‧‧Substrate

2, 12a, 12b, 22‧‧‧ heating elements

3, 13‧‧‧ heat sink

4,14,24‧‧‧Hot-conducting elastic pressure-contact sheet-like formed body

1(A) to 1(C) are schematic diagrams showing an example of use of the heat conduction-sensitive pressure-sensitive sheet-like molded body (G).

[Formation of the Invention]

In order to provide flame-retardant properties of the heat-conductive pressure-sensitive adhesive composition and the heat-conductive pressure-sensitive sheet-like molded article, it is conceivable to add a filler which improves the flame retardancy. However, as the filler, for example, when a polar group-denatured halogenated hydrocarbon fiber is to be added in a large amount, the viscosity of the composition of the heat conduction-induced pressure-sensitive adhesive composition and the heat-conducting pressure-sensitive sheet-like molded body precursor is excessively increased, and Suspicion of reduced productivity or difficulty in production. The inventors of the present invention know that the composition of the heat-conducting pressure-sensitive adhesive composition and the heat-conductive elastic pressure-sensitive sheet-like formed body are all simultaneously mixed, and the composition is produced through a predetermined stage, even if the addition of the polar group-denatured halogenated hydrocarbon fiber is increased. The amount also inhibits excessive viscosity rise of the composition. The present invention is based on the foregoing knowledge. The details will be described below.

1. Method for producing heat conduction sexy pressure adhesive composition (F)

The method for producing a heat conductive and sexy pressure-sensitive adhesive composition (F) of the present invention comprises the steps of: preparing a fatty acid ester comprising a polar group-modified halogenated hydrocarbon fiber (C) and a polyol polymer in a first mixing step (D) a first mixed composition; a second mixing step to prepare a (meth) propyl group containing a (meth) acrylate polymer (A1) and a (meth) acrylate monomer (α1) An olefinic resin composition (A), a thermally conductive filler (B), and a second mixed composition of the first mixed composition; and a polymerization step in which at least the methyl group is Polymerization of acrylate monomer (α1).

1.1. The first mixing step

The fatty acid ester (D) of the polar group-modified halogenated hydrocarbon fiber (C) and the polyol polymer used in the first mixing step will be described below.

<Polar-based modified halogenated hydrocarbon fiber (C)>

The polar group-modified halogenated hydrocarbon fiber (C) used in the present invention may be a fiber-like modified halogenated hydrocarbon which is a halogenated hydrocarbon having a polar group in the structure, since it is required to be fibrous, Usually, it is a solid form, and it is a polymer compound. The polar group may be only one type or a plurality of different polar groups. Specific examples of the polar group include a (meth)acryl group, a hydroxyl group, a carbonyl group, a carboxyl group, an epoxy group, a glycidyl group, an amine group, a decylamino group, a quinone group, a cyano group, and the like. Among them, a (meth)acrylic group is preferred. In addition, examples of the halogen atom contained in the structure of the polar group-denatured halogenated hydrocarbon constituting the polar group-modified halogenated hydrocarbon fiber (C) include a fluorine atom, a chlorine atom, a bromine atom, etc., among which fluorine atoms are relatively ideal. Further, as the halogenated hydrocarbon constituting the polar group-containing portion of the polar group-modified halogenated hydrocarbon fiber (C), the total of the halogen atom and the hydrogen atom bonded by all the carbon atoms constituting the halogenated hydrocarbon in the polar group portion is excluded as 100. In the case of mol%, the halogen atom is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 90 mol% or more, and most preferably 100 mol%. According to the foregoing, as a polar group-denatured halogenated hydrocarbon fiber (C), (meth)acryl-based modified halogenated hydrocarbon fiber, polar-based denatured polytetrafluoroethylene Ethylene fiber (hereinafter, polytetrafluoroethylene is abbreviated as "PTFE") is preferable, and (meth)acryl-based modified PTFE fiber (for example, "METABLEN A-3000" manufactured by Mitsubishi Rayon Co., Ltd.) is particularly preferable.

The amount of the polar group-modified halogenated hydrocarbon fiber (C) used in the first mixing step is 0.3 parts by mass or more, based on 100 parts by mass of the (meth)acrylic resin composition (A) used in the second mixing step. 3.5 parts by mass or less, preferably 0.5 parts by mass or more and 3 parts by mass or less, more preferably 0.5 parts by mass or more and 2 parts by mass or less. By setting the amount of the polar group-denatured halogenated hydrocarbon fiber (C) to the lower limit or more of the above range, the heat conductive and sexy pressure-sensitive adhesive composition (F) can have sufficient flame retardancy. On the other hand, when the amount of the polar group-denatured halogenated hydrocarbon fiber (C) is equal to or less than the upper limit of the above range, the excessive increase in the viscosity of the second mixed composition described below can be suppressed.

<Fatty acid ester of polyol polymer (D)>

Next, the fatty acid ester (D) of the polyol polymer will be described.

The inventors of the present invention have found that by preparing a first mixed composition comprising the above-described polar-based denatured halogenated hydrocarbon fiber (C) and a fatty acid ester (D) of a polyol polymer in the first mixing step, the heat-conducting pressure is prepared. The amount of the polar group-modified halogenated hydrocarbon fiber (C) which functions as a flame retardant and the second mixed composition of the first composition and the second mixed composition of the first composition are higher than the conventional one. Further, it is also possible to suppress an excessive rise in the viscosity of the second mixed composition and to improve the productivity of the thermally conductive pressure-sensitive adhesive composition (F). That is, it has been found that the productivity of the heat-conductive sexy pressure-sensitive adhesive composition (F) having high flame retardancy can be improved.

Examples of the fatty acid ester (D) used in the polyol polymer of the present invention include polyglycerol fatty acid esters and polysorbate fatty acids. Ester, polypropylene glycol fatty acid ester, and the like. Among them, polyglycerol fatty acid esters are more preferable.

Examples of the polyglycerol fatty acid ester include polyglycerol condensed ricinoleate, polyglycerol ricinoleate, polyglycerol oleate, and polyglycerol stearate. Among them, polyglycerol condensed ricinoleate is particularly preferred.

Examples of the polysorbate fatty acid ester include polysorbate condensed ricinoleate, polysorbate ricinoleate, polysorbate oleate, and polysorbate. Fatty acid esters, etc.

Examples of the polypropylene glycol fatty acid ester include polypropylene glycol condensed ricinoleate, polypropylene glycol ricinoleate, polypropylene glycol oleate, and polypropylene glycol stearate.

The "condensed ricinoleic acid" described above will be described below. Ricinoleic acid is a compound having both a carboxyl group and a hydroxyl group. However, it is called "condensed ricinoleic acid" by esterification of a carboxyl group of ricinoleic acid with a hydroxyl group of ricinoleic acid of another molecule. . Further, the polyglycerol-condensed ricinoleic acid ester is obtained by esterifying a carboxyl group in ricinoleic acid with a hydroxyl group in a compound having a hydroxyl group.

Further, as the fatty acid ester (D) of the polyol polymer, the number average molecular weight is preferably 1,000 or more and 10,000 or less. Further, the fatty acid ester (D) of the polyol polymer is preferably a liquid at a temperature of from 10 ° C to 40 ° C.

The (meth)acrylic resin composition (A) used in the second mixing step is used in the first mixing step as 100 parts by mass. The amount of the fatty acid ester (D) of the polyol polymer is 2 parts by mass or more and 13 parts by mass or less, preferably 3 parts by mass or more and 10 parts by mass or less, more preferably 4 parts by mass or more and 10 parts by mass or less. When the amount of the fatty acid ester (D) of the polyol polymer is at least the lower limit of the above range, excessive viscosity increase of the second mixed composition can be suppressed, and the thermally conductive pressure-sensitive adhesive composition (F) can be prevented. Easy to shape. On the other hand, when the amount of the fatty acid ester (D) of the polyol polymer is equal to or less than the upper limit of the above range, the cohesive force of the second mixed composition can be suppressed from decreasing, and the heat conductive and sexy pressure-sensitive adhesive composition (F) can be prevented. Forming becomes difficult.

1.2. 2nd mixing step

Next, the second mixing step will be described. The second mixing step is a step of producing a second mixed composition comprising the (meth)acrylic resin composition (A), the thermally conductive filler (B), and the first mixed composition. The (meth)acrylic resin composition (A) and the thermally conductive filler (B) used in the second mixing step will be described below.

<(Meth)acrylic resin composition (A)>

The (meth)acrylic resin composition (A) used in the second mixing step contains a (meth) acrylate polymer (A1) and a (meth) acrylate monomer (α1), and may also contain A polyfunctional monomer to be described later. Further, at the time of obtaining the thermally conductive pressure-sensitive adhesive composition (F), at least a polymerization reaction of the (meth) acrylate monomer (α1) is carried out. By carrying out the polymerization reaction, the polymer containing the structural unit derived from the (meth) acrylate monomer (α1) is mixed with a component of the (meth) acrylate polymer (A1) and/or a part of the bond.

(Meth)acrylate polymer (A1) and (meth)acrylic acid The mixing ratio of the ester monomer (α1) is preferably 100% by mass of the (meth)acrylic resin composition (A) and 20% by mass or more and 80% by mass or less of the (meth)acrylate polymer (A1). The (meth) acrylate monomer (α1) is preferably 20% by mass or more and 80% by mass or less, and the (meth) acrylate polymer (A1) is preferably 30% by mass or more and 69.5% by mass or less. The acrylate monomer (α1) is preferably 30% by mass or more and 69.5% by mass or less. When the ratio of use of the (meth) acrylate monomer (α1) is within the above range, the heat conductive and sexy pressure-sensitive adhesive composition (F) can be easily molded.

((Meth)acrylate polymer (A1))

The (meth) acrylate polymer (A1) which can be used in the present invention is not particularly limited, but includes a unit of a (meth) acrylate monomer which forms a single polymer having a glass transition temperature of -20 ° C or lower (a1). And a monomer unit (a2) having an organic acid group is preferred.

The (meth) acrylate monomer (a1m) to which the unit (a1) of the above (meth) acrylate monomer is added is not particularly limited, and for example, ethyl acrylate (the glass transition temperature of the individual polymer is - 24 ° C), n-propyl acrylate (glass transition temperature of -37 ° C for individual polymers), n-butyl acrylate (glass transition temperature of -54 ° C for individual polymers), second butyl acrylate (polymer alone) Glass transition temperature is -22 ° C), n-heptyl acrylate (glass transition temperature of -60 ° C for individual polymers), n-hexyl acrylate (glass transition temperature of -61 ° C for individual polymers), n-octyl acrylate (alone The glass transition temperature of the polymer is -65 ° C), 2-ethylhexyl acrylate (glass transition temperature of -50 ° C for the individual polymer), n-octyl methacrylate (the glass transition temperature of the individual polymer is -25) °C), the formation of n-decyl methacrylate (glass transition temperature of -49 ° C for individual polymers) An alkyl (meth)acrylate having a glass transition temperature of -20 ° C or lower; 2-methoxyethyl acrylate (glass transition temperature of -50 ° C for a single polymer), 3-methoxypropene acrylate Ester (glass transition temperature of -75 ° C for individual polymers), 3-methoxybutyl acrylate (glass transition temperature of -56 ° C for individual polymers), ethoxymethyl acrylate (glass conversion of individual polymers) The alkyl (meth) acrylate or the like which forms a single polymer having a glass transition temperature of -20 ° C or lower, such as a temperature of -50 ° C). Among them, an alkyl (meth)acrylate which forms a single polymer having a glass transition temperature of -20 ° C or lower, and an alkoxyalkyl (meth)acrylate which forms a single polymer having a glass transition temperature of -20 ° C or less are preferred. Further, an alkyl (meth)acrylate which forms a single polymer having a glass transition temperature of -20 ° C or lower is more preferable, and 2-ethylhexyl acrylate is particularly preferable.

These (meth) acrylate monomers (a1m) may be used alone or in combination of two or more.

The (meth) acrylate monomer (a1m), the monomer unit (a1) thus derived is preferably 80% by mass or more and 99.9% by mass or less, more preferably in the (meth) acrylate polymer (A1). The polymerization is carried out in an amount of 85% by mass or more and 99.5% by mass or less. When the amount of use of the (meth) acrylate monomer (a1m) is within the above range, it is easy to maintain the viscosity of the polymerization system during polymerization in an appropriate range.

Next, the monomer unit (a2) having an organic acid group will be described. The monomer (a2m) to which the monomer unit (a2) having an organic acid group is imparted is not particularly limited, and examples thereof include a monomer having an organic acid group such as a carboxyl group, an acid anhydride group or a sulfonic acid group. Further, in addition to these, a monomer containing a sulfenic acid group, a sulfinic acid group, a phosphoric acid group or the like can also be used.

Specific examples of the monomer having a carboxyl group include, for example, α,β-ethylenically unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid or crotonic acid, or itaconic acid, maleic acid, fumaric acid or the like. Further, in addition to the β-ethylenically unsaturated polycarboxylic acid, an α,β-ethylenically unsaturated polycarboxylic acid moiety such as monomethyl itaconate, monobutyl maleate or monopropyl fumarate may be mentioned. Ester and the like. Further, a base such as maleic anhydride or itaconic anhydride which can be induced to be a carboxyl group by hydrolysis or the like can be used in the same manner.

Specific examples of the monomer having a sulfonic acid group include allylsulfonic acid, methallylsulfonic acid, vinylsulfonic acid, styrenesulfonic acid, acrylamide-2-methylpropanesulfonic acid, and the like. The α,β-unsaturated sulfonic acid, and the salts thereof.

As the monomer (a2m), among the monomers having an organic acid group exemplified above, a monomer having a carboxyl group is more preferable, and an α,β-ethylenically unsaturated monocarboxylic acid is particularly preferable, and (meth)acrylic acid is most preferable. These monomers are industrially inexpensive and easily available, and have good copolymerizability with other monomer components, and are also preferable from the viewpoint of productivity. Further, the monomer (a2m) may be used alone or in combination of two or more.

The monomer (a2m) having an organic acid group, and the monomer unit (a2) thus derived is preferably 0.1% by mass or more and 20% by mass or less, more preferably in the (meth) acrylate polymer (A1). The amount is 0.5% by mass or more and 15% by mass or less and is supplied to the polymerization. When the amount of the monomer (a2m) having an organic acid group is within the above range, it is easy to maintain the viscosity of the polymerization system during polymerization in an appropriate range.

Further, the monomer unit (a2) having an organic acid group is introduced into (A) by polymerization of a monomer (a2m) having an organic acid group as described above. The acrylate polymer (A1) is preferred because it is simple. However, after the (meth) acrylate polymer (A1) is produced, an organic acid group can also be introduced by a well-known polymer reaction.

Further, the (meth) acrylate polymer (A1) may further contain a monomer unit (a3) derived from a monomer (a3m) having a functional group other than an organic acid group. The functional group other than the above organic acid group may, for example, be a hydroxyl group, an amine group, a decylamino group, an epoxy group or a decyl group.

Examples of the monomer having a hydroxyl group include a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate or 3-hydroxypropyl (meth)acrylate.

Examples of the monomer having an amine group include N,N-dimethylaminomethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and aminostyrene.

Examples of the monomer having a guanamine group include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and N,N-dimethylpropene. An α,β-ethylenically unsaturated phthalamide monomer such as guanamine.

Examples of the monomer having an epoxy group include glycidyl (meth)acrylate and allyl epoxidized ether.

The monomer (a3m) having a functional group other than the organic acid group may be used alone or in combination of two or more.

The monomer (a3m) having a functional group other than the organic acid group, and the monomer unit (a3) derived therefrom is preferably 10% by mass or less in the (meth) acrylate polymer (A1). The amount is used for aggregation. By using 10% by mass or less of the monomer (a3m), it becomes easy to polymerize The viscosity of the polymerization system is maintained in an appropriate range.

(meth) acrylate polymer (A1), in addition to the aforementioned (meth) acrylate monomer unit (a1) which forms a single polymer having a glass transition temperature of -20 ° C or lower, a monomer unit having an organic acid group ( A2) and a monomer unit (a3) having a functional group other than the organic acid group may further contain a monomer unit (a4) derived from a monomer (a4m) copolymerizable with the above monomer.

The monomer (a4m) is not particularly limited, and specific examples thereof include a (meth) acrylate monomer other than the above (meth) acrylate monomer (a1m), and α,β-ethylenically unsaturated plural. A carboxylic acid complete ester, an alkenyl aromatic monomer, a vinyl cyanide monomer, a carboxylic acid unsaturated alcohol ester, an olefin type monomer, or the like.

Specific examples of the (meth) acrylate monomer other than the (meth) acrylate monomer (a1m) include methyl acrylate (the glass transition temperature of the individual polymer is 10 ° C), and methacrylic acid Ester (glass transition temperature of 105 ° C for individual polymers), ethyl methacrylate (glass transition temperature of 63 ° C for individual polymers), n-propyl methacrylate (glass transition temperature of individual polymers is 25 ° C) , n-butyl methacrylate (glass transition temperature of the individual polymer is 20 ° C) and the like.

Specific examples of the α,β-ethylenically unsaturated polycarboxylic acid complete ester include dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, and clothing. Dimethyl benzoate and the like.

Specific examples of the alkenyl aromatic monomer include styrene, α-methylstyrene, methyl α-methylstyrene, and vinyltoluene.

Specific examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and α-ethyl acrylonitrile.

Specific examples of the carboxylic acid unsaturated alcohol ester monomer include vinyl acetate and the like.

Specific examples of the olefin-based monomer include ethylene, propylene, butene, and pentene.

The monomer (a4m) may be used alone or in combination of two or more.

The amount of the monomer unit (a4) to be derived from the monomer (a4m) is preferably 10% by mass or less, more preferably 5% by mass or less, based on the (meth) acrylate polymer (A1). And for aggregation.

(meth)acrylate polymer (A1), a (meth) acrylate monomer (a1m) having a glass transition temperature of -20 ° C or less, a monomer having an organic acid group ( A2m), if necessary, a monomer (a3m) containing a functional group other than an organic acid group, and optionally a monomer (a4m) copolymerizable with the monomers, particularly suitably obtained .

The polymerization method for obtaining the (meth) acrylate polymer (A1) is not particularly limited, and may be any of solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization, and may be a method other than the above. . However, in such a polymerization method, solution polymerization is preferred, and among them, a carboxylate such as ethyl acetate or ethyl lactate or an aromatic solvent such as benzene, toluene or xylene is more preferably used as the polymerization solvent. At the time of polymerization, the monomer may be added to the polymerization reaction vessel in a divided manner, but it is preferable to add the entire amount at one time. The method of starting the polymerization is not particularly limited, but thermal polymerization is used. The initiator is preferably used as a polymerization initiator. The thermal polymerization initiator is not particularly limited, and for example, a peroxide polymerization initiator or an azo compound polymerization initiator can be used.

Examples of the peroxide polymerization initiator include hydrogen peroxide such as t-butyl hydroperoxide or persulfuric acid such as peroxide such as benzamidine peroxide or cyclohexanone peroxide. Persulfate such as potassium, sodium persulfate or ammonium persulfate. These peroxides may also be suitably combined with a reducing agent and used as a redox catalyst.

Examples of the polymerization initiator of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-couple. Nitrogen bis(2-methylbutyronitrile) and the like.

The amount of the polymerization initiator to be used is not particularly limited, but is preferably in the range of 0.01 part by mass or more and 50 parts by mass or less based on 100 parts by mass of the monomer.

Other polymerization conditions (polymerization temperature, pressure, stirring conditions, and the like) of the monomers are not particularly limited.

After completion of the polymerization reaction, the obtained polymer is separated from the polymerization medium as needed. The method of separation is not particularly limited. For example, in the case of solution polymerization, the (meth) acrylate polymer (A1) can be obtained by subjecting the polymerization solution to a reduced pressure and distilling off the polymerization solvent.

The weight average molecular weight (Mw) of the (meth) acrylate polymer (A1) is measured by colloidal permeation chromatography (GPC method), and is preferably in the range of 1,000 or more and 1,000,000 or less in terms of standard polystyrene. It is better in the range of 100,000 to 500,000. The weight average molecular weight of the (meth) acrylate polymer (A1) can be adjusted by appropriate adjustment at the time of polymerization The amount of the polymerization initiator used, or the amount of the chain transfer agent, is controlled.

((meth)acrylate monomer (α1))

The (meth) acrylate monomer (α1) is not particularly limited as long as it contains a (meth) acrylate monomer, but contains (meth)acrylic acid which forms a single polymer having a glass transition temperature of -20 ° C or lower. The ester monomer (a5m) is preferred.

Examples of the (meth) acrylate monomer (a5m) which forms a single polymer having a glass transition temperature of -20 ° C or lower include the synthesis of (meth) acrylate polymer (A1) ( The methyl (meth) acrylate monomer (a1m) is the same (meth) acrylate monomer. The (meth) acrylate monomer (a5m) may be used alone or in combination of two or more.

The ratio of the (meth) acrylate monomer (a5m) of the (meth) acrylate monomer (α1) is preferably 50% by mass or more and 100% by mass or less, and more preferably 75% by mass or more and 100% by mass or less. By setting the ratio of the (meth) acrylate monomer (a5m) of the (meth) acrylate monomer (α1) to the above range, it is easy to obtain a heat-conductive sexy pressure-sensitive adhesive excellent in pressure-sensitive adhesiveness or flexibility. Composition (F).

Further, the (meth) acrylate monomer (α1) may be used as a (meth) acrylate monomer (a5m) which forms a single polymer having a glass transition temperature of -20 ° C or lower, and may be copolymerized with the same. A mixture of monomers (a6m) having an organic acid group.

An example of the monomer (a6m) is a monomer having an organic acid group similar to those exemplified as the monomer (a2m) used for the synthesis of the (meth)acrylate polymer (A1). The monomer (a6m) may be used alone or in combination of two or more.

The ratio of the monomer (a6m) of the (meth) acrylate monomer (α1) is preferably 30% by mass or less, more preferably 10% by mass or less. By setting the ratio of the monomer (a6m) of the (meth) acrylate monomer (α1) to the above range, it is easy to obtain a heat-conductive pressure-sensitive adhesive composition (F) excellent in pressure-sensitive adhesiveness or flexibility.

The (meth) acrylate monomer (α1) may be included in addition to the (meth) acrylate monomer (a5m) and the monomer (a6m) having an organic acid group which may be copolymerized as desired. A mixture with the copolymerized monomers (a7m).

Examples of the monomer (a7m) include the same monomers as those of the monomer (a3m) and the monomer (a4m) used for the synthesis of the (meth)acrylate polymer (A1). The monomer (a7m) may be used alone or in combination of two or more.

The ratio of the monomer (a7m) of the (meth) acrylate monomer (α1) is preferably 20% by mass or less, more preferably 15% by mass or less.

(multifunctional monomer)

In the present invention, a polyfunctional monomer may be used in the (meth)acrylic resin composition (A). Usually, in the polymerization of radical thermal polymerization or the like, a certain degree of crosslinking reaction can be carried out without using a polyfunctional monomer. However, in order to be more precise and to form the desired amount of crosslinked structure, a polyfunctional monomer can also be used.

As the polyfunctional monomer which can be used in the present invention, those which are copolymerizable with the monomer contained in the (meth) acrylate monomer (α1) are used. Further, the polyfunctional monomer has a plurality of polymerizable unsaturated bonds, and it is preferred to have the unsaturated bond at the terminal. By using as much as mentioned above The functional monomer can be crosslinked within the copolymer-introduced molecule and/or intermolecularly, and the cohesive force of the pressure-sensitive adhesive as the heat conductive and sexy pressure-sensitive adhesive composition (F) can be improved.

As the above polyfunctional monomer, for example, in addition to 1,6-hexanediol di(meth)acrylate, 1,2-ethanediol 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, di-trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Substituted polyfunctional (meth) acrylate such as (meth) acrylate or 2,4-bis(trichloromethyl)-6-p-methoxystyrene-5-triazabenzene In addition to the triazabenzene, a monoethylenically unsaturated aromatic ketone such as 4-propenyl oxybenzophenone may be used. Among them, a polyfunctional (meth) acrylate is preferable, and pentaerythritol di(meth) acrylate, pentaerythritol tri(meth) acrylate, or pentaerythritol tetra (meth) acrylate is more preferable. The polyfunctional monomer may be used alone or in combination of two or more.

The (meth)acrylic resin composition (A) is used as 100% by mass, and the polyfunctional monomer is preferably used in an amount of 10% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less. When the amount of the polyfunctional monomer used is in the above range, it is easy to impart an appropriate cohesive force to the thermally conductive pressure-sensitive adhesive composition (F).

<Polymerization initiator>

When the heat conductive sexy pressure-sensitive adhesive composition (F) is obtained, it is as described above. A component contained in the (meth)acrylic resin composition (A). In order to promote the polymerization, it is preferred to use a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator, an azo-based thermal polymerization initiator, and an organic peroxide thermal polymerization initiator. However, from the viewpoint of imparting a strong adhesive force to the obtained heat-conductive pressure-sensitive adhesive composition (F), it is preferred to use an organic peroxide thermal polymerization initiator.

As the photopolymerization initiator, various known photopolymerization initiators can be used. Among them, a mercaptophosphine oxide compound is preferable. The mercaptophosphine oxide-based compound which is a preferred photopolymerization initiator may, for example, be bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide or 2,4,6-trimethyl. Benzobenzyldiphenylphosphine oxide and the like.

Examples of the azo thermal polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'- Azobis(2-methylbutyronitrile) and the like.

Examples of the organic peroxide thermal polymerization initiator include hydrogen peroxide such as t-butyl hydroperoxide or, for example, benzamidine peroxide, cyclohexanone peroxide, and 1,6-bis (first) A peroxide such as tributylperoxycarbonyloxy)hexane or 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexanone. However, it is preferable that a volatile substance which is a cause of odor is not released during thermal decomposition. Further, in the organic peroxide thermal polymerization initiator, the one-minute half-life temperature is preferably from 100 ° C to 170 ° C.

The amount of the polymerization initiator to be used is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.1 part by mass or more and 5 parts by mass or less, based on 100 parts by mass of the (meth)acrylic resin composition (A). quality The amount of the above is preferably 2 parts by mass or less.

When the amount of the polymerization initiator to be used is in the above range, the polymerization conversion ratio of the (meth) acrylate monomer (α1) is easily made into an appropriate range, and it becomes easy to prevent the composition of the thermally conductive and sexy pressure-sensitive adhesive. (F) residual monomer bromine.

Further, the polymerization conversion ratio of the (meth) acrylate monomer (α1) is preferably 95% by mass or more. When the polymerization conversion ratio of the (meth) acrylate monomer (α1) is 95% by mass or more, it is easy to prevent the monomer bromine from remaining in the thermally conductive pressure-sensitive adhesive composition (F).

In addition, when the amount of the polymerization initiator to be used is in the above range, it is easy to prevent the polymerization reaction from proceeding excessively, and the surface of the heat-conductive pressure-sensitive adhesive composition (F) is not smooth, and irregularities or pinholes are generated.

<Thermal conductive filler (B)>

Next, the thermally conductive filler (B) will be described. As the thermally conductive filler (B), the thermal conductivity of the heat-conducting pressure-sensitive adhesive composition (F) can be improved by the addition, and the thermal conductivity of itself is 0.3 W/m. Filler above K.

Specific examples of the thermally conductive filler (B) include metal hydroxides such as aluminum hydroxide, gallium hydroxide, indium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and barium hydroxide; and alumina (alumina), metal oxides such as magnesium oxide, vermiculite (yttria), zinc oxide, etc.; metal carbonates such as calcium carbonate and aluminum carbonate; metal nitrides such as boron nitride and aluminum nitride; zinc borate hydrate Kaolin; calcium aluminate hydrate; silk dawsonite; expanded graphite powder, artificial graphite, carbon black, carbon fiber and other conductive fillers containing carbon. Among these, metal hydroxides, A metal oxide and a conductive filler containing carbon are preferable, and a metal hydroxide and a conductive filler containing carbon are more preferable, and aluminum hydroxide and expanded graphite powder are particularly preferable. The heat conductive filler (B) may be used alone or in combination of two or more.

<Expanded graphite powder>

Here, the expanded graphite powder which can be used as the heat conductive filler (B) will be described.

The expanded graphite powder has high thermal conductivity, and the thermal conductivity of the heat-conductive elastic pressure-sensitive adhesive composition (F) and the heat-conductive elastic pressure-sensitive sheet-like molded body (G) can be improved by adding the expanded graphite powder. In addition, by adding the expanded graphite powder, it is possible to suppress dissolution even when the heat-conductive elastic pressure-sensitive adhesive composition (F) and the heat-conductive pressure-sensitive adhesive sheet-like molded body (G) are heated, and the flame retardancy can be improved.

Further, the expanded graphite powder is preferably added in the second mixing step.

The expanded graphite powder is obtained by pulverizing graphite and then pulverizing it. As an example of the expanded graphite powder used in the present invention, the graphite containing the acid-treated graphite is heat-treated at 500 ° C to 1200 ° C or lower and expanded to 100 ml / g or more and 300 ml / g or less, followed by pulverizing the graphite. The method of the step is obtained. More preferably, it is contained by sintering the graphite in a base after being treated with a strong acid, and then heat-treating the resin at 500 ° C or more and 1200 ° C or less to remove the acid, and expanding to 100 ml / g or more and 300 ml / Below g, the method of pulverizing is followed. The temperature of the above heat treatment is particularly preferably 800 ° C or more and 1000 ° C or less.

The amount of the heat conductive filler (B) to be used in the second mixing step is 50 parts by mass or more and 1000 parts by mass or less based on 100 parts by mass of the (meth)acrylic resin composition (A), and 100 parts by mass or more and 900 parts by mass or more It is preferably 15 parts by mass or more and 800 parts by mass or less, more preferably 150 parts by mass or more and 300 parts by mass or less. When the amount of the thermally conductive filler (B) is not more than the above upper limit, it is easy to suppress the viscosity of the second mixed composition from becoming excessively high. Therefore, it is possible to prevent the heat conduction-sensitive pressure-sensitive adhesive composition (F) from being formed, and the hardness of the formed heat-conductive pressure-sensitive adhesive composition (F) is increased, and the shape is uniform (adhesiveness to the coating body) ) The state of decline. On the other hand, when the content of the thermally conductive filler (B) is at least the above lower limit, the effect of improving the thermal conductivity of the thermally conductive pressure-sensitive adhesive composition (F) is easily exhibited.

In addition, when a metal hydroxide and a conductive filler containing carbon are used as the heat conductive filler (B), the heat conductive pressure-sensitive adhesive composition (F) and the heat-conductive elastic pressure-sensitive sheet-like molded body (G) are insulated. The amount of the conductive filler containing carbon used in the second mixing step is 50 parts by mass or less based on 100 parts by mass of the (meth)acrylic resin composition (A), and It is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 2 parts by mass or more and 15 parts by mass or less, and particularly preferably 3 parts by mass or more and 10 parts by mass or less.

The average particle diameter of the entire filler used as the thermally conductive filler (B) is preferably 0.5 μm or more and 15 μm or less, more preferably 0.8 μm or more and 12 μm or less. Moreover, the BET specific surface area of the entire filler used as the thermally conductive filler (B) is preferably 0.3 m ² /g or more and 10 m ² /g or less, more preferably 0.5 m ² /g or more and 5 m ² /g or less. When the average particle diameter and the BET specific surface area of the entire filler used as the thermally conductive filler (B) are within the above range, the viscosity of the mixed composition can be made appropriate even if the content of the thermally conductive filler (B) is increased. Further, the heat-conductive elastic pressure-sensitive adhesive composition (F) and the heat-conductive elastic pressure-sensitive sheet-like molded body (G) are less likely to become brittle, and the strength reduction can be further suppressed.

In the present invention, the "average particle diameter" means a person measured by the method described below. In other words, a laser-type particle size measuring machine (manufactured by SEISHIN ENTERPRISE CO., LTD.) is used for measurement by a micro-gradation control method (method of passing the measurement target particles only in the measurement region to improve the reliability of the measurement). According to the measurement method, 0.01 g to 0.02 g of the measurement target particles are caused to flow in the cartridge, and the measurement target particles flowing in the measurement region are irradiated with semiconductor laser light having a wavelength of 670 nm, and the laser light at this time is measured by a measuring device. The scattering and diffraction are used to calculate the average particle size and particle size distribution according to the diffraction principle of Fraunhofer.

Further, in the present invention, "BET specific surface area" means a person who measures by the following method. First, a mixed gas of nitrogen and helium is introduced into a BET specific surface area measuring device, and a sample cartridge to which a sample (measured object of BET specific surface area) is added is immersed in liquid nitrogen to adsorb nitrogen gas on the surface of the sample. After reaching the adsorption equilibrium, the sample box was placed in a water bath, and the temperature was raised to normal temperature to desorb the nitrogen attached to the sample. Since the mixing ratio of the gas before and after passing the sample cartridge during the adsorption and desorption of nitrogen changes, the mixing ratio of nitrogen and helium is a certain gas as a control, and the change is detected by a thermal conductivity detector (TCD). And determine the amount of nitrogen adsorption and desorption. A unit amount of nitrogen gas is introduced into the apparatus before the measurement, and correction is performed to obtain a value corresponding to the surface area of the value detected by TCD. The surface area of the sample can be obtained. Then, by dividing the obtained surface area by the mass of the sample, the BET specific surface area can be obtained.

1.3. Aggregation steps

Next, the polymerization step will be described. The polymerization step is a step of performing at least a polymerization reaction of the (meth) acrylate monomer (α1) in the second mixed composition. It is preferable to carry out heating at the time of carrying out this polymerization reaction. In the heating, for example, hot air, an electric heater, infrared rays, or the like can be used. At the heating temperature at this time, the polymerization initiator can be efficiently decomposed, and the temperature at which the (meth) acrylate monomer (α1) is polymerized is preferably carried out. The specific preferred temperature range varies depending on the type of the polymerization initiator to be used, etc., but is preferably 100 ° C or more and 200 ° C or less, and more preferably 120 ° C or more and 180 ° C or less.

1.4. Effect

The method for producing the thermally conductive and sexy pressure-sensitive adhesive composition (F) according to the present invention is carried out by dividing into a first mixing step and a second mixing step, even if the amount of the polar-denatured halogenated hydrocarbon fiber (C) is higher than that of the conventional one. When the amount is further increased, the viscosity of the second mixed composition is excessively increased, and the productivity of the heat-conductive pressure-sensitive adhesive composition (F) can be suppressed from being lowered. Therefore, the productivity of the heat-conductive sexy pressure-sensitive adhesive composition (F) having high flame retardancy can be improved.

1.5. Other additives

In the heat-conductive pressure-sensitive adhesive composition (F) of the present invention, in addition to the materials described so far, the effect of the method for producing the heat-conductive elastic pressure-sensitive adhesive composition (F) of the present invention is further enhanced, or You can add a variety of well-known additions without hindering the effects. Additives.

Examples of well-known additives include flame retardants such as phosphate esters; foaming agents (including foaming aids); glass fibers; external crosslinking agents; pigments; and other fillers other than thermally conductive fillers; An antioxidant such as a phenol type, a hydroquinone type or a hindered amine type; or a tackifier such as an acrylic polymer particle.

2. Method for producing heat-conducting elastic pressure-contact sheet-like formed body (G)

Next, a method of producing the heat-conductive elastic pressure-sensitive sheet-like molded body (G) of the present invention will be described. The method for producing a thermally conductive and pressure-sensitive sheet-like formed article (G) according to the present invention comprises the steps of: preparing a fatty acid ester comprising a polar group-modified halogenated hydrocarbon fiber (C) and a polyol polymer in a first mixing step a first mixed composition of (D); and a second mixing step for preparing a (meth)acrylic resin comprising a (meth) acrylate polymer (A1) and a (meth) acrylate monomer (α1) a material (A), a thermally conductive filler (B), and a second mixed composition of the first mixed composition; and a molding step and a polymerization step, after the second mixed composition is formed into a sheet shape, or The second mixed composition is formed into a sheet shape, and at least the polymerization reaction of the (meth) acrylate monomer (α1) is carried out.

Since the first mixing step, the second mixing step, and other additives are the same as the method of producing the thermally conductive pressure-sensitive adhesive composition (F), the description thereof is omitted.

2.1. Forming step and polymerization step

The molding step and the polymerization step of the method for producing the heat-conductive elastic pressure-sensitive sheet-like molded article (G) of the present invention will be described. Forming step And the polymerization step is a step of forming at least a polymerization reaction of the (meth) acrylate monomer (α1) after molding the second mixed composition into a sheet shape or by molding the second mixed composition into a sheet shape. . In the polymerization step, it is preferred to carry out the heating while the polymerization reaction is carried out. In this heating, for example, hot air, an electric heater, infrared rays, or the like can be used. At the heating temperature at this time, the polymerization initiator can be efficiently decomposed, and the temperature at which the (meth) acrylate monomer (α1) is polymerized is preferably carried out. The specific preferred temperature range varies depending on the type of the polymerization initiator to be used, etc., but is preferably 100 ° C or more and 200 ° C or less, and more preferably 120 ° C or more and 180 ° C or less.

Further, in the molding step, the method of forming the second mixed composition into a sheet shape is not particularly limited. As a suitable method, for example, a method of applying a second mixed composition onto a step paper such as a release-treated polyester film to form a sheet shape, and holding the paper between the two sheets of the release process may be mentioned. The second mixed composition is formed into a sheet shape by compression between the rolls, and the second mixed composition is extruded by using an extruder, and at this time, the mold is controlled to have a thickness to be formed into a sheet shape. Wait. The above-mentioned step paper is not particularly limited, and for example, a release-treated polyethylene terephthalate film or a release-treated polyethylene naphthalate film or the like can be used. Among them, a polyethylene terephthalate film which is especially treated by release is preferable.

The heat-conductive elastic pressure-contact sheet-like formed body (G) can reduce the thermal resistance in the thickness direction by making the thickness thin. From the above viewpoint, the upper limit of the thickness of the heat-conductive elastic pressure-sensitive sheet-like formed body (G) is preferably about 2 mm. On the other hand, the lower limit of the thickness of the heat-conductive elastic pressure-sensitive sheet-like formed body (G) is preferably 0.1 mm. Sexy crimping by heat conduction The thickness of the sheet-like molded article (G) is a certain thickness, and it is easy to prevent air from being caught when the heat-conductive pressure-sensitive sheet-like molded body (G) is attached to the heat generating body and the heat sink. As a result, an increase in thermal resistance can be prevented, and the workability of the step of attaching the covering body becomes good and easy.

Further, the heat-conductive elastic pressure-sensitive sheet-like molded body (G) may be formed on one side or both sides of the substrate. The material constituting the substrate is not particularly limited. Specific examples of the substrate include a metal having excellent thermal conductivity such as aluminum, copper, stainless steel, and beryllium copper, and a foil of an alloy, and a polymer having excellent thermal conductivity such as heat-conductive fluorenone. A sheet, a thermally conductive plastic film containing a thermally conductive additive, various nonwoven fabrics, a glass cloth, a honeycomb structure, and the like. Examples of the plastic film include polyimine; polyesters such as polyethylene terephthalate and polyethylene naphthalate; fluororesins such as polytetrafluoroethylene; polyether ketone; and polyether oxime; Polymethylpentene; polyether quinone imine; polyfluorene; polyphenylene sulfide; polyamidoximine; polyester quinone imine; polyamine.

2.2. Effect

According to the method for producing a heat-conductive elastic pressure-sensitive sheet-like formed article (G) of the present invention, the first mixing step and the second mixing step are carried out, even if the amount of the polar group-modified halogenated hydrocarbon fiber (C) is increased. Further, the amount of the conventionally increased amount can be suppressed, and the viscosity of the second mixed composition can be prevented from being excessively increased. Therefore, the productivity of the thermally conductive and pressure-sensitive sheet-like molded article (G) can be suppressed from being lowered. Therefore, the productivity of the heat-conductive elastic pressure-sensitive sheet-like formed body (G) having high flame retardancy can be improved.

3. Use cases

The heat-conductive elastic pressure-sensitive adhesive composition (F) obtained by the method for producing a heat-conductive elastic pressure-sensitive adhesive composition (F) of the present invention, and the heat-conductive elastic pressure-sensitive sheet-like molded body (G) produced by the present invention The heat-conductive elastic pressure-sensitive sheet-like molded body (G) obtained by the method has high thermal conductivity and pressure-sensitive adhesiveness, so that it can be sandwiched between the heat generating body and the heat radiating body, and is used to effectively perform heat generation. The use of heat transfer from the body to the heat sink. In addition, the heat conductive elastic pressure-sensitive adhesive composition (F) and the heat-conductive elastic pressure-sensitive sheet-like molded body (G) can be attached to an electronic component of a heat generating body provided in an electronic device, and can be used as a part of the electronic component. The use examples of the heat conductive pressure-sensitive adhesive composition (F) and the heat-conductive elastic pressure-sensitive sheet-like molded body (G) will be described with reference to Fig. 1 . Fig. 1 is a view for explaining an example of use of a heat conduction-sensitive pressure-sensitive sheet-like formed body (G).

Fig. 1(A) is a perspective view schematically showing a part of an electronic device such as a personal computer. In FIG. 1(A), the substrate 1, the electronic component 2 as a heat generating body provided on the substrate 1, the heat sink 3 as a heat sink, and the heat conduction pressure between the electronic component 2 and the heat sink 3 are shown. Next, the sheet-like formed body (G) 4 is used.

As shown in Fig. 1(A), the heat-conductive elastic pressure-sensitive sheet-like molded body (G) 4 is sandwiched between the electronic component 2 and the heat sink 3 and fixed, and the heat-conductive elastic pressure-sensitive sheet-like formed body (G) is used. The thermal pressure-sensitive adhesive sheet-like molded body (G) 4 can be attached to the electronic component 2 and the heat sink 3 in accordance with the pressure-sensitive adhesive property of 4 . Then, the heat-conductive elastic pressure-sensitive sheet-like molded body (G) 4 has high thermal conductivity, and the heat generated by the electronic component 2 can be efficiently conducted through the heat-conductive elastic pressure-sensitive sheet-like molded body (G) 4 . To the scattered The heat exchanger 3 performs heat dissipation from the heat sink 3.

FIG. 1(B) is a view schematically showing a state in which the NPN transistor 12a and the PNP transistor 12b as the heating elements are mounted on the heat sink 13 as the heat sink, via the heat conduction-sensitive pressure-sensitive sheet-like molded bodies (G) 14 and 14. Oblique view.

As shown in Fig. 1(B), the NPN transistor 12a and the PNP transistor 12b are mounted on the heat sink elastic pressure-bonding sheet-like molded bodies (G) 14 and 14 via the heat sink 13 in accordance with the heat conduction. The pressure-sensitive adhesive sheet (G) 14 has a pressure-sensitive adhesive property, and one of the heat-conductive elastic pressure-sensitive sheet-like formed bodies (G) 14 can be followed by the NPN transistor 12a and the heat sink 13, and the other heat conduction is pressed. The sheet-like formed body (G) 14 can be followed by the PNP transistor 12b and the heat sink 13. Then, the heat-conductive elastic pressure-sensitive sheet-like molded body (G) 14 has high thermal conductivity, and the heat generated by the NPN transistor 12a and the PNP transistor 12b can be separated from the heat-conductive elastic pressure-sensitive sheet-like formed body (G). 14 and 14 are efficiently conducted to the heat sink 13 and radiated from the heat sink 13. At this time, the NPN transistor 12a and the PNP transistor 12b are simultaneously mounted on a heat sink 13 via a heat-conducting pressure-sensitive sheet-like molded body (G) 14, 14 having high thermal conductivity, and can be suppressed in the NPN transistor. 12a produces a temperature difference from the PNP transistor 12b.

FIG. 1(C) is a cross-sectional view schematically showing a state in which two transistors 22 and 22 as heat generating bodies are fixed via a heat conduction-type pressure-sensitive adhesive sheet-like molded body (G) 24.

As shown in Fig. 1(C), the two heat generating bodies 22 and 22 are fixed via the heat-conducting pressure-sensitive sheet-like molded body (G) 24, and the heat-transformable pressure-sensitive sheet-like molded body (G) is thermally bonded. 24 has pressure-sensing adhesion, thermal conductivity The pressure-sensitive adhesive sheet-like formed body (G) 24 can be followed by the two heat generating bodies 22 and 22. Then, the heat-conducting pressure-sensitive sheet-like molded body (G) 24 has high thermal conductivity. When the temperature of one of the two heat generating bodies 22 and 22 is higher than the other, heat is quickly transferred from one side to the other. On the other hand, it is possible to suppress a temperature difference between the two heating elements 22 and 22.

Further, in the example shown in Fig. 1, although the heat conduction type pressure-sensitive sheet-like molded body (G) is used, the heat conduction-type pressure-sensitive adhesive composition (F) may be used in place of the heat conduction type pressure-sensitive adhesive sheet. Shaped body (G). Further, in the above example, the heat sink is used as the heat sink, but the casing of the electronic component or the like may be used as the heat sink. Hereinafter, other examples of use of the heat conductive and sexy pressure-sensitive adhesive composition (F) and the heat-conductive and elastic pressure-sensitive sheet-like molded body (G) of the present invention will be described.

As described above, the thermally conductive pressure-sensitive adhesive composition (F) and the heat-conductive elastic pressure-sensitive sheet-like molded article (G) of the present invention can be used as part of an electronic component included in an electronic device. Specific examples of the electronic device and the electronic component include a component around a heat generating portion of a device having an electroluminescence (EL) or a light emitting diode (LED) light source, a component around a power component such as an automobile, and a fuel cell. , solar cells, batteries, mobile phones, personal digital assistants (PDAs), notebook computers, liquid crystal panels, surface conduction electronic output device displays (SED), plasma display panels (PDP), integrated circuits (IC), etc. A machine or part that has a heat generating part.

In addition, as an example of the method of using the heat conductive and sexy pressure-sensitive adhesive composition (F) and the heat-conductive and elastic pressure-sensitive sheet-like molded body (G) of the present invention for an electronic device, the LED light source is exemplified as an example. The method of use as described below is used. That is, it is directly attached to the LED light source; is sandwiched between the LED light source and the heat dissipating material (heat sink, fan, Peltier element, heat pipe, graphite sheet, etc.); attached to the LED light source Heat-dissipating material (heat sink, fan, Peltier element, heat pipe, graphite sheet, etc.); used as a casing surrounding the LED light source; attached to a casing surrounding the LED light source; method of filling the gap between the LED light source and the casing, etc. . Examples of the use of the LED light source include a backlight device (a television, a mobile phone, a PC, a notebook PC, a PDA, etc.) having a display device of a transmissive liquid crystal panel; a vehicle lamp; industrial lighting; commercial lighting; Residential lighting, etc.

Moreover, as a specific example other than an LED light source, the following are mentioned. It is also a PDP panel; IC heating part; cold cathode tube (CCFL); organic EL light source; inorganic EL light source; high brightness light emitting LED light source; high brightness light emitting organic EL light source; high brightness light emitting inorganic EL light source; CPU; MPU; Components, etc.

In addition, as a method of using the heat conductive and sexy pressure-sensitive adhesive composition (F) and the heat-conductive elastic pressure-sensitive sheet-like molded body (G) of the present invention, a case attached to the device or the like can be mentioned. For example, when it is used in a device such as an automobile, it is attached to the inside of a casing provided in an automobile or the like, attached to an outer side of a casing provided by an automobile, or the like, and is connected to a casing provided in an automobile or the like. The heat generating portion (car navigation system/fuel cell/heat exchanger) and the casing are attached to a heat generating portion (car navigation system/fuel cell/heat exchanger) inside a casing provided in an automobile or the like. Heat sink, etc.

Furthermore, in addition to cars, the same method can be used. The heat conductive and sexy pressure-sensitive adhesive composition (F) of the present invention and the heat-conductive elastic pressure-sensitive sheet-like formed body (G) are used. As the object, for example, a computer; a house; a television; a mobile phone; a vending machine; a refrigerator; a solar cell; a surface conduction type electronic radiation element display (SED); an organic EL display; an inorganic EL display; Inorganic EL illumination; organic EL display; notebook computer; PDA; fuel cell; semiconductor device; electric kettle; washing machine; cleaning and drying machine; optical semiconductor device combining optical semiconductor component and phosphor; various power components; toy machine; Wait.

In addition, the heat-conductive elastic pressure-sensitive adhesive composition (F) and the heat-conductive elastic pressure-sensitive sheet-like molded body (G) of the present invention are not limited to the above-described methods of use, and may be used in other methods depending on the application. For example, it can be used for homogenization of heat such as carpets or electric blankets; as a sealing agent for LED light sources/heat sources; as a sealant for solar battery cases; as a cover for solar cells; for solar cells Use between the back cover and the roof; use on the inside of the insulation inside the vending machine; use with the desiccant or moisture absorbent inside the casing of the organic EL illumination; heat conduction inside the casing of the organic EL illumination a layer and thereon for use with a desiccant or a moisture absorbent; a heat conducting layer, a heat dissipating layer inside the casing of the organic EL illumination, and a desiccant or a moisture absorbent thereon; inside the casing of the organic EL illumination a heat conducting layer, an epoxy heat dissipating layer, and the like, together with a desiccant or a moisture absorbent; for a cooling member for cooling a person or an animal, clothes, towels, sheets, etc., used in contrast to the body Pressurization of a fixing device mounted on an image forming apparatus such as an electrophotographic copying machine or an electrophotographic printer It is used as a pressurizing member of a fixing device mounted on an image forming apparatus such as an electrophotographic copying machine or an electrophotographic printer; and is used as a heat transfer control heat transfer unit for a processing target body of the film forming apparatus; The heat transfer unit for heat flow control of the processing target body of the film forming apparatus; used between the outer layer and the interior of the radioactive material storage container; used in a case of a solar panel that absorbs sunlight; used in CCFL backlighting Between the reflective sheet and the aluminum chassis.

[Examples]

The invention will be described in more detail by way of examples, but the invention is not limited to the examples. In addition, unless otherwise indicated, the "part" or "%" used here is a quality standard.

<viscosity>

The viscosity of the second mixed composition described later was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.). The results are shown in Table 2 and Table 3. When the viscosity of the second mixed composition is too high, the productivity of the heat-conductive elastic pressure-sensitive sheet-like formed body is deteriorated. The result of this evaluation is 20,000 mPa. In the case of s or less, it can be said that the productivity of the heat-conductive elastic pressure-sensitive sheet-like formed body is good. The method of measuring the viscosity is as follows.

The measurement of the viscosity of the B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) was carried out in the order shown below.

(1) 300 ml of a measurement object was measured at a normal temperature, and it was added to a 500 ml container.

(2) It is selected from any of the stirring rotors No. 1, 2, 3, 4, 5, 6, and 7, and is attached to a viscometer.

(3) The container to be measured is placed on a viscometer, and the rotor is sunk into the measurement object in the container. At this time, the groove which becomes the mark of the rotor sinks just toward the liquid interface of the measurement object.

(4) The number of rotations is selected from the group consisting of 20, 10, 4, and 2.

(5) Press the agitator switch to read the value after 1 minute.

(6) The value of the read value multiplied by the coefficient A becomes the viscosity [mPa. s].

Further, the coefficient A is determined by the selected rotor No. and the number of rotations as shown in Table 1 below.

<Flame retardancy>

After the heat conduction-type pressure-sensitive sheet-like formed body was produced as described below, it was prepared to cut into five pieces of a rectangular test piece having a width of 10 mm and a length of 150 mm. Adjust the flow of air and gas of the Bunsen burner to make a cyan flame with a height of about 20 mm. Hold the flame of the lamp at the bottom end of the test piece that is perpendicular (make the test piece and the flame of the lamp intersect about 10 mm) for 10 seconds. Thereafter, the test piece is allowed to leave the flame of the lamp. Thereafter, if the flame of the test piece disappeared, the flame of the lamp was immediately abutted against the test piece, and after holding for 10 seconds, the test piece was allowed to leave the flame of the lamp. The flame of the test piece against the lamp was measured as described above to investigate the presence or absence of the burning drip (dropping liquid). the result Shown in Table 2 and Table 3. In this evaluation, when no dripping liquid was produced, it was said that it was excellent in flame retardance.

<Production of heat-conducting elastic pressure-contact sheet-like formed body>

(Example 1)

First, the first mixing step is carried out as follows. That is, one part of acrylic-modified PTFE fiber (trade name "METABLEN A-3000", manufactured by Mitsubishi Rayon Co., Ltd.) and fatty acid ester of polyol polymer (CHIRABASOL H-818, Sun Chemicals Co., Ltd.) were measured by electronic balance. Co., Ltd., a number average molecular weight: 4000) 5 parts, and the mixture was stirred for 1 minute with a spatula to obtain a first mixed composition.

On the other hand, 100 parts of a monomer mixture containing 94% of 2-ethylhexyl acrylate and 6% of acrylic acid, 0.03 parts of 2,2'-azobisisobutyronitrile and 700 parts of ethyl acetate were added to the reactor, and After uniformly dissolving and substituting nitrogen, the polymerization was carried out at 80 ° C for 6 hours. The polymerization conversion ratio was 97%. The obtained polymer was dried under reduced pressure, and ethyl acetate was evaporated to give a viscous solid (meth) acrylate polymer (A1-1). The (meth) acrylate polymer (A1-1) had a weight average molecular weight (Mw) of 270,000 and a weight average molecular weight (Mw) / number average molecular weight (Mn) of 3.1. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined by colloidal permeation chromatography using tetrahydrofuran as a dissolution liquid in terms of standard polystyrene.

Next, 49 parts of 2-ethylhexyl acrylate (2EHA, manufactured by Wako Pure Chemical Co., Ltd.) and an organic peroxide thermal polymerization initiator (1,6-bis(t-butylperoxy) were measured by electronic balance. Carbonyloxy)hexane (1 minute half-life temperature is 150 ° C)) 1 part, pentaerythritol triacrylate, 1 part of a polyfunctional monomer (Light Acrylate PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) which is a cross-linking agent of pentaerythritol tetraacrylate and pentaerythritol diacrylate in a ratio of 60:35:5, and These were mixed with 50 parts of the above (meth)acrylate polymer (A1-1). In the mixing, a thermostatic chamber (Viscomate 150III, manufactured by Toki Sangyo Co., Ltd.) and a Hubert mixer (manufactured by Kodaira Seisakusho Co., Ltd., ACM-5LVT type, capacity: 5 L) were used. The temperature adjustment of the Hubert's container was set to 23 ° C, and the number of revolutions was set to 5 and stirred for 10 minutes.

Next, 200 parts of aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., BF-083, average particle diameter: 8 μm, BET specific surface area: 0.8 m ² /g) as the thermally conductive filler (B), and the above first mixed composition were measured. 6 parts, 6 parts of expanded graphite powder (trade name "EC-500", manufactured by Ito Graphite Co., Ltd., average particle diameter (D50): 30 μm), and put into the above Hubeite container, and carried out the second In the mixing step, a second mixed composition is obtained. In the second mixing step, the temperature adjustment of the Hubert container was set to 23 ° C, the vacuum was changed to (-0.1 MPaG), and the number of revolutions was set to 5, and the mixture was stirred for 10 minutes.

Next, the second mixed composition was dropped on a release PET film having a thickness of 75 μm, and another release PET film having a thickness of 75 μm was further coated on the second mixed composition. The second mixed composition was sandwiched between the two layers of the release PET film, and the second mixed composition was formed into a sheet shape by adjusting the interval between the two rolls of 650 μm. Thereafter, the laminate was placed in an oven and heated at 150 ° C for 15 minutes to carry out a polymerization step. By the polymerization step, the (meth) acrylate monomer and the polyfunctional single Bulk polymerization, and almost simultaneously using a polyfunctional monomer as a crosslinking agent, the (meth) acrylate polymer (A1-1) and a polymer comprising a structural unit derived from a (meth) acrylate monomer By cross-linking, a heat-conducting pressure-sensitive sheet-like formed body (hereinafter simply referred to as "sheet") (G1) is obtained. Further, when the polymerization conversion ratio of the all monomers was calculated from the amount of residual monomers in the sheet (G1), it was 99.9%.

(Examples 2 to 5, and Comparative Examples 1 to 6)

As shown in Table 2 and Table 3, sheets (G2 to G5) of Examples 2 to 5 and sheets of Comparative Examples 1 to 6 were produced in the same manner as in Example 1 except that the blending of the respective materials was changed. (GC1 to GC6). In Tables 2 and 3, the blending amount of each substance is shown in parts by mass. Further, in Comparative Example 3, a titanate coupling agent (PLENACT TTS, isopropyl triisostearyl titanate, manufactured by Ajinomoto Fine-Techno Co., Ltd.) was used instead of the fatty acid ester of the polyol polymer. Further, Tables 2 and 3 show the presence or absence of the first mixing step. That is, except for Comparative Example 4, the first mixing step was carried out in the same manner as in Example 1, and in Comparative Example 4, the first mixing step was not performed, and the mixed polar group was also denatured in the step corresponding to the second mixing step. The mixed composition obtained by halogenating the hydrocarbon fiber and the fatty acid ester of the polyol polymer is formed into a sheet form to carry out a polymerization step.

As shown in Table 2 and Table 3, the second mixed composition of any of the sheets (G1 to G5) of the examples had a low viscosity and high flame retardancy. That is, it has good productivity and high flame retardancy.

On the other hand, in the sheet (GC1) of Comparative Example 1 in which the amount of the polar-based denatured halogenated hydrocarbon fiber is more than the range specified in the present invention, the second mixed composition has a high viscosity and is inferior in flame retardancy. Also, the fatty acid of the polyol polymer The sheet (GC2) of Comparative Example 2 in which the amount of the ester added was less than the range specified in the present invention had a high viscosity (poor productivity) and poor flame retardancy. Further, in the sheet (GC3) of Comparative Example 3 in which a titanate coupling agent was used instead of the fatty acid ester of the polyol polymer, the viscosity of the second mixed composition was also high (poor productivity), and the flame retardancy was also inferior. Further, the sheet (GC4) of Comparative Example 4 in which the first mixing step was not carried out was the same as the blending amount of each of the materials of Example 1, and the viscosity of the second mixed composition was high (productivity was poor), and the flame retardancy was also difference. Further, the sheet of the comparative example 5 (GC5) in which the polar group-denatured halogenated hydrocarbon fiber was added in an amount lower than the range specified in the present invention was inferior in flame retardancy. Further, the sheet (GC6) of Comparative Example 6 in which the fatty acid ester of the polyol polymer was added in an amount exceeding the range specified in the present invention was also inferior in flame retardancy.

1‧‧‧Substrate

2, 12a, 12b, 22‧‧‧ heating elements

3, 13‧‧‧ heat sink

4,14,24‧‧‧Hot-conducting elastic pressure-contact sheet-like formed body

Claims (3)

A method for producing a thermally conductive and sexy pressure-sensitive adhesive composition (F), comprising the steps of: preparing a polar group-containing denatured halogenated hydrocarbon fiber (C) in an amount of 0.3 part by mass or more and 3.5 parts by mass or less based on the first mixing step; a fatty acid ester (D) of 2 parts by mass or more and 13 parts by mass or less of the first mixed composition; and a second mixing step for producing a (meth) acrylate-containing polymer (A1) and (meth) acrylate monomer 100 parts by mass of the (meth)acrylic resin composition (A) (a1), 50 parts by mass or more and 1000 parts by mass or less of the thermally conductive filler (B), and a second mixed composition of the first mixed composition; In the polymerization step, at least the polymerization reaction of the (meth) acrylate monomer (α1) is carried out in the second mixed composition. A method for producing a heat-conductive elastic pressure-sensitive sheet-like formed article (G), comprising the steps of: preparing a polar group-containing denatured halogenated hydrocarbon fiber (C) in an amount of 0.3 part by mass or more and 3.5 parts by mass or less based on the first mixing step; a first mixed composition of 2 parts by mass or more and 13 parts by mass or less of the fatty acid ester (D) of the polymer; and a second mixing step for producing a (meth) acrylate polymer (A1) and (meth) acrylate 100 parts by mass of the (meth)acrylic resin composition (A) of the monomer (α1), 50 parts by mass or more and 1000 parts by mass or less of the thermally conductive filler (B), and the second mixed composition of the first mixed composition ;as well as a molding step and a polymerization step of forming at least the (meth) acrylate monomer (α1) after molding the second mixed composition into a sheet shape or by molding the second mixed composition into a sheet shape Polymerization. An electronic device comprising a heat-generating body and a heat-conducting pressure-sensitive adhesive composition (F) obtained by the method for producing a heat-conductive elastic pressure-sensitive adhesive composition (F) according to claim 1 And a heat-conducting pressure-sensitive sheet-like molded body (G) obtained by the method of producing the heat-conductive elastic pressure-sensitive sheet-like molded body (G) of the second aspect of the present invention.