WO2012132656A1

WO2012132656A1 - Heat-conductive, pressure-sensitive adhesive composition, heat-conductive, pressure-sensitive adhesive sheet formed body, method for producing each, and electronic component

Info

Publication number: WO2012132656A1
Application number: PCT/JP2012/054289
Authority: WO
Inventors: 拓朗熊本; 明子川村
Original assignee: 日本ゼオン株式会社
Priority date: 2011-03-29
Filing date: 2012-02-22
Publication date: 2012-10-04
Also published as: JPWO2012132656A1

Abstract

Provided are: a heat-conductive, pressure-sensitive adhesive composition that can be provided with superior strength and fire resistance even when formed thinly, and that is characterized by, in a mixed composition containing predetermined amounts of each of a (meth)acrylate resin composition (A), which contains a (meth)acrylic ester polymer (A1) and a (meth)acrylic ester monomer (α1), a heat-conductive filler (B1) having a BET specific surface area of 1.0-10 m²/g inclusive, a phosphate ester (C), a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds, and a polyfunctional epoxy compound (E) having 2-10,000 functional groups inclusive, performing at least a polymerization reaction of the (meth)acrylic ester monomer (α1) and the polyfunctional monomer (D), and a cross-linking reaction of the polymer containing a structural unit derived from the (meth)acrylic ester monomer (α1) and/or the (meth)acrylic ester polymer (A1); a heat-conductive, pressure-sensitive adhesive sheet formed body; a method for producing the composition and body; and an electronic component provided with the heat-conductive, pressure-sensitive adhesive composition or the heat-conductive, pressure-sensitive adhesive sheet formed body.

Description

Thermally conductive pressure-sensitive adhesive composition, thermally conductive and pressure-sensitive adhesive sheet-like molded product, production method thereof, and electronic component

The present invention relates to a heat conductive pressure-sensitive adhesive composition, a heat conductive pressure-sensitive adhesive sheet-like molded article, a production method thereof, and the heat conductive pressure-sensitive adhesive composition or the heat conductive pressure-sensitive adhesive sheet-like molding. The present invention relates to an electronic component having a body.

In recent years, electronic parts such as a plasma display panel (PDP), an integrated circuit (IC) chip and the like have increased in calorific value 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 dissipating heat by attaching a heat sink such as a metal heat sink, a heat radiating plate, or a heat radiating fin to a heat generator provided in an electronic component or the like is employed. In order to efficiently conduct heat conduction from the heat generating body to the heat radiating body, various heat conducting sheets are used. In general, in applications for fixing a heating element and a radiator, a composition having pressure-sensitive adhesiveness in addition to thermal conductivity (hereinafter referred to as “thermally conductive pressure-sensitive adhesive composition”), or A sheet having pressure-sensitive adhesiveness in addition to thermal conductivity (hereinafter referred to as “thermally conductive pressure-sensitive adhesive sheet-like molded product”) is required.

The heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded body are used as one of the purposes for transferring heat from the heat generating element to the heat radiating element. The flexibility etc. which can be performed are calculated | required. As a technique regarding the heat conductive pressure-sensitive-adhesive sheet-like molded body having excellent flexibility, for example, there are a flame-retardant heat dissipation sheet disclosed in Patent Document 1 and a heat conductive sheet disclosed in Patent Document 2.

JP 2006-176640 A JP 2010-132856 A

In order to efficiently transfer heat from the heating element to the heat radiating body using the heat conductive pressure-sensitive adhesive composition or the heat conductive pressure-sensitive adhesive sheet-like molded body, as described above, heat is generated by improving flexibility. It is conceivable to improve the adhesion between the body and the radiator. In order to efficiently transfer heat from the heating element to the radiator using the heat conductive pressure-sensitive adhesive composition and the heat conductive pressure-sensitive adhesive sheet-like molded body, the thermal resistance in the thickness direction must be lowered. Conceivable. In order to reduce the thermal resistance in the thickness direction, in addition to improving the thermal conductivity, it is conceivable to form a thin film.

However, the conventional heat conductive pressure-sensitive adhesive sheet-like molded article has a problem that it is difficult to obtain strength and flame retardancy required as a product when it is molded thinly. In order to improve the flame retardancy of the heat conductive pressure-sensitive adhesive sheet-like molded article, it is known to add additives such as phosphate esters, but it is difficult to form a sheet when using a large amount of these. There was a problem of becoming. As described above, in the conventional technique, it is difficult to provide various performances required for the heat conductive pressure-sensitive adhesive sheet-like molded body in a balanced manner.

Therefore, the present invention provides a thermally conductive pressure-sensitive adhesive composition and a thermally conductive pressure-sensitive adhesive sheet-like molded body that can be provided with excellent strength and flame retardancy even when molded thinly, and a method for producing these, It is an object of the present invention to provide an electronic component comprising the thermally conductive pressure-sensitive adhesive composition or the thermally conductive pressure-sensitive adhesive sheet-like molded body.

In the first aspect of the present invention, 100 mass of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1). 90 parts by mass or more and 1200 parts by mass or less of the thermally conductive filler (B1) having a BET specific surface area of 1.0 m ² / g or more and 10 m ² / g or less, and 45 parts by mass or more of the phosphate ester (C). 190 parts by mass or less, 0.2 to 15 parts by mass of a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds, and a polyfunctional epoxy compound (E) having 2 to 10,000 functional groups ) In a mixed composition containing 0.05 parts by mass or more and 15 parts by mass or less, and a polymerization reaction of the (meth) acrylic acid ester monomer (α1) and the polyfunctional monomer (D), (Meth) acrylic acid ester polymer (A ) And / or (meth) and the cross-linking reaction of acrylic acid ester monomer ([alpha] 1) polymerization comprising a structural unit derived from material comprising been made at least a thermally conductive pressure-sensitive adhesive composition (F).

The definitions of the words used in this specification are described below. “(Meth) acryl” means “acryl and / or methacryl”. The “BET specific surface area” means that measured by the following method. First, a mixed gas of nitrogen and helium is introduced into a BET specific surface area measuring apparatus, and a sample cell containing a sample (an object to be measured for BET specific surface area) is immersed in liquid nitrogen to adsorb nitrogen gas to the sample surface. After reaching adsorption equilibrium, the sample cell is placed in a water bath and warmed to room temperature, and nitrogen adhering to the sample is desorbed. Since the mixing ratio of the gas before and after passing through the sample cell changes during the adsorption and desorption of nitrogen gas, this change is detected by a thermal conductivity detector (TCD) using a gas with a constant mixing ratio of nitrogen and helium as a control. Then, the adsorption amount and desorption amount of nitrogen gas are obtained. Before the measurement, a unit amount of nitrogen gas is introduced into the apparatus for calibration, and the surface area value corresponding to the value detected by TCD is obtained to obtain the surface area of the sample. Further, the BET specific surface area can be obtained by dividing the surface area by the mass of the sample. The “thermally conductive filler” is added to improve the thermal conductivity of the thermally conductive pressure-sensitive adhesive composition (F) or the thermally conductive pressure-sensitive adhesive sheet-like molded body (G) described later. Means a filler that can. In addition, “polymerization reaction of (meth) acrylic acid ester monomer (α1) and polyfunctional monomer (D)” means (meth) acrylic acid ester monomer (α1) and polyfunctional monomer Among the copolymerization reaction with the body (D), the polymerization reaction of the (meth) acrylate monomer (α1), and the polymerization reaction of the polyfunctional monomer (D), one or more polymerization reactions are performed. means. In addition, “(meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer (α1) -derived polymer cross-linking reaction” means (meth) acrylic acid ester Cross-linking reaction between polymers (A1), cross-linking reaction between polymers containing structural units derived from (meth) acrylate monomer (α1), and (meth) acrylate polymer (A1) and ( Among crosslinking reactions with a polymer containing a structural unit derived from a (meth) acrylate monomer (α1), it means one or a plurality of crosslinking reactions.

In the heat conductive pressure-sensitive adhesive composition (F) of the first aspect of the present invention, the (meth) acrylic resin composition (A) is a monomer unit having an organic acid group or a monomer having an organic acid group It is preferable to contain. Further, BET specific surface area of 1.0 m ² / g or more ^{10 m} 2 / g or less thermally conductive filler is (B1) is, BET specific surface area is less aluminum oxide 1.0 m ² / g or more ^{10 m} 2 / g It is preferable.

In the heat conductive pressure-sensitive adhesive composition (F) of the first aspect of the present invention, the mixed composition further contains 200 heat conductive filler (B2) having a BET specific surface area of less than 1.0 m ² / g. It is preferable to contain at least 800 parts by mass. Moreover, it is preferable that the said heat conductive filler (B2) is an aluminum hydroxide whose BET specific surface area is less than 1.0 m < ² > / g.

In the second aspect of the present invention, 100 mass of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1). 90 parts by mass or more and 1200 parts by mass or less of the thermally conductive filler (B1) having a BET specific surface area of 1.0 m ² / g or more and 10 m ² / g or less, and 45 parts by mass or more of the phosphate ester (C). 190 parts by mass or less, 0.2 to 15 parts by mass of a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds, and a polyfunctional epoxy compound (E) having 2 to 10,000 functional groups ) In the form of a sheet, or while forming the mixture composition into a sheet, the (meth) acrylic acid ester monomer (α1) ) And multifunctional monomers ( ) And a crosslinking reaction of a polymer containing a structural unit derived from the (meth) acrylate polymer (A1) and / or the (meth) acrylate monomer (α1). A heat conductive pressure-sensitive adhesive sheet-like molded body (G).

In the thermally conductive pressure-sensitive adhesive sheet-like molded product (G) of the second aspect of the present invention, the (meth) acrylic resin composition (A) is a monomer unit having an organic acid group or a single unit having an organic acid group. It is preferable to include a monomer. Further, BET specific surface area of 1.0 m ² / g or more ^{10 m} 2 / g or less thermally conductive filler is (B1) is, BET specific surface area is less aluminum oxide 1.0 m ² / g or more ^{10 m} 2 / g It is preferable.

In the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the second aspect of the present invention, the mixed composition further has a BET specific surface area of less than 1.0 m ² / g, a heat conductive filler (B2). It is preferable that 200 mass parts or more and 800 mass parts or less are included. Moreover, it is preferable that the said heat conductive filler (B2) is an aluminum hydroxide whose BET specific surface area is less than 1.0 m < ² > / g.

In the third aspect of the present invention, 100 mass of (meth) acrylic resin composition (A) containing (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1). 90 parts by mass or more and 1200 parts by mass or less of the thermally conductive filler (B1) having a BET specific surface area of 1.0 m ² / g or more and 10 m ² / g or less, and 45 parts by mass or more of the phosphate ester (C). 190 parts by mass or less, 0.2 to 15 parts by mass of a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds, and a polyfunctional epoxy compound (E) having 2 to 10,000 functional groups ) In an amount of 0.05 parts by mass or more and 15 parts by mass or less, and in the mixture composition, the (meth) acrylate monomer (α1) and the multifunctional monomer Polymerization reaction of the monomer (D) A step of performing at least a crosslinking reaction of a polymer containing a structural unit derived from the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer (α1). It is a manufacturing method of adhesive composition (F).

In the method for producing a heat conductive pressure-sensitive adhesive composition (F) of the third aspect of the present invention, a heat conductive filler (B1) having a BET specific surface area of 1.0 m ² / g or more and 10 m ² / g or less is provided. The aluminum oxide preferably has a BET specific surface area of 1.0 m ² / g or more and 10 m ² / g or less. Further, the mixed composition preferably further contains 200 to 800 parts by mass of a thermally conductive filler (B2) having a BET specific surface area of less than 1.0 m ² / g. ) Is preferably aluminum hydroxide having a BET specific surface area of less than 1.0 m ² / g.

The 4th aspect of this invention is 100 masses of (meth) acrylic-ester resin compositions (A) containing the (meth) acrylic-ester polymer (A1) and the (meth) acrylic-ester monomer ((alpha) 1). 90 parts by mass or more and 1200 parts by mass or less of the thermally conductive filler (B1) having a BET specific surface area of 1.0 m ² / g or more and 10 m ² / g or less, and 45 parts by mass or more of the phosphate ester (C). 190 parts by mass or less, 0.2 to 15 parts by mass of a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds, and a polyfunctional epoxy compound (E) having 2 to 10,000 functional groups ) 0.05 parts by mass or more and 15 parts by mass or less, and after forming the mixed composition into a sheet, or while forming the mixed composition into a sheet, (Meth) acrylic acid ester Polymerization reaction of monomer (α1) and polyfunctional monomer (D), and structural unit derived from (meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer (α1) It is a manufacturing method of a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) including the process of performing at least the crosslinking reaction of the polymer containing this.

In the manufacturing method of the fourth aspect of the heat-conductive and pressure-sensitive adhesive sheet-like molded article of the present invention (G), the thermally conductive filler has a BET specific surface area of not more than 1.0 m ² / g or more ^10m 2 / g (B1 ) Is preferably an aluminum oxide having a BET specific surface area of 1.0 m ² / g or more and 10 m ² / g or less. Further, the mixed composition preferably further contains 200 to 800 parts by mass of a thermally conductive filler (B2) having a BET specific surface area of less than 1.0 m ² / g. ) Is preferably aluminum hydroxide having a BET specific surface area of less than 1.0 m ² / g.

According to a fifth aspect of the present invention, there is provided a heat radiator and the heat conductive pressure-sensitive adhesive composition (F) of the first aspect of the present invention bonded to the heat radiator, or the heat radiator and the heat radiator. An electronic component comprising the thermally conductive pressure-sensitive adhesive sheet-like molded body (G) according to the second aspect of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, even if it shape | molds thinly, the heat conductive pressure-sensitive-adhesive composition which can be provided with the outstanding intensity | strength and flame retardance, a heat conductive pressure-sensitive-adhesive sheet-like molded object, and these manufacturing methods And an electronic component provided with the heat conductive pressure-sensitive adhesive composition or the heat conductive pressure-sensitive adhesive sheet-like molded article.

1. Thermally conductive pressure-sensitive adhesive composition (F), thermally conductive pressure-sensitive adhesive sheet-like molded body (G)
The heat conductive pressure-sensitive adhesive composition (F) of the present invention comprises a (meth) acrylic resin containing a (meth) acrylic acid ester polymer (A1) and a (meth) acrylic acid ester monomer mixture (α1). The composition (A) and a thermally conductive filler (B1) having a BET specific surface area of 1.0 m ² / g or more and 10 m ² / g or less (hereinafter, simply referred to as “thermally conductive filler (B1)”). ), A phosphate ester (C), a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds (hereinafter sometimes simply referred to as “polyfunctional monomer (D)”). And a polyfunctional epoxy compound (E) having a functional group of 2 or more and 10,000 or less (hereinafter sometimes simply referred to as “polyfunctional epoxy compound (E)”), (meth) acrylic acid Ester monomer (α1) and multifunctional monomer At least one of a copolymerization reaction with (D), a polymerization reaction of the (meth) acrylic acid ester monomer (α1), and a polymerization reaction of the polyfunctional monomer (D), and ( Cross-linking reaction between (meth) acrylic acid ester polymers (A1), cross-linking reaction between polymers containing structural units derived from (meth) acrylic acid ester monomers (α1), and (meth) acrylic acid ester polymers At least any cross-linking reaction among the cross-linking reaction between (A1) and the polymer containing the structural unit derived from the (meth) acrylic acid ester monomer (α1) is performed.

Moreover, the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention is (meth) acrylic acid after shape | molding the said mixed composition in a sheet form, or shape | molding the said mixed composition in a sheet form. Copolymerization reaction of ester monomer (α1) and polyfunctional monomer (D), polymerization reaction of (meth) acrylic acid ester monomer (α1), and polyfunctional monomer (D) A polymer containing a structural unit derived from a (meth) acrylate monomer (α1), a crosslinking reaction between (meth) acrylate polymers (A1), and Cross-linking reaction between each other and at least one of cross-linking reaction between the (meth) acrylic acid ester polymer (A1) and the cross-linking reaction between the polymer containing the structural unit derived from the (meth) acrylic acid ester monomer (α1). The reaction is performed at least It become one.

The materials constituting the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) will be described below.

<(Meth) acrylic resin composition (A)>
The (meth) acrylic resin composition (A) used in the present invention contains a (meth) acrylic acid ester polymer (A1) and a (meth) acrylic acid ester monomer (α1). In addition, as mentioned above, when obtaining a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G), (meth) acrylic acid ester monomer ((alpha) 1) and Polymerization reaction of polyfunctional monomer (D) and crosslinking of polymer containing structural unit derived from (meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer (α1) At least the reaction takes place. By performing the polymerization reaction and the crosslinking reaction, the polymer containing the structural unit derived from the (meth) acrylate monomer (α1) is mixed with the component of the (meth) acrylate polymer (A1) and / or Or partly combined. Moreover, the crosslinking reaction by the polyfunctional monomer (D) mentioned later and the crosslinking reaction by the polyfunctional epoxy compound (E) mentioned later depending on the case may occur.

In this invention, the usage-amount of an acrylic ester polymer (A1) and the (meth) acrylic ester monomer ((alpha) 1) is (meth) with respect to 100 mass% of (meth) acrylic resin compositions (A). The acrylate polymer (A1) is preferably 5% by mass or more and 40% by mass or less, and the (meth) acrylic acid ester monomer (α1) is preferably 60% by mass or more and 95% by mass or less. By setting the content ratio of the (meth) acrylic acid ester monomer (α1) in the above range, molding of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). It becomes easy to do.

((Meth) acrylic acid ester polymer (A1))
The (meth) acrylic acid ester polymer (A1) that can be used in the present invention is not particularly limited, but the (meth) acrylic acid ester monomer that forms a homopolymer having a glass transition temperature of −20 ° C. or lower. It is preferable to contain the unit (a1) and the monomer unit (a2) having an organic acid group.

The (meth) acrylic acid ester monomer (a1m) which gives the unit (a1) of the (meth) acrylic acid ester monomer is not particularly limited. For example, ethyl acrylate (the glass transition temperature of the homopolymer is -24 ° C), n-propyl acrylate (-37 ° C), n-butyl acrylate (-54 ° C), sec-butyl acrylate (-22 ° C), n-heptyl acrylate (- 60 ° C), n-hexyl acrylate (-61 ° C), n-octyl acrylate (-65 ° C), 2-ethylhexyl acrylate (-50 ° C), 2-methoxyethyl acrylate (-50) ° C), 3-methoxypropyl acrylate (-75 ° C), 3-methoxybutyl acrylate (-56 ° C), ethoxymethyl acrylate (-50 ° C), n-octyl methacrylate (- 5 ° C.), and the like methacrylic acid n- decyl (the -49 ° C.). Among them, n-butyl acrylate, 2-ethylhexyl acrylate, and 2-methoxyethyl acrylate are preferable, n-butyl acrylate and 2-ethylhexyl acrylate are more preferable, and 2-ethylhexyl acrylate is more preferable.

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

In the (meth) acrylic acid ester monomer (a1m), the monomer unit (a1) derived therefrom is preferably 80% by mass or more and 99.9% by mass in the (meth) acrylic acid ester polymer (A1). In the following, it is preferable to use it in the polymerization in such an amount that it is 85 mass% or more and 99.5 mass% or less. When the amount of the (meth) acrylic acid ester monomer (a1m) is within the above range, the viscosity of the polymerization system at the time of polymerization can be easily maintained within an appropriate range.

Next, the monomer unit (a2) having an organic acid group will be described. The monomer (a2m) that gives the monomer unit (a2) having an organic acid group is not particularly limited, but representative examples thereof include organic acid groups such as a carboxyl group, an acid anhydride group, and a sulfonic acid group. The monomer which has can be mentioned. 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, for example, α, β-ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and α, β such as itaconic acid, maleic acid, and fumaric acid. In addition to β-ethylenically unsaturated polyvalent carboxylic acid, α, β-ethylenically unsaturated polyvalent carboxylic acid partial esters such as monomethyl itaconate, monobutyl maleate and monopropyl fumarate can be exemplified. 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 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 a monomer having acrylic acid or methacrylic acid is particularly preferable. . These monomers are industrially inexpensive and can be easily obtained, have good copolymerizability with other monomer components, and are preferable in terms of productivity. In addition, a monomer (a2m) may be used individually by 1 type, and may use 2 or more types together.

In the monomer (a2m) having an organic acid group, the monomer unit (a2) derived therefrom is 0.1% by mass or more and 20% by mass or less in the (meth) acrylic acid ester polymer (A1), preferably It is preferable to use it for the polymerization in such an amount that it is 0.5 to 15% by mass. When the amount of the monomer (a2m) having an organic acid group is within the above range, it is easy to keep the viscosity of the polymerization system at the time of polymerization within an appropriate range, and a (meth) acrylic acid ester polymer It becomes possible to form an appropriate amount of a crosslinked structure between (A1) and a polyfunctional epoxy compound (E) described later.

The monomer unit (a2) having an organic acid group is introduced into the (meth) acrylic acid ester polymer (A1) by polymerization of the monomer (a2m) having an organic acid group as described above. Although it is simple and preferable to perform, an organic acid group may be introduced by a known polymer reaction after the (meth) acrylic acid ester polymer (A1) is formed.

Further, the (meth) acrylic acid ester polymer (A1) may contain a monomer unit (a3) derived from a monomer (a3m) having a functional group other than an organic acid group.

Examples of the functional group other than the organic acid group include a hydroxyl group, an amino group, an amide group, an epoxy group, and a mercapto group.

Examples of the monomer having a hydroxyl group include (meth) acrylic acid hydroxyalkyl esters such as (meth) acrylic acid 2-hydroxyethyl and (meth) acrylic acid 3-hydroxypropyl.

Examples of the monomer having 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) having a functional group other than the organic acid group, one type may be used alone, or two or more types may be used in combination.

In the monomer (a3m) having a functional group other than these organic acid groups, the monomer unit (a3) derived therefrom is 10% by mass or less in the (meth) acrylate polymer (A1). It is preferable to use it for polymerization in such an amount. By using the monomer (a3m) of 10% by mass or less, it becomes easy to keep the viscosity of the polymerization system during polymerization in an appropriate range.

The (meth) acrylic acid ester polymer (A1) has a (meth) acrylic acid ester monomer unit (a1) that forms a homopolymer having a glass transition temperature of −20 ° C. or lower, and an organic acid group. In addition to the monomer unit (a2) and the monomer unit (a3) having a functional group other than an organic acid group, a monomer derived from the monomer (a4m) copolymerizable with the above-described monomer. The monomer unit (a4) 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 mass or less, more preferably 5% by mass or less, based on the acrylate polymer (A1).

The monomer (a4m) is not particularly limited, and specific examples thereof include (meth) acrylate monomers other than the (meth) acrylate monomer (a1m), α, β-ethylenic monomers. Saturated polycarboxylic acid complete ester, alkenyl aromatic monomer, conjugated diene monomer, non-conjugated diene monomer, vinyl cyanide monomer, carboxylic acid unsaturated alcohol ester, olefin monomer, etc. Can be mentioned.

Specific examples of the (meth) acrylate monomer other than the (meth) acrylate monomer (a1m) include methyl acrylate (homopolymer having a glass transition temperature of 10 ° C.), methyl methacrylate. (105 ° C.), ethyl methacrylate (63 ° C.), n-propyl methacrylate (25 ° C.), n-butyl methacrylate (20 ° C.), and the like.

Specific examples of the α, β-ethylenically unsaturated polyvalent carboxylic acid complete ester include dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate and the like.

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 (synonymous with isoprene), 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene. 2-chloro-1,3-butadiene, cyclopentadiene and the like.

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 measured by gel permeation chromatography (GPC method) and is in the range of 100,000 to 1,000,000 in terms of standard polystyrene. It is more preferable that it is in the range of 200,000 or more and 500,000 or less.

The (meth) acrylic acid ester polymer (A1) is a (meth) acrylic acid ester monomer (a1m), a monomer having an organic acid group, which forms a homopolymer having a glass transition temperature of −20 ° C. or lower. (A2m), a monomer containing a functional group other than an organic acid group (a3m) used as required, and a monomer copolymerizable with these monomers used as needed ( a4m) can be obtained particularly preferably by copolymerization.

The polymerization method is not particularly limited, and any of solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and the like may be used. Solution polymerization is preferred, and among them, solution polymerization using a carboxylic acid ester such as ethyl acetate or ethyl lactate or an aromatic solvent such as benzene, toluene or xylene as the polymerization solvent 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 method for initiating the polymerization is not particularly limited, but it is preferable to use a thermal polymerization initiator as the polymerization initiator. The thermal polymerization initiator is not particularly limited, and may be either a peroxide or an azo compound.

Peroxide polymerization initiators include hydroperoxides such as t-butyl hydroperoxide, peroxides such as benzoyl peroxide and cyclohexanone peroxide, and persulfates such as potassium persulfate, sodium persulfate and ammonium persulfate. Can be mentioned. These peroxides can also be used as a redox catalyst in appropriate combination with a reducing agent.

As azo compound polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile) And so on.

Although the usage-amount of a polymerization initiator is not specifically limited, It is preferable that it is the range of 0.01 to 50 mass parts with respect to 100 mass parts of monomers.

Other polymerization conditions (polymerization temperature, pressure, stirring conditions, etc.) of these monomers are not particularly limited.

After completion of the polymerization reaction, the obtained polymer is separated from the polymerization medium if necessary. The separation method is not particularly limited. For example, 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 weight average molecular weight of the (meth) acrylic acid ester polymer (A1) can be controlled by appropriately adjusting the amount of the polymerization initiator used in the polymerization and the amount of the chain transfer agent.

((Meth) acrylic acid ester monomer (α1))
The (meth) acrylate monomer (α1) is not particularly limited as long as it contains a (meth) acrylate monomer, but a homopolymer having a glass transition temperature of −20 ° C. or lower is molded. It is preferable to contain the (meth) acrylic acid ester monomer (a5m).

As an example of the (meth) acrylate monomer (a5m) for forming a homopolymer having a glass transition temperature of −20 ° C. or lower, it is used for the synthesis of a (meth) acrylate polymer (A1) (meth) ) The same (meth) acrylate monomer as the acrylate monomer (a1m) can be mentioned. A (meth) acrylic acid ester monomer (a5m) may be used individually by 1 type, and may use 2 or more types together.

The ratio of the (meth) acrylate monomer (a5m) in the (meth) acrylate monomer (α1) is preferably 50% by mass to 100% by mass, more preferably 75% by mass to 100% by mass. It is as follows. By making the ratio of the (meth) acrylic acid ester monomer (a5m) in the (meth) acrylic acid ester monomer (α1) in the above range, the heat conductive pressure-sensitive adhesive having excellent pressure-sensitive adhesiveness and flexibility. It becomes easy to obtain the agent composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G).

The (meth) acrylic acid ester monomer (α1) may be a mixture of a (meth) acrylic acid ester monomer (a5m) and a monomer copolymerizable therewith.

Particularly preferred (meth) acrylate monomer (α1) is (meth) acrylate monomer (a5m) that forms a homopolymer having a glass transition temperature of −20 ° C. or less, and a copolymer thereof. It contains a monomer (a6m) having a polymerizable organic acid group.

Examples of the monomer (a6m) include monomers having an organic acid group similar to those exemplified as the monomer (a2m) used for the synthesis of the (meth) acrylic acid ester polymer (A1). be able to. A monomer (a6m) may be used individually by 1 type, and may use 2 or more types together.

The ratio of the monomer (a6m) in the (meth) acrylic acid ester monomer (α1) is preferably 30% by mass or less, and more preferably 10% by mass or less. By setting the ratio of the monomer (a6m) in the (meth) acrylic acid ester monomer (α1) to the above range, the heat conductive pressure-sensitive adhesive composition (F) excellent in pressure-sensitive adhesiveness and flexibility. And it becomes easy to obtain a heat conductive pressure-sensitive-adhesive sheet-like molded object (G).

The (meth) acrylic acid ester monomer (α1), in addition to the (meth) acrylic acid ester monomer (a5m) and the monomer (a6m) having an organic acid group that can be optionally copolymerized, It is good also as a mixture with the monomer (a7m) which can be copolymerized with these. The ratio of the monomer (a7m) in the (meth) acrylic acid ester monomer (α1) is preferably 20% by mass or less, and more preferably 10% by mass or less.

Examples of the monomer (a7m) include the monomer (a3m) used for the synthesis of the (meth) acrylic acid ester polymer (A1) and the same amount as those exemplified as the monomer (a4m). The body can be mentioned. A monomer (a7m) may be used individually by 1 type, and may use 2 or more types together.

<Polymerization initiator>
When obtaining the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G), the (meth) acrylic acid ester monomer (α1) and a polyfunctional monomer described below are used. Body (D) polymerizes. In order to accelerate the polymerization, it is preferable to use a polymerization initiator.

Examples of the polymerization initiator that can be used in the present invention include a photopolymerization initiator, an azo thermal polymerization initiator, and an organic peroxide thermal polymerization initiator. From the viewpoint of imparting excellent adhesiveness to the obtained heat conductive pressure-sensitive adhesive composition (F) and heat conductive pressure-sensitive adhesive sheet-like molded body (G), an organic peroxide thermal polymerization initiator is used. It is preferable to use it.

As the photopolymerization initiator, various known photopolymerization initiators can be used. Of these, acylphosphine oxide compounds are preferred. Preferred examples of the acylphosphine oxide compound that is a photopolymerization initiator include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

As the azo-based thermal polymerization initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile) ) And the like.

Examples of the organic peroxide thermal polymerization initiator include hydroperoxides such as t-butyl hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, 1,6-bis (t-butylperoxycarbonyloxy) hexane, 1,1-bis ( and a peroxide such as t-butylperoxy) -3,3,5-trimethylcyclohexanone. However, those that do not release volatile substances that cause odor during thermal decomposition are preferred. Among organic peroxide thermal polymerization initiators, those having a 1-minute half-life temperature of 100 ° C. or more and 170 ° C. or less are preferable.

The amount of the polymerization initiator used is preferably 0.01 parts by mass or more and 10 parts by mass or less, and 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic resin composition (A). It is more preferable that it is 0.3 mass part or more and 1 mass part or less. By making the usage-amount of a polymerization initiator into the said range, it becomes easy to make the polymerization conversion rate of (meth) acrylic acid ester monomer mixture ((alpha) 1) into an appropriate range, and a heat conductive pressure sensitive adhesive composition (F). And it becomes easy to prevent the monomer odor from remaining in the heat conductive pressure-sensitive adhesive sheet-like molded product (G). The polymerization conversion rate of the (meth) acrylic acid ester monomer (α1) is preferably 95% by mass or more. If the polymerization conversion rate of the (meth) acrylic acid ester monomer (α1) is 95% by mass or more, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G). It is easy to prevent the monomer odor from remaining on the surface. Moreover, by making the usage-amount of a polymerization initiator into the said range, the progress of polymerization reaction is induced excessively by adding a polymerization initiator, As a result, a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) However, it does not become a smooth sheet, and it is easy to prevent a situation in which material destruction occurs.

<Polyfunctional monomer (D)>
A polyfunctional monomer (D) is used for the heat conductive pressure-sensitive-adhesive composition (F) and heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention. As the polyfunctional monomer (D), one that can be copolymerized with the monomer contained in the (meth) acrylic acid ester monomer (α1) is used. The polyfunctional monomer (D) preferably has a plurality of polymerizable unsaturated bonds, and preferably has the unsaturated bond at the terminal. By using such a polyfunctional monomer (D), intramolecular and / or intermolecular crosslinking is introduced into the copolymer, and the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive are introduced. The cohesive force as a pressure-sensitive adhesive of the adhesive sheet-like molded body (G) can be increased.

Examples of the polyfunctional monomer (D) 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, Polyfunctional (meth) acrylates such as ditrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 2,4-bis (to Other substituted triazines, such as chloromethyl) -6-p-methoxystyrene-5-triazine, etc. monoethylenically unsaturated aromatic ketones such as 4-acryloxy benzophenone can be used. Among these, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate are preferable. A polyfunctional monomer (D) may be used individually by 1 type, and may use 2 or more types together.

The amount of the polyfunctional monomer (D) used in the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is 100 masses of the acrylic resin composition (A). Parts are 0.2 parts by mass or more and 15 parts by mass or less, preferably 0.5 parts by mass or more and 5 parts by mass or less, and more preferably 0.7 parts by mass or more and 2 parts by mass or less. By making the usage-amount of a polyfunctional monomer (D) into the said range, it is a pressure sensitive adhesive to a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure sensitive adhesive sheet-like molded object (G). It becomes easy to achieve both strength and adhesiveness.

<Thermal conductive filler (B1)>
A heat conductive filler (B1) is used for the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G) of the present invention. A heat conductive filler (B1) is a filler which can improve the heat conductivity of a heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) by adding. Yes, the BET specific surface area is 1.0 m ² / g or more and 10 m ² / g or less. BET specific surface area of the thermally conductive filler (B1), it is preferable, 1.0 m ² / g or more 3.0 m ² / g or less or less 1.0 m ² / g or more 5.0 m ² / g Is more preferable. By keeping the BET specific surface area of the heat conductive filler (B1) in the above range, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet are maintained while maintaining the improvement in the sol viscosity during molding. It becomes easy to achieve both strength and adhesion to the shaped molded body (G).

Specific examples of the thermally conductive filler (B1) that can be used in the present invention include aluminum hydroxide, gallium hydroxide, indium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, and boric acid. Examples thereof include zinc hydrate, kaolin clay, calcium aluminate hydrate, calcium carbonate, aluminum carbonate, dawsonite, aluminum oxide (alumina), magnesium oxide, zinc oxide, boron nitride, aluminum nitride, and silica. Among these, calcium carbonate, aluminum hydroxide, and aluminum oxide are preferable because they are easily available, chemically stable, and can be added in a large amount, and aluminum oxide is particularly preferable. One type of heat conductive filler (B1) may be used alone, or two or more types may be used in combination.

The amount of the heat conductive filler (B1) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is (meth) acrylic resin composition (A) 100. It is 90 to 1200 parts by mass, preferably 100 to 1000 parts by mass, and more preferably 200 to 800 parts by mass with respect to parts by mass. When the content of the heat conductive filler (B1) exceeds the above range, the heat conductive pressure sensitive adhesive composition (F) and the mixed composition that becomes the basis of the heat conductive pressure sensitive adhesive sheet-like molded body (G) Viscosity increases and it becomes difficult to form the heat conductive pressure-sensitive adhesive composition (E) and the heat conductive pressure-sensitive adhesive sheet-like molded body (F), or the heat conductive pressure-sensitive adhesive composition (F) and the heat conduction There is a possibility that the hardness of the pressure-sensitive adhesive sheet-like molded body (G) increases and the shape followability decreases. On the other hand, when the content of the heat conductive filler (B1) is less than the above range, the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet are obtained by using the heat conductive filler (B1). There is a possibility that the effect of improving the thermal conductivity of the shaped molded body (G) becomes insufficient.

In addition, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention have a BET specific surface area described later having a BET specific surface area of less than 1.0 m ² / g. The conductive filler (B2) (hereinafter sometimes simply referred to as “thermal conductive filler (B2)”) may be used in combination.

<Thermal conductive filler (B2)>
The heat conductive filler (B2) has a BET specific surface area of less than 1.0 m ² / g. As the heat conductive filler (B2), the same materials can be used except that the BET specific surface area is different from that of the heat conductive filler (B1), but aluminum hydroxide is particularly preferable. By using the thermally conductive filler (B2) in combination with the thermally conductive filler (B1), it becomes possible to mix a large amount of filler in the mixed composition while suppressing improvement in the sol viscosity of the mixed composition.

The amount of the heat conductive filler (B2) contained in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is (meth) acrylic resin composition (A) 100. It is preferable that it is 200 to 800 mass parts with respect to a mass part, and it is more preferable that it is 300 to 600 mass parts. By making content of a heat conductive filler (B2) below the upper limit of the said range, it becomes the element | base of a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure sensitive adhesive sheet-like molded object (G). When the viscosity of the mixed composition increases, it becomes difficult to mold the heat conductive pressure-sensitive adhesive composition (E) and the heat conductive pressure-sensitive adhesive sheet-like molded body (F), or the heat conductive pressure-sensitive adhesive composition (F ) And the heat-conductive pressure-sensitive adhesive sheet-like molded body (G), it is easy to prevent the shape followability from being decreased due to an increase in hardness. On the other hand, when the content of the heat conductive filler (B2) is not less than the lower limit of the above range, the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive are obtained by using the heat conductive filler (B2). It becomes easy to exhibit the effect which improves the heat conductivity of an adhesive sheet-like molded object (G).

<Phosphate ester (C)>
Phosphate ester (C) is used for the heat conductive pressure-sensitive-adhesive composition (F) and heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention. By using phosphate ester (C), the flame retardancy of the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) can be improved. Further, when a large amount of the phosphate ester (C) is used, it becomes difficult to form the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G). By using the ester (C) and the heat conductive filler (B1) in combination, the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet can be used even if the amount of the phosphate ester (C) is suppressed. The flame retardancy of the shaped molded body (G) can be improved, and the moldability is easily compatible.

The phosphate ester (C) used in the present invention preferably has a viscosity at 25 ° C. of 3000 mPa · s or more. By making the viscosity of the phosphoric ester (C) within the above range, it is prevented that the moldability of the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is deteriorated. It becomes easy to do. In the present invention, the “viscosity” of the phosphate ester means the viscosity measured by the method described below.

(Method for measuring viscosity of phosphate ester)
The viscosity of the phosphate ester is measured by the procedure shown below using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.).
(1) Weigh 300 ml of phosphate ester in a normal temperature environment and place it in a 500 ml container.
(2) Stirring rotor No. Select one from 1, 2, 3, 4, 5, 6, and 7 and attach to the viscometer.
(3) The container containing the phosphate ester is placed on the viscometer, and the rotor is submerged in the condensed phosphate ester in the container. At this time, the dent which becomes a mark of a rotor sinks so that it may just come to the liquid interface of phosphate ester.
(4) The rotation speed is selected from 20, 10, 4, and 2.
(5) Turn on the stirring switch and read the value after 1 minute.
(6) The value obtained by multiplying the read numerical value by the coefficient A is the viscosity [mPa · s].
The coefficient A is the selected rotor No. as shown in Table 1 below. And the number of revolutions.

Further, it is preferable that the phosphate ester (C) used in the present invention is always liquid in a temperature range of 15 ° C. or more and 100 ° C. or less under atmospheric pressure. If the phosphate ester (C) is liquid when mixed, the workability is good and the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is formed. It becomes easy. When molding the heat conductive pressure-sensitive adhesive composition (F) or the heat conductive pressure-sensitive adhesive sheet-like molded product (G) containing the phosphoric ester (C), heat is applied in an environment of 15 ° C. or higher and 100 ° C. or lower. It is preferable to mix each substance which comprises a conductive pressure sensitive adhesive composition (F) or a heat conductive pressure sensitive adhesive sheet-like molded object (G). By setting the mixing temperature within the above range, the glass transition temperature of the acrylic resin composition (A) is set to be higher than that, and the volatilization or polymerization reaction of the monomers and the like contained in the acrylic resin composition (A) starts. Therefore, environmental performance and workability can be improved.

In the present invention, either a condensed phosphate ester or a non-condensed phosphate ester can be used as the phosphate ester (C). As used herein, “condensed phosphate ester” means one having a plurality of phosphate ester moieties in one molecule, and “non-condensed phosphate ester” means one phosphate ester moiety in one molecule. It means something that exists only. Specific examples of the phosphate ester (C) satisfying the conditions described so far are listed below.

Specific examples of the condensed phosphate ester include aromatic condensed phosphate esters such as 1,3-phenylene bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate); polyoxyalkylene bisdichloroalkyl And halogen-containing condensed phosphates such as phosphates; non-aromatic non-halogen-based condensed phosphates; Of these, aromatic condensed phosphates are preferred because of their relatively low specific gravity, no risk of releasing harmful substances (such as halogens), and availability, and 1,3-phenylenebis (diphenyl phosphate). ), Bisphenol A bis (diphenyl phosphate) is more preferred.

Specific examples of the non-condensed phosphate ester include aromatics such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate, 2-ethylhexyl diphenyl phosphate And phosphoric acid esters; halogen-containing phosphoric acid esters such as tris (β-chloropropyl) phosphate, trisdichloropropylphosphate, tris (tribromoneopentyl) phosphate; Of these, aromatic phosphates are preferred because no harmful substances (such as halogen) are generated.

As the phosphate ester (C), one type may be used alone, or two or more types may be used in combination.

The amount of the phosphoric ester (C) used in the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention is 100% of the acrylic resin composition (A). The mass part is 45 to 190 parts by mass, preferably 55 to 150 parts by mass, and more preferably 70 to 120 parts by mass. By making content of phosphate ester (C) into the said range, it is easy to improve the flame retardance of a heat conductive pressure sensitive adhesive composition (F) or a heat conductive pressure sensitive adhesive sheet-like molded object (G). Become.

<Polyfunctional epoxy compound (E)>
A polyfunctional epoxy compound (E) is used for the heat conductive pressure-sensitive-adhesive composition (F) and heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention. By using the thermally conductive filler (B1), the polyfunctional monomer (D), and the polyfunctional epoxy compound (E) in combination, it is possible to provide excellent strength and flame retardancy even when molded thinly. A heat conductive pressure-sensitive-adhesive composition (F) and a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) can be obtained.

The polyfunctional epoxy compound (E) can react with an organic acid group in the (meth) acrylic acid ester polymer (A1) to form a crosslinked structure. Similarly, when the (meth) acrylate monomer (α1) contains a monomer having an organic acid group, it can react with the organic acid group. A crosslinked structure can be formed in the polymer containing the structural unit derived from the monomer (α1).

The polyfunctional epoxy compound (E) used in the present invention has 2 or more and 10,000 or less functional groups, and the number of functional groups is preferably 2 or more and 1000 or less, and more preferably 2 or more and 10 or less. preferable. Since the number of functional groups of the polyfunctional epoxy compound (E) is in the above range, the heat conductive pressure sensitive adhesive composition (F) and the heat conductive pressure sensitive adhesive sheet-like molded body (G) have strength and adhesion. It becomes easy to achieve both.

Specific examples of the polyfunctional epoxy compound (E) used in the present invention include resorcinol diglycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrogenated bisphenol A di Glycidyl ether, glycerol polyglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, diglycerol tetraglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. Is mentioned. Among them, pentaerythritol tetraglycidyl ether is preferable because a crosslinked structure can be effectively formed even in a small amount. A polyfunctional epoxy compound (E) may be used individually by 1 type, and may use 2 or more types together.

The amount of the polyfunctional epoxy compound (E) used for the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention is the acrylic resin composition (A). As 100 parts by mass, it is 0.05 parts by mass or more and 15 parts by mass or less, preferably 0.08 parts by mass or more and 10 parts by mass or less, and more preferably 0.1 parts by mass or more and 5 parts by mass or less. . By making the usage-amount of a polyfunctional epoxy compound (E) into the said range, intensity | strength and adhesiveness are made to a heat conductive pressure sensitive adhesive composition (F) and a heat conductive pressure sensitive adhesive sheet-like molded object (G). It becomes easy to achieve both.

<Other additives>
In addition to the above-described components, the above-described effects due to the addition of the above-described components are hindered in the heat-conductive pressure-sensitive adhesive composition (F) and the heat-conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention. Various known additives can be added within the range. Known additives include: foaming agents (including foaming aids); heat conductive fillers whose specific surface area is not included in the range of heat conductive filler (B1) and heat conductive filler (B2); Flame retardant thermally conductive inorganic compounds such as hydroxides and metal salt hydrates; Glass fibers; Thermally conductive inorganic compounds such as expanded graphite powder and PITCH carbon fibers; External cross-linking agents; Pigments such as carbon black and titanium dioxide; Other fillers such as clay; nanoparticles such as fullerenes and carbon nanotubes; antioxidants such as polyphenols, hydroquinones and hindered amines; thickeners such as acrylic polymer particles, fine silica and magnesium oxide; Can do.

2. Production Method The thermally conductive pressure-sensitive adhesive composition (F) of the present invention is prepared by mixing the materials described so far, and then (meth) acrylic acid ester monomer (α1) and multifunctional monomer (D ) And a crosslinking reaction of a polymer containing a structural unit derived from the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer (α1). be able to.

That is, the manufacturing method of the heat conductive pressure-sensitive-adhesive composition (F) of this invention contains the (meth) acrylic acid ester polymer (A1) and the (meth) acrylic acid ester monomer ((alpha) 1) ( (Meth) acrylic resin composition (A), thermal conductive filler (B1) having a BET specific surface area of 1.0 m ² / g or more and 10 m ² / g or less, phosphate ester (C), and polymerizable unsaturated A step of producing a mixed composition comprising a polyfunctional monomer (D) having a plurality of bonds and a polyfunctional epoxy compound (E) having a functional group of 2 or more and 10,000 or less, and in the mixed composition , (Meth) acrylic acid ester monomer (α1) and polyfunctional monomer (D) polymerization reaction, (meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester Including structural units derived from the body (α1) And a cross-linking reaction of the polymer. In addition, the substance which can be used, the preferable content ratio of each substance, the preferable average particle diameter of each substance, and the like are as described above, and the description is omitted.

In the production method of the heat conductive pressure-sensitive adhesive composition (F) of the present invention, it is preferable to heat the polymerization and crosslinking reaction of the (meth) acrylic acid ester monomer (α1). For the heating, for example, hot air, an electric heater, infrared rays, or the like can be used. The heating temperature at this time is preferably a temperature at which the polymerization initiator is efficiently decomposed and the polymerization of the (meth) acrylic acid ester monomer (α1) and the polyfunctional monomer (D) proceeds. Although a temperature range changes with kinds of polymerization initiator to be used, 100 to 200 degreeC is preferable and 130 to 180 degreeC is more preferable.

The heat conductive pressure-sensitive adhesive sheet-shaped molded product (G) of the present invention is obtained by mixing the materials described above into a sheet shape, or while forming into a sheet shape. Polymerization reaction of monomer (α1) and polyfunctional monomer (D), and structural unit derived from (meth) acrylic acid ester polymer (A1) and / or (meth) acrylic acid ester monomer (α1) It can obtain by performing at least crosslinking reaction of the polymer containing.

That is, the manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded product (G) of the present invention comprises (meth) acrylic acid ester polymer (A1) and (meth) acrylic acid ester monomer (α1). A (meth) acrylic resin composition (A), a thermally conductive filler (B1) having a BET specific surface area of 1.0 m ² / g or more and 10 m ² / g or less, a phosphate ester (C), and a polymerizable property A step of producing a mixed composition comprising a polyfunctional monomer (D) having a plurality of unsaturated bonds and a polyfunctional epoxy compound (E) having a functional group of 2 to 10,000, and the mixed composition Or a polymerization reaction of the (meth) acrylic acid ester monomer (α1) and the polyfunctional monomer (D), while forming the mixed composition into a sheet shape, (Meth) acrylic acid ester polymer (A1) and / Or (meth) comprises at least performing step a crosslinking reaction of a polymer containing structural units derived from an acrylic acid ester monomer ([alpha] 1). In addition, the preferable content ratio of each material, a preferable average particle diameter, etc. are as above-mentioned, and description is abbreviate | omitted.

In the method for producing the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention, the polymerization reaction of the (meth) acrylic acid ester monomer (α1) and the polyfunctional monomer (D), It is preferable to heat at least the crosslinking reaction of the polymer containing the structural unit derived from the acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer (α1). For the heating, for example, hot air, an electric heater, infrared rays, or the like can be used. The heating temperature at this time is preferably a temperature at which the polymerization initiator is efficiently decomposed and the polymerization of the (meth) acrylic acid ester monomer (α1) proceeds. Although a temperature range changes with kinds of polymerization initiator to be used, 100 to 200 degreeC is preferable and 130 to 180 degreeC is more preferable.

The method for forming the mixed composition into a sheet is not particularly limited. Suitable methods include, for example, a casting method in which the mixed composition is applied onto process paper such as a peeled polyester film, and the mixed composition is sandwiched between two peeled process papers if necessary. , A method of passing between rolls, and a method of controlling the thickness through a die when the mixed composition is extruded using an extruder.

As described above, the heat conductive pressure-sensitive adhesive sheet-like molded article (G) of the present invention can be formed thinner than the conventional heat conductive pressure-sensitive adhesive sheet-like molded article. Specifically, the thickness of the heat conductive pressure-sensitive adhesive sheet-shaped product (G) of the present invention can be 0.05 mm or more and 3.0 mm or less. By reducing the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded article (G), the thermal resistance in the thickness direction of the heat conductive pressure-sensitive adhesive sheet-like molded article (G) can be reduced. From such a viewpoint, the upper limit of the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded body (G) is preferably 1.0 mm, more preferably 0.5 mm. On the other hand, the lower limit of the thickness of the heat conductive pressure-sensitive adhesive sheet-like molded product (G) is preferably 0.1 mm. By setting the heat conductive pressure-sensitive adhesive sheet-shaped molded body (G) to 0.05 mm or more, air is applied when the heat conductive pressure-sensitive adhesive sheet-shaped molded body (G) is applied to the heating element and the heat radiating body. It is easy to prevent entrainment, and as a result, an increase in thermal resistance is prevented, and workability in the step of attaching to the adherend is easily improved.

Also, the heat conductive pressure-sensitive adhesive sheet-like molded body (G) can be molded on one side or both sides of the substrate. The material which comprises the said base material is not specifically limited. Specific examples of the substrate include metals having excellent thermal conductivity such as aluminum, copper, stainless steel, and beryllium copper, and polymers having excellent thermal conductivity such as foils of alloys and thermally conductive silicone. And a sheet-like material made of the above, a heat-conductive plastic film containing a heat-conductive additive, various non-woven fabrics, a glass cloth, and a honeycomb structure. Plastic films include polyimide, polyethylene terephthalate, polyethylene naphthalate, polytetrafluoroethylene, polyether ketone, polyethersulfone, polymethylpentene, polyetherimide, polysulfone, polyphenylene sulfide, polyamideimide, polyesterimide, aromatic polyamide, etc. A heat-resistant polymer film can be used.

3. Use example The heat conductive pressure-sensitive-adhesive composition (F) and heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of this invention can be used as some electronic components. At that time, it can be directly molded on a base material such as a radiator and provided as a part of the electronic component. Specific examples of the electronic component include components around a heat generating part in a device having an electroluminescence (EL) light emitting diode (LED) light source, components around a power device such as an automobile, a fuel cell, a solar cell, a battery, and a mobile phone. And devices and parts having a heat generating part such as a personal digital assistant (PDA), a notebook computer, a liquid crystal, a surface conduction electron-emitting device display (SED), a plasma display panel (PDP), or an integrated circuit (IC). .

In addition, as an example of a method for using the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention in an electronic device, an LED light source is described below as a specific example. The usage method to do can be mentioned. That is, it is directly attached to the LED light source; sandwiched between the LED light source and a heat dissipation material (heat sink, fan, Peltier element, heat pipe, graphite sheet, etc.); , Heat pipe, graphite sheet, etc.); used as a casing surrounding the LED light source; affixed to the casing surrounding the LED light source; and filling a gap between the LED light source and the casing. Application examples of LED light sources include backlight devices for display devices having a transmissive liquid crystal panel (TVs, mobile phones, PCs, notebook PCs, PDAs, etc.); vehicle lamps; industrial lighting; commercial lighting; Lighting; and the like.

Also, specific examples other than the LED light source include the following. That is, PDP panel; IC heating part; Cold cathode tube (CCFL); Organic EL light source; Inorganic EL light source; High luminance light emitting LED light source; High luminance light emitting organic EL light source; And so on.

Furthermore, examples of the method of using the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded body (G) of the present invention include affixing to the housing of the apparatus. For example, in an apparatus used for an automobile or the like, it is attached to the inside of a casing provided in the automobile; it is attached to the outside of the casing provided in the automobile; a heat generating part (car navigation / A fuel cell / heat exchanger) and the casing; and affixing to a heat sink connected to a heat generating part (car navigation / fuel cell / heat exchanger) in the casing of the automobile; Can be mentioned.

In addition to the automobile, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-shaped product (G) of the present invention can be used in the same manner. For example, personal computers; homes; TVs; mobile phones; vending machines; refrigerators; solar cells; surface-conduction electron-emitting device displays (SEDs); organic EL displays; inorganic EL displays; Organic EL display; laptop computer; PDA; fuel cell; semiconductor device; rice cooker; washing machine; washing dryer; optical semiconductor device combining optical semiconductor elements and phosphors; various power devices; Is mentioned.

Furthermore, the heat conductive pressure-sensitive adhesive composition (F) and the heat conductive pressure-sensitive adhesive sheet-like molded product (G) of the present invention are not limited to the above-described usage methods, and may be used in other methods depending on the application. It is also possible to use it. For example, used for heat equalization of carpets and warm mats, etc .; used as LED light source / heat source sealant; used as solar cell sealant; used as solar cell backsheet Used between the backsheet of the solar cell and the roof; used inside the heat insulating layer inside the vending machine; used inside the housing of the organic EL lighting with a desiccant or a hygroscopic agent; organic EL lighting Use with desiccant and hygroscopic agent on the heat conductive layer inside the housing of the LED; Use with desiccant and hygroscopic agent on the heat conductive layer and heat dissipation layer inside the housing of the organic EL lighting Used for heat conduction layer inside the housing of organic EL lighting, epoxy heat dissipation layer, and on top of it with desiccant and hygroscopic agent; cooling equipment, clothing, towels, sheets, etc. for cooling humans and animals On the opposite side of the body to the member Used for a pressure member of a fixing device mounted on an image forming apparatus such as an electrophotographic copying machine or an electrophotographic printer; Pressurizing a fixing device mounted on an image forming apparatus such as an electrophotographic copying machine or an electrophotographic printer Used as a member itself; used as a heat flow control heat transfer part for placing a treatment object of a membrane control device; used as a heat flow control heat transfer part for placing a treatment object of a film control device; outer layer of a radioactive substance storage container It can be used between the interior and interior; used in a box body with a solar panel that absorbs sunlight; used between the reflective sheet of the CCFL backlight and the aluminum chassis.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples. The “parts” and “%” used here are based on mass unless otherwise specified.

<Fluidity>
The fluidity of the mixed composition obtained through the first and second mixing steps or the first to third mixing steps described later was evaluated. Specifically, the Hobart container in which the mixed composition was put was tilted by 30 ° with respect to the horizontal plane, and the state of the mixed composition after 1 minute was evaluated. The results are shown in Tables 2 and 3. The case where the mixed composition flowed along the inclination was indicated as “◯”, and the case where it did not move was indicated as “X”. The fluidity of the mixed composition makes it easier to form the mixed composition into a sheet. That is, it becomes easy to manufacture a heat conductive pressure-sensitive-adhesive sheet-like molded object (G).

<Break strength>
As will be described later, a heat-conductive pressure-sensitive adhesive sheet-like molded body (G) having a thickness of 0.3 mm was prepared, and from a base material (polyethylene terephthalate film, hereinafter referred to as “release PET film”) used at the time of preparation. About the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) which could be peeled, the breaking strength was measured with the following method. The results are shown in Tables 2 and 3. In addition, when peeling from a mold release PET film, what was not able to be peeled off was described as evaluation impossible.

The punching blade (dumbbell No. 1) was attached to a punching device (Dum Bell Ltd., SDL-100), and the screws were securely fastened. Set the plastic plate and punched plate, and punch the heat conductive pressure-sensitive adhesive sheet-shaped product (G) so that the longitudinal direction of the punching device is the MD direction of the heat conductive pressure-sensitive adhesive sheet-shaped product (G). A test piece was prepared. Autograph (manufactured by Shimadzu Corp., AGIS-20kN) was set, the power was turned on and waited for 15 minutes (load cell: 1kN). The test conditions (test speed: 300 mm / min) were selected, and the thickness of the test piece measured with a thickness meter (manufactured by TOYOSEIKI, a digital thickness gauge) was input. The test was started with the test piece sandwiched between chucks, and the breaking stress was read.

<Flame retardance>
As will be described later, five test pieces were prepared by cutting a thermally conductive pressure-sensitive adhesive sheet-shaped molded body (G) having a thickness of 0.3 mm into a size of 10 mm width × 150 mm length. A Bunsen burner air and gas flow rate was adjusted to produce a blue flame of about 20 mm in height, and a burner flame was applied to the lower end of a vertically supported specimen (so that it crossed the flame about 10 mm) and held for 10 seconds. After that, the test piece and the burner flame were released. Thereafter, as soon as the flame of the test piece disappeared, the burner flame was applied to the test piece and held for another 10 seconds, and then the test piece and the burner flame were separated. The flame- and flame-free combustion durations after the first and second flame contact and the presence / absence of combustion drops (drip) were evaluated, and UL-94 (flame retardant standard) was determined. That is, the flaming combustion duration after the end of the first and second flame contact, the total of the flammable combustion duration and the flameless combustion duration after the end of the second flame contact, The determination was made based on the total flame-free combustion time and the presence or absence of combustion drops (drip). In both the first and second times, the flammable combustion was completed within 10 seconds, and the total of the second flammable combustion duration and the flameless combustion time was within 30 seconds. The total flame burning time was within 50 seconds, and there was no burning fallen thing as V-0. In addition, the first and second flames were burned within 30 seconds, and the total of the second flame burning time and the flameless burning time was within 60 seconds, and another 5 flames were burned. And the flameless combustion time was within 250 seconds, and there was a burning fallen thing as V-2. Furthermore, all burned items were out of specification. The results are shown in Tables 2 and 3. If this evaluation satisfies the V-0 condition, it can be said that the flame retardancy is excellent. In addition, about the thing which was not able to peel from a release PET film at the time of preparation, it was set as evaluation impossible.

Example 1
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). The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A1-1) was 270,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) was 3.1. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined in terms of standard polystyrene by gel permeation chromatography using tetrahydrofuran as an eluent.

Next, 1.0 part of a polyfunctional monomer obtained by mixing pentaerythritol triacrylate, pentaerythritol tetraacrylate and pentaerythritol diacrylate in a ratio of 60: 35: 5, and 2-ethylhexyl acrylate (Tables 2 and 4) 3 is abbreviated as “2EHA”) and organic peroxide thermal polymerization initiator (1,6-bis (t-butylperoxycarbonyloxy) hexane (1 minute half-life temperature is 150 ° C.). )) 1.0 part and 1.0 part of a polyfunctional epoxy compound (manufactured by Nagase ChemteX Corporation, EX-411, pentaerythritol tetraglycidyl ether) are weighed with an electronic balance, ) Mixed with 13 parts of acrylic ester polymer (A1-1). For the mixing, a thermostatic bath (manufactured by Toki Sangyo Co., Ltd., trade name “Viscomate 150III”) and a Hobart mixer (manufactured by Kodaira Seisakusho Co., Ltd., trade name “ACM-5LVT type”, capacity: 5 L) were used. The temperature control of the Hobart container was set to 60 ° C., the rotation speed scale was set to 3, and the mixture was stirred for 10 minutes. This process is referred to as a first mixing process.

Next, 100 parts of phosphoric acid ester (Ajinomoto Fine Techno Co., Ltd., trade name “Reophos 65”, compound name “Triaryl isopropylated product”) and aluminum hydroxide (Nihon Light Metal Co., Ltd., trade name “BF”) -083 ”, average particle size: 8 μm, BET specific surface area: 0.8 m ² / g) and alumina (made by Showa Denko KK, trade name“ AL-47-H ”, average particle size: 2 μm, BET 500 parts of specific surface area: 1.1 m ² / g) were weighed and put into the Hobart container, the temperature control of the Hobart container was set to 60 ° C., the rotation speed scale was set to 5, and the mixture was stirred for 10 minutes. This process is referred to as a second mixing process.

Next, the mixed composition obtained through the first and second mixing steps was hung on the release PET film, and the release PET film was further covered on the mixture composition. This laminate in which the mixed composition was sandwiched between the release PET films was passed through a roll having a distance of 0.3 mm between them to form a sheet. Thereafter, the laminate was put into an oven and heated at 150 ° C. for 15 minutes. By this heating step, the (meth) acrylic acid ester monomer and the polyfunctional monomer are polymerized and almost simultaneously, the (meth) acrylic acid ester polymer (A1-1) and the (meth) acrylic acid ester The monomer polymer was subjected to a crosslinking reaction to obtain a heat conductive pressure-sensitive adhesive sheet-like molded body (hereinafter simply referred to as “sheet”) (G1). In addition, it was 99.9% when the polymerization conversion rate of the (meth) acrylic acid ester monomer was computed from the amount of residual monomers in a sheet | seat (G1).

(Examples 2 to 11 and Comparative Examples 1 to 8)
Sheets (G2 to 11, GC1 to 8) were obtained in the same manner as in Example 1 except that the composition of each material was changed as shown in Tables 2 and 3. In Example 11, an additive other than expanded graphite (trade name “EC-500”, particle size: 30 μm, manufactured by Ito Graphite Industries Co., Ltd.) was added in the second mixing step, and then the rotational speed scale was adjusted. 3. While degassing the inside of the Hobart container at −0.1 MPaG, the temperature control of the Hobart container was set to 60 ° C. and stirred for 10 minutes. This process is referred to as a third mixing process.

The additives which have not been described so far and used in Examples 2 to 11 and Comparative Examples 1 to 8 are as follows.
Phosphoric ester: manufactured by Daihachi Chemical Industry Co., Ltd., trade name “CR-741”, viscosity at 25 ° C .: 32000 mPa · s (rotation speed 10, rotor N0.5 (see Table 1), numerical value 80), atmospheric pressure Always liquid in the temperature range of 15 to 100 ° C., compound name “bisphenol A bis (diphenyl phosphate)”)
Aluminum hydroxide: manufactured by Nippon Light Metal Co., Ltd., trade name “B-083”, average particle size: 8 μm, BET specific surface area: 0.8 m ² / g
Aluminum hydroxide: manufactured by Nippon Light Metal Co., Ltd., trade name “B-103”, average particle size: 8 μm, BET specific surface area: 3 m ² / g
Aluminum hydroxide: manufactured by Nalvac, trade name “APYRAL 120E”, average particle size: 0.8 μm, BET specific surface area: 11 m ² / g
Alumina: Showa Denko KK, spherical alumina, trade name “AS-10”, average particle size: 40 μm, BET specific surface area: 0.6 m ² / g

As shown in Table 2, the sheets (G1) to (G11) according to the examples all have good fluidity of the mixed composition before forming into a sheet, and after forming into a sheet, the sheet has high tensile strength and is difficult. The flammability was also excellent. On the other hand, as shown in Table 3, any of the above performances of the sheets (GC1) to (GC8) according to the comparative examples was inferior. Specifically, it was as follows.
-Comparative example 1: The sheet | seat (GC1) of the comparative example 1 which does not contain a polyfunctional epoxy compound was damaged when peeling from a mold release PET film, and was a thing which cannot be used as a product. It is presumed that crosslinking between the (meth) acrylate polymer (A1-1) and the polymer of the (meth) acrylate monomer was insufficient.
-Comparative example 2: The sheet | seat (GC2) of the comparative example 2 which does not contain a polyfunctional monomer was damaged when peeling from a mold release PET film, and was a thing which cannot be used as a product. It is estimated that crosslinking between the (meth) acrylate polymer (A1-1) and the polymer of the (meth) acrylate monomer is insufficient.
Comparative Example 3: The sheet (GC3) of Comparative Example 3 that did not use a filler having a BET specific surface area in the range specified in the present invention has high hardness and is damaged when peeled from the release PET film. The product could not be used.
Comparative Example 4: The sheet (GC4) of Comparative Example 4 in which the content of the filler having a BET specific surface area in the range specified in the present invention was less than the range specified in the present invention was used when peeling the release PET film. It was damaged and could not be used as a product.
Comparative Example 5: The content of the filler having the BET specific surface area in the range specified in the invention was larger than the range specified in the present invention (GC5), the mixed composition before forming into a sheet It was not fluid and could not be made into a sheet.
-Comparative example 6: The sheet | seat (GC6) of the comparative example 6 in which content of phosphate ester was less than the range prescribed | regulated by this invention melted away in the flame retardance test.
-Comparative example 7: The sheet | seat (GC7) of the comparative example 7 whose content of phosphate ester was more than the range prescribed | regulated by this invention was not able to be made into a sheet.
Comparative Example 8: The sheet (GC8) of Comparative Example 8 using a filler having a BET specific surface area larger than the range specified in the present invention was not fluidized in the mixed composition before forming into a sheet and could not be formed into a sheet. .

Claims

100 parts by weight of (meth) acrylic acid ester polymer (A1) and (meth) acrylic resin composition (A1) containing (meth) acrylic acid ester monomer (α1),
90 to 1200 parts by mass of a thermally conductive filler (B1) having a BET specific surface area of 1.0 m 2 / g to 10 m 2 / g,
45 parts by weight or more and 190 parts by weight or less of phosphate ester (C),
0.2 to 15 parts by mass of a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds;
0.05 to 15 parts by mass of a polyfunctional epoxy compound (E) having a functional group of 2 to 10,000,
In the mixed composition containing, the polymerization reaction of the (meth) acrylic acid ester monomer (α1) and the polyfunctional monomer (D), the (meth) acrylic acid ester polymer (A1) and A heat-conductive pressure-sensitive adhesive composition (F), wherein at least a crosslinking reaction of a polymer containing a structural unit derived from the (meth) acrylic acid ester monomer (α1) is performed.
The thermally conductive filler has a BET specific surface area of not more than 1.0 m 2 / g or more 10m 2 / g (B1) is, BET specific surface area of less aluminum oxide 1.0 m 2 / g or more 10 m 2 / g, The heat conductive pressure-sensitive-adhesive composition (F) of Claim 1.
The thermal conductivity feeling according to claim 1 or 2, wherein the mixed composition further comprises 200 parts by mass or more and 800 parts by mass or less of a thermal conductive filler (B2) having a BET specific surface area of less than 1.0 m 2 / g. Pressure adhesive composition (F).
The thermally conductive filler has a BET specific surface area of less than 1.0m 2 / g (B2) is, BET specific surface area of aluminum hydroxide is less than 1.0 m 2 / g, thermal conductivity feeling of claim 3 Pressure adhesive composition (F).
The thermally conductive pressure-sensitive adhesive composition according to claim 1 or 2, wherein the (meth) acrylic resin composition (A) includes a monomer unit having an organic acid group or a monomer having an organic acid group. F).
100 parts by weight of (meth) acrylic acid ester polymer (A1) and (meth) acrylic resin composition (A1) containing (meth) acrylic acid ester monomer (α1),
90 to 1200 parts by mass of a thermally conductive filler (B1) having a BET specific surface area of 1.0 m 2 / g to 10 m 2 / g,
45 parts by weight or more and 190 parts by weight or less of phosphate ester (C),
0.2 to 15 parts by mass of a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds;
0.05 to 15 parts by mass of a polyfunctional epoxy compound (E) having a functional group of 2 to 10,000,
The (meth) acrylic acid ester monomer (α1) and the polyfunctional monomer (D) after forming the mixture composition containing a sheet into a sheet or while forming the mixture composition into a sheet And a crosslinking reaction of a polymer containing a structural unit derived from the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer (α1). The heat conductive pressure-sensitive-adhesive sheet-like molded object (G) which becomes.
The thermally conductive filler has a BET specific surface area of not more than 1.0 m 2 / g or more 10m 2 / g (B1) is, BET specific surface area of less aluminum oxide 1.0 m 2 / g or more 10 m 2 / g, The heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of Claim 6.
The thermal conductivity feeling according to claim 6 or 7, wherein the mixed composition further comprises 200 parts by mass or more and 800 parts by mass or less of a thermal conductive filler (B2) having a BET specific surface area of less than 1.0 m 2 / g. Pressure-adhesive sheet-like molded body (G).
The thermally conductive filler has a BET specific surface area of less than 1.0m 2 / g (B2) is, BET specific surface area of aluminum hydroxide is less than 1.0 m 2 / g, thermal conductivity feeling of claim 8 Pressure-adhesive sheet-like molded body (G).
The heat conductive pressure-sensitive adhesive sheet-like molding according to claim 6 or 7, wherein the (meth) acrylic resin composition (A) comprises a monomer unit having an organic acid group or a monomer having an organic acid group. Body (G).
100 parts by weight of (meth) acrylic acid ester polymer (A1) and (meth) acrylic resin composition (A1) containing (meth) acrylic acid ester monomer (α1),
90 to 1200 parts by mass of a thermally conductive filler (B1) having a BET specific surface area of 1.0 m 2 / g to 10 m 2 / g,
45 parts by weight or more and 190 parts by weight or less of phosphate ester (C),
0.2 to 15 parts by mass of a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds;
0.05 to 15 parts by mass of a polyfunctional epoxy compound (E) having a functional group of 2 to 10,000,
Producing a mixed composition comprising:
In the mixed composition, a polymerization reaction of the (meth) acrylic acid ester monomer (α1) and the polyfunctional monomer (D), the (meth) acrylic acid ester polymer (A1) and / or Or a step of performing at least a crosslinking reaction of a polymer containing a structural unit derived from the (meth) acrylic acid ester monomer (α1),
The manufacturing method of a heat conductive pressure-sensitive-adhesive composition (F) containing.
The thermally conductive filler has a BET specific surface area of not more than 1.0 m 2 / g or more 10m 2 / g (B1) is, BET specific surface area of less aluminum oxide 1.0 m 2 / g or more 10 m 2 / g, The manufacturing method of the heat conductive pressure-sensitive-adhesive composition (F) of Claim 11.
The heat conductive feeling according to claim 11 or 12, wherein the mixed composition further contains 200 parts by mass or more and 800 parts by mass or less of a heat conductive filler (B2) having a BET specific surface area of less than 1.0 m 2 / g. A method for producing the pressure-sensitive adhesive composition (F).
The thermally conductive filler has a BET specific surface area of less than 1.0m 2 / g (B2) is, BET specific surface area of aluminum hydroxide is less than 1.0 m 2 / g, thermal conductivity feeling of claim 13 A method for producing the pressure-sensitive adhesive composition (F).
100 parts by weight of (meth) acrylic acid ester polymer (A1) and (meth) acrylic resin composition (A1) containing (meth) acrylic acid ester monomer (α1),
90 to 1200 parts by mass of a thermally conductive filler (B1) having a BET specific surface area of 1.0 m 2 / g to 10 m 2 / g,
45 parts by weight or more and 190 parts by weight or less of phosphate ester (C),
0.2 to 15 parts by mass of a polyfunctional monomer (D) having a plurality of polymerizable unsaturated bonds;
0.05 to 15 parts by mass of a polyfunctional epoxy compound (E) having a functional group of 2 to 10,000,
Producing a mixed composition comprising:
The (meth) acrylic acid ester monomer (α1) and the polyfunctional monomer (D) after forming the mixed composition into a sheet or while forming the mixed composition into a sheet And a step of performing at least a polymerization reaction of the polymer containing a structural unit derived from the (meth) acrylic acid ester polymer (A1) and / or the (meth) acrylic acid ester monomer (α1),
The manufacturing method of a heat conductive pressure-sensitive-adhesive sheet-like molded object (G) including this.
The thermally conductive filler has a BET specific surface area of not more than 1.0 m 2 / g or more 10m 2 / g (B1) is, BET specific surface area of less aluminum oxide 1.0 m 2 / g or more 10 m 2 / g, The manufacturing method of the heat conductive pressure-sensitive-adhesive sheet-like molded object (G) of Claim 15.
The heat conductive feeling according to claim 15 or 16, wherein the mixed composition further contains 200 parts by mass or more and 800 parts by mass or less of a heat conductive filler (B2) having a BET specific surface area of less than 1.0 m 2 / g. Manufacturing method of pressure-adhesive sheet-like molded object (G).
The thermally conductive filler has a BET specific surface area of less than 1.0m 2 / g (B2) is, BET specific surface area of aluminum hydroxide is less than 1.0 m 2 / g, thermal conductivity feeling of claim 17 Manufacturing method of pressure-adhesive sheet-like molded object (G).
The heat conductive pressure-sensitive adhesive composition (F) according to any one of claims 1 to 5, which is bonded to the heat radiator and the heat radiator, or the heat radiator and the heat bonded to the heat radiator. Item 11. An electronic component comprising the heat conductive pressure-sensitive adhesive sheet-like molded body (G) according to any one of Items 6 to 10.