JP2012224765A - Composition for thermally conductive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition which can produce a thermally conductive sheet which excels in flexibility, heat resistance, thermal conductivity, adhesion, and reworkability, and does not volatilize a siloxane of a low molecular weight even if heated by a given condition.SOLUTION: The composition for a thermally conductive sheet includes: (A) an acrylic rubber in which the weight-average molecular weight is 2-200 million and the content of a structural unit originating in an unsaturated nitrile monomer is 5-40 mass%; and (B) a thermally conductive filler. Protective sheets 2, 3 are laminated on both sides 4a, 4b of a thermally conductive sheet 4 comprising curing the composition, and a sheet laminate 1 convenient for storage can be made.

Description

  The present invention relates to a composition for a heat conductive sheet using an acrylic polymer. More specifically, the present invention relates to a composition for use as a material for a thermally conductive sheet, which is a molded product used for improving thermal conductivity between a heat generating portion and a heat radiating portion of an electronic device.

  In recent years, the amount of heat generated from the heat generating portion has increased with the reduction in size and performance of electronic devices. As a result, issues such as product performance degradation, product life shortening, and safety degradation (burns, fires) have become obvious, and heat sinks such as heat sinks and product housings against heat generated from heat generating parts Heat dissipation measures to release heat to the outside are important. In general, heat generating portions such as CPUs and LED boards and heat radiating portions such as heat sinks and product housings are made of materials having poor flexibility such as metals, ceramics, and resins. Therefore, it is known to sandwich and use a heat conductive sheet in order to enhance the adhesion between the heat generating part and the heat radiating part and efficiently radiate heat.

  As the heat conductive sheet, in order to increase the heat conductivity, a heat conductive sheet in which a heat conductive filler such as aluminum oxide, boron nitride, aluminum nitride, zinc oxide, silicon carbide, quartz, aluminum hydroxide is added to silicone is used. Is disclosed (for example, see Patent Documents 1 to 3). However, low molecular weight siloxanes evaporating from silicone have the problem of causing contact failure by depositing insulating silicon oxide after thermal decomposition by current on the surface of electrode contacts and the like.

  In order to prevent volatilization of low molecular weight siloxane from the heat conductive sheet, a polymer other than silicone has been proposed as a base polymer of the heat conductive sheet. For example, a heat conductive sheet in which a heat conductive filler such as aluminum oxide, aluminum nitride, titanium dioxide, copper, aluminum, boron nitride, silicon nitride, silicon carbide, metal powder, and titanium boride is added to an acrylic polymer is disclosed. (For example, see Patent Documents 4 to 5).

  Also, a block copolymer hydrogenated product comprising a conjugated diene and an aromatic vinyl, having a specific structure, paraffinic oil, and zinc oxide, needle nitride, aluminum nitride having needle-like crystal parts as fillers In addition, a thermally conductive sheet to which silicon carbide, boron nitride or the like is added is also disclosed (for example, see Patent Document 6).

Japanese Patent No. 3183502 Japanese Patent No. 2728607 Japanese Patent Application Laid-Open No. 2000-233452 Japanese Patent No. 3636884 Japanese Patent No. 4086322 JP 2007-277300 A

  The heat conductive sheet using an acrylic polymer as a base polymer has a cross-linked structure due to a chemical bond like silicone, so the sheet-like molded product cross-linked after adding the heat conductive filler is hard, There is a problem that processing cannot be added. In addition, the heat conductive sheet made of a conjugated diene and aromatic vinyl and using a hydrogenated block copolymer with a specific structure as a base polymer has low paraffin oil content and improved flexibility. There remains room for.

  The present invention has been made in view of such problems of the prior art, and the subject is excellent in flexibility, heat resistance, thermal conductivity, adhesion, and reworkability, An object of the present invention is to provide a composition for a heat conductive sheet capable of producing a molded article (heat conductive sheet) that does not volatilize low molecular weight siloxane even when heated under conditions.

As a result of intensive studies to solve the above problems, the present inventor has found that the above object can be achieved according to the composition for a heat conductive sheet including a specific acrylic rubber and a heat conductive filler. . That is, the present invention provides the following [1] to [6].
[1] (A) Acrylic rubber having a weight average molecular weight of 2,000,000 to 20,000,000 and a content of structural units derived from unsaturated nitrile monomers of 5 to 40% by mass, and (B) A composition for a heat conductive sheet comprising a heat conductive filler.
[2] The thermal conductivity according to [1], wherein the volume ratio ((A) / (B)) of the acrylic rubber (A) and the thermal conductive filler (B) is 15/85 to 85/15. Sheet composition.
[3] The thermally conductive filler (B) is at least one selected from the group consisting of metals, metal oxides, metal hydroxides, carbon, boron nitride, aluminum nitride, silicon nitride, silicon carbide, and silica. The composition for heat conductive sheets according to [1] or [2].
[4] The composition for a heat conductive sheet according to any one of [1] to [3], including a flame retardant (C).
[5] A thermally conductive sheet obtained by curing the composition for thermally conductive sheet according to any one of [1] to [4].
[6] A sheet laminate including the thermally conductive sheet according to [5] and a protective sheet laminated on each of both surfaces of the thermally conductive sheet.

  By using the composition for a heat conductive sheet of the present invention, it is excellent in flexibility, heat resistance, heat conductivity, adhesion, and reworkability, and does not volatilize low molecular weight siloxane even when heated under predetermined conditions. The heat conductive sheet which is a product can be manufactured.

It is a figure for demonstrating the method to laminate | stack a protective sheet on both surfaces of the heat conductive sheet formed by hardening the composition for heat conductive sheets of this invention, and to produce a sheet laminated body.

Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments. It is understood that the scope of the present invention includes modifications, improvements, and the like as appropriate to the following embodiments based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. Should.
Each component which comprises the composition for heat conductive sheets of this invention is demonstrated.

[Acrylic rubber (A)]
The acrylic rubber (A) is an acrylic rubber having a weight average molecular weight of 2 million to 20,000,000 and a content of structural units derived from an unsaturated nitrile monomer of 5 to 40% by mass.
The acrylic rubber (A) can include a structural unit having a crosslinkable group. In this case, the content rate of the structural unit which has group which can be bridge | crosslinked is 0.1-10 mass%, for example.
Examples of the unsaturated nitrile monomer (unsaturated nitrile compound) include (meth) acrylonitriles such as acrylonitrile, methacrylonitrile, α-ethylacrylonitrile, methyl α-isopropylacrylonitrile, methyl α-n-butylacrylonitrile; 2 -Cyanoethyl (meth) acrylate, 2- (2-cyanoethoxy) ethyl (meth) acrylate, 3- (2-cyanoethoxy) propyl (meth) acrylate, 4- (2-cyanoethoxy) butyl (meth) acrylate, 2 Examples include cyano group-containing (meth) acrylic esters such as-[2- (2-cyanoethoxy) ethoxy] ethyl (meth) acrylate. Among these, acrylonitrile is preferable. In addition, an unsaturated nitrile monomer may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the structural unit derived from the unsaturated nitrile monomer is 5 to 40% by mass, preferably 8 to 35% by mass, more preferably 10 to 30% by mass, and particularly preferably 15 to 25% by mass. If the value is less than 5% by mass, the hardness of the sheet is too low and the reworkability may be poor. When this value exceeds 40% by mass, the flexibility may decrease.

In the present specification, the monomer for constituting the “structural unit having a crosslinkable group” (also referred to as “curing monomer” in the present specification) is the component (A) ( After obtaining an acrylic rubber), a curing initiator such as a crosslinking agent (eg, organic peroxide, sulfur, etc.), a photopolymerization initiator (eg, a photo radical generator, etc.), a photo acid generator, a thermal acid generator, etc. Or a monomer having a crosslinkable group that is a portion capable of curing the composition of the present invention by heating or light irradiation without using a curing initiator.
Here, as a group which can be bridge | crosslinked, an ethylenic double bond (for example, (meth) acryloyl group etc.), an epoxy group, etc. are mentioned, for example.
As the curing monomer, (a) a polyfunctional monomer (having two or more polymerizable groups) having a portion capable of curing the composition of the present invention by heating or a photoradical generator after polymerization. Monomer) and (b) a monomer having a crosslinkable functional group (for example, epoxy group or the like) that can cure the composition of the present invention with a photoacid generator after polymerization.
Examples of the (a) polyfunctional monomer include vinyl (meth) acrylate, allyl (meth) acrylate, 1,1-dimethylpropenyl (meth) acrylate, 3,3-dimethylbutenyl (meth) acrylate, and itaconic acid. Divinyl, divinyl maleate, vinyl-1,1-dimethylpropenyl ether, vinyl 3,3-dimethylbutenyl ether, 1-acryloyloxy-1-phenylethene, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meta ) Acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) Ak Rate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) Di (meth) acrylate of acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A ethylene oxide or propylene oxide adduct diol, hydrogenated bisphenol A ethylene oxide or propylene oxide adduct diol di (Meth) acrylate, epoxy di (meth) acrylate obtained by adding (meth) acrylate to diglycidyl ether of bisphenol A, triethylene glycol divinyl ether , Dicyclopentenyloxyethyl (meth) acrylate, conjugated diene compounds such as 1,3-butadiene and isoprene, and nonconjugated diene compounds such as 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene. .

  Examples of the epoxy group-containing monomer (b) as an example of a monomer having a crosslinkable functional group include allyl glycidyl ether, (meth) acrylic acid glycidyl ether, (meth) allyl glycidyl ether, and (meth) acrylic. Acid-2-ethyl glycidyl ether, 2-methylallyl glycidyl ether, glycidyl (meth) acrylate, etc. are mentioned.

The introduction of the “structural unit having a crosslinkable group” contributes to an increase in molecular weight in addition to being crosslinkable by post-treatment after the production of the composition for a heat conductive sheet.
The content of the “structural unit having a crosslinkable group” is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, still more preferably 1 to 5% by mass, and particularly preferably 1 ˜3 mass%. When the value is 0.1% by mass or more, permanent distortion due to repeated deformation can be reduced and thermal conductivity can be improved. If the value exceeds 10% by mass, gelation may occur in the process of synthesizing the acrylic rubber, and the processability may be deteriorated.
In the present invention, the “structural unit having a crosslinkable group” is not essential. In the present invention, the effects of the present invention can be obtained even if the “structural unit having a crosslinkable group” is not included.

The acrylic rubber as the component (A) includes a structural unit derived from (meth) acrylate. Examples of compounds for providing such structural units include alicyclic structures such as isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. (Meth) acrylate; benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine and the like. Furthermore, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, Propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, Hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrelane , Decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) Acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) ) Acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene Propylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( And (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, and the like.
Especially, what has a C1-C10 alkyl group is more preferable.
Examples of the (meth) acrylate having an alkyl group having 1 to 10 carbon atoms include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like.

The weight average molecular weight of the acrylic rubber as the component (A) is 2 million to 20 million, preferably 3 million to 17,000,000, more preferably 5 million to 100,000, and particularly preferably 5 million to 5 10 million. If the value is less than 2 million, the mechanical properties of the material are poor and the reworkability may be poor. When this value exceeds 20,000,000, workability may be deteriorated.
In this specification, a weight average molecular weight is a polystyrene conversion value by gel permeation chromatography (GPC).
The polymerization method of the component (A) can be performed by a known technique such as emulsion polymerization or solution polymerization. Among these, emulsion polymerization using a small amount of a polymerization initiator is suitable for obtaining a high molecular weight acrylic rubber. Each monomer may be polymerized in a lump, or may be added and polymerized in a divided manner, but it is more preferable to add and polymerize in a divided manner. This is because the composition distribution of the monomer constituting the acrylic rubber as the component (A) is uniformized and the flexibility is improved.

[Thermal conductive filler (B)]
(B) As a heat conductive filler, what has insulation (insulating filler) and what does not have insulation (conductive filler) are mentioned. Which of the insulating filler and the conductive filler is used is determined according to the use of the heat conductive sheet.
(B) The thermal conductivity of the thermally conductive filler is preferably 3 W / (m · K) or more, more preferably 10 W / (m · K) or more, and 20 W / (m · K) or more. It is particularly preferred that
The thermal conductivity of the thermal conductive sheet is preferably 3 W / (m · K) or more, although it depends on the filling rate of the (B) thermal conductive filler.

  (B) Examples of the thermally conductive filler include conductive materials such as metal particles (for example, particles such as aluminum and copper), metal fibers (for example, fibers such as aluminum and copper), carbon fibers, and carbon particles, Particles or powders of metal oxides such as alumina, magnesium oxide, zinc oxide, beryllium oxide, particles or powders of metal hydroxides such as aluminum hydroxide and magnesium hydroxide, boron nitride, aluminum nitride, silicon nitride, etc. And metal or metalloid nitride particles or powder, silica powder such as quartz and crystalline silica, and the like. Among these, from the viewpoint of improving thermal conductivity, at least one selected from the group consisting of metal oxides, metal hydroxides, metal or metalloid nitrides, and silica powder is preferable, boron nitride and alumina More preferably, it is at least one of the following. These (B) thermally conductive fillers can be used singly or in combination of two or more. For the purpose of improving the affinity with the acrylic rubber (A), it is also preferable to use a surface-treated (B) thermally conductive filler.

  (B) The shape of a heat conductive filler is not specifically limited. (B) Specific examples of the shape of the heat conductive filler include a spherical shape, a needle shape, a fiber shape, a scale shape, a dendritic shape, a flat plate shape, and an indefinite shape.

  (B) The number average particle diameter of the thermally conductive filler is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm, and particularly preferably 1 to 20 μm. When the number average particle diameter is 0.1 μm or more, an increase in the viscosity of the composition of the present invention can be suppressed, and the fluidity during kneading can be favorably maintained. On the other hand, when the number average particle diameter is 100 μm or less, the fluidity of the composition of the present invention can be improved.

  The volume ratio ((A) / (B)) of the acrylic rubber (A) and the thermally conductive filler (B) is preferably 15/85 to 85/15, more preferably 20/80 to 80/20, and further It is preferably 20/80 to 60/40, particularly preferably 20/80 to 40/60. When the volume ratio is 15/85 or less, the fluidity of the composition of the present invention can be improved. When the volume ratio is 85/15 or less, the thermal conductivity of the heat conductive sheet obtained by curing the composition of the present invention can be easily set to 3 W / (m · K) or more.

[Flame retardant]
The composition of the present invention may contain a generally known flame retardant. As the flame retardant, a phosphorus flame retardant, a halogen flame retardant, and a hydrate flame retardant may be appropriately blended.
Examples of phosphorus flame retardants include phosphate esters.
The blending amount of the flame retardant is preferably 10 to 90 parts by mass, more preferably 100 parts by mass, more preferably 100 parts by mass in total with the acrylic rubber (A), from the viewpoint of achieving both the effect of flame retardancy and the effect of the present invention. 20 to 80 parts by mass, particularly preferably 30 to 70 parts by mass.

[Other additives]
As components of the composition of the present invention, anti-aging agents, antioxidants, antistatic agents, weathering stabilizers, ultraviolet absorbers, lubricants, antiblocking agents, sealability improvers, crystal nucleating agents, flame retardants, Additives such as fungicides, fungicides, tackifiers, softeners, plasticizers, colorants, fillers and the like may be appropriately blended.

[Method for producing composition of the present invention]
When kneading the acrylic rubber (A), the thermally conductive filler (B), and other optional components, a conventionally known kneading apparatus can be used. Examples of the kneading apparatus include a plast mill, a biaxial kneader, a single screw kneader, a heatable biaxial or single screw feeder, a feeder ruder, a Banbury mixer, a roll mill, and the like.
The composition or pellet kneaded by the above production method was used to obtain a sheet having a constant thickness using a known roll press or flat plate press.

[Sheet Laminate]
In the present invention, as shown in FIG. 1, the heat conductive sheets 2 and 3 are subjected to the release treatment so that the surfaces 2 a and 3 a are in contact with both surfaces 4 a and 4 b of the heat conductive sheet 4. The sheet laminate 1 may be produced by laminating the both sides. In this case, the mold release treatment method and the protective sheet base material can be appropriately selected from conventionally known methods and base materials.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
In Examples, parts and% are based on mass unless otherwise specified.
Various measurements in the examples were based on the following methods.
[Weight average molecular weight]
The weight average molecular weight is a measured value obtained as a polystyrene-converted value using a calibration curve created from the measurement results of standard polystyrene by gel permeation chromatography (GPC). Moreover, in the area | region where a weight average molecular weight exceeds 7 million, the created calibration curve was extrapolated and the polystyrene conversion value was measured. “HLC-8120 (trade name)” (manufactured by Tosoh Corporation) as a measuring device, “GMHHR-H column (trade name)” (manufactured by Tosoh Corporation) as a column, a differential refractometer as a detector, a temperature of 40 ° C., The measurement was conducted with tetrahydrofuran as the solvent and a flow rate of 0.4 ml / min.
The sample used for the measurement was prepared by dissolving 25 mg of the polymer after coagulation in 10 ml of tetrahydrofuran, followed by filter filtration (MILLIPORE, Millex-FA, pore size: 1.0 μm). .
[Total amount of structural units derived from unsaturated nitrile monomer]
The total amount (% by mass) of structural units derived from the unsaturated nitrile monomer was calculated from the nitrogen content measured by elemental analysis.
[Thermal conductivity]
The thermal conductivity was measured in the thickness direction of the sheet.
The thermal conductivity of the sheet was measured at 25 ° C. using a laser flash method thermal constant measuring device “TR-7000R” (model name) manufactured by ULVAC-RIKO. The test specimen for measurement is a disk (outer diameter: 10 mm, thickness: 0.8 mm) obtained by processing a sheet.
[hardness]
The hardness is a duro A hardness measured according to ISO7619. Hardness is a physical property for evaluating the flexibility of a sheet. The case where the hardness after 5 seconds of measurement was “60A-5s” or less was evaluated as having passed the flexibility.
[Reworkability]
With regard to reworkability, the thermal conductive sheet of 10 cm × 1 cm × 0.5 mm thick stuck to an aluminum plate of 1mm thickness at a pressure of 1 kgf / cm ^2, the case dimensional change after peeling in the longitudinal direction is less than 1% And passed.

[Acrylic rubber production method]
(Synthesis Example 1)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the obtained aqueous solution, a monomer component consisting of 89 parts of ethyl acrylate, 10 parts of acrylonitrile, 1 part of dicyclopentenyloxyethyl acrylate, 0.18 part of t-dodecyl mercaptan as a molecular weight regulator, redox After the catalyst was charged into the reactor and the temperature was adjusted to 15 ° C., 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction to obtain a polymer latex (1).
Thereafter, 1 part of an anti-aging agent (product name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (1) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salted out. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (1)).
The obtained copolymer (1) has a weight average molecular weight of 3.84 million and is a structural unit derived from acrylonitrile (a structural unit derived from an unsaturated nitrile monomer; also referred to as “AN amount” in the present specification). )) Was 10% by mass. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 1% by mass.

(Synthesis Example 2)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the obtained aqueous solution, a monomer component consisting of 84 parts of ethyl acrylate, 15 parts of acrylonitrile, 1 part of dicyclopentenyloxyethyl acrylate, 0.18 part of t-dodecyl mercaptan as a molecular weight regulator, redox catalyst Were adjusted to 15 ° C., and 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction, thereby obtaining a polymer latex (2).
Thereafter, 1 part of an anti-aging agent (trade name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (2) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salting out is performed. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (2)).
The obtained copolymer (2) had a weight average molecular weight of 6.63 million, and the content ratio of the structural unit derived from acrylonitrile (the structural unit derived from the unsaturated nitrile monomer) was 15% by mass. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 1% by mass.

(Synthesis Example 3)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the obtained aqueous solution, a monomer component composed of 28 parts of ethyl acrylate, 5 parts of acrylonitrile, 0.33 part of dicyclopentenyloxyethyl acrylate, 0.18 part of t-dodecyl mercaptan as a molecular weight regulator, The redox catalyst was charged into the reactor and the temperature was adjusted to 15 ° C., and then 0.02 part of paramentane hydroperoxide was added as a polymerization initiator and reacted for 30 minutes. Thereafter, a monomer component consisting of a mixture of 56 parts of ethyl acrylate, 10 parts of acrylonitrile and 0.67 part of dicyclopentenyloxyethyl acrylate was added over 2 hours, and emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction to obtain a polymer latex (3).
Thereafter, 1 part of an anti-aging agent (trade name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (3) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salting out is performed. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (3)).
The obtained copolymer (3) had a weight average molecular weight of 3.5 million, and the content ratio of structural units derived from acrylonitrile (structural units derived from unsaturated nitrile monomers) was 15% by mass. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 1% by mass.

(Synthesis Example 4)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the obtained aqueous solution, a monomer component consisting of 42 parts of ethyl acrylate, 4 parts of acrylonitrile, 0.5 part of dicyclopentenyloxyethyl acrylate, 0.18 part of t-dodecyl mercaptan as a molecular weight regulator, A redox catalyst was charged into the reactor and the temperature was adjusted to 15 ° C., and 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Two hours later, a monomer component consisting of 42 parts of ethyl acrylate, 11 parts of acrylonitrile and 0.5 part of dicyclopentenyloxyethyl acrylate was added, and emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction, thereby obtaining a polymer latex (4).
Thereafter, 1 part of an anti-aging agent (product name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (4) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salting out is performed. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (4)).
The obtained copolymer (4) had a weight average molecular weight of 5940,000, and the content ratio of the structural unit derived from acrylonitrile (the structural unit derived from the unsaturated nitrile monomer) was 15% by mass. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 1% by mass.

(Synthesis Example 5)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the obtained aqueous solution, a monomer component consisting of 84 parts of ethyl acrylate, 15 parts of acrylonitrile, 1 part of dicyclopentenyloxyethyl acrylate, 0.18 part of t-dodecyl mercaptan as a molecular weight regulator, redox catalyst Were adjusted to 15 ° C., and 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 96%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction to obtain a polymer latex (5).
Thereafter, 1 part of an anti-aging agent (product name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (5) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salting out is performed. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (5)).
The obtained copolymer (5) had a weight average molecular weight of 23.34 million, and the content ratio of the structural unit derived from acrylonitrile (the structural unit derived from the unsaturated nitrile monomer) was 15% by mass. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 1% by mass.

(Synthesis Example 6)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the resulting aqueous solution, a monomer component consisting of 79 parts of ethyl acrylate, 20 parts of acrylonitrile, 1 part of dicyclopentenyloxyethyl acrylate, 0.18 part of t-dodecyl mercaptan as a molecular weight regulator, redox catalyst Were adjusted to 15 ° C., and 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction, thereby obtaining a polymer latex (6).
Thereafter, 1 part of an anti-aging agent (trade name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (6) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salted out. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (6)).
The obtained copolymer (6) had a weight average molecular weight of 421.5 million, and the content ratio of the structural unit derived from acrylonitrile (the structural unit derived from the unsaturated nitrile monomer) was 20% by mass. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 1% by mass.

(Synthesis Example 7)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the obtained aqueous solution, a monomer component consisting of 64 parts of 2-ethylhexyl acrylate, 35 parts of acrylonitrile, 1 part of dicyclopentenyloxyethyl acrylate, 0.18 parts of t-dodecyl mercaptan as a molecular weight regulator, A redox catalyst was charged into the reactor and the temperature was adjusted to 15 ° C., and 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction, thereby obtaining a polymer latex (7).
Thereafter, 1 part of an anti-aging agent (trade name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (7) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salted out. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (7)).
The obtained copolymer (7) had a weight average molecular weight of 11.72 million, and the content ratio of structural units derived from acrylonitrile (structural units derived from unsaturated nitrile monomers) was 35% by mass. It was. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 1% by mass.

(Synthesis Example 8)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the resulting aqueous solution, a monomer component comprising 81 parts of ethyl acrylate, 15 parts of acrylonitrile, 4 parts of dicyclopentenyloxyethyl acrylate, 0.53 part of t-dodecyl mercaptan as a molecular weight regulator, redox catalyst Were adjusted to 15 ° C., and 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction, thereby obtaining a polymer latex (8).
Then, 1 part of an anti-aging agent (trade name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (8) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salting out is performed. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (8)).
The obtained copolymer (8) had a weight average molecular weight of 15,509,000 and the content ratio of structural units derived from acrylonitrile (structural units derived from unsaturated nitrile monomers) was 15% by mass. It was. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 4% by mass.

(Synthesis Example 9)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the obtained aqueous solution, a monomer component consisting of 77 parts of ethyl acrylate, 15 parts of acrylonitrile, 8 parts of dicyclopentenyloxyethyl acrylate, 0.53 part of t-dodecyl mercaptan as a molecular weight regulator, redox catalyst Were adjusted to 15 ° C., and 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction, thereby obtaining a polymer latex (8).
Then, 1 part of an anti-aging agent (trade name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (8) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salting out is performed. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (9)).
The obtained copolymer (9) had a weight average molecular weight of 160,860,000, and the content ratio of structural units derived from acrylonitrile (structural units derived from unsaturated nitrile monomers) was 15% by mass. It was. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 8% by mass.

(Synthesis Example 10)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the resulting aqueous solution, a monomer component consisting of 42 parts of methyl acrylate, 42 parts of butyl acrylate, 15 parts of acrylonitrile and 1 part of dicyclopentenyloxyethyl acrylate, and t-dodecyl mercaptan 0.18 as a molecular weight regulator. And a redox catalyst were charged into a reactor and the temperature was adjusted to 15 ° C., and 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction to obtain a polymer latex (10).
Thereafter, 1 part of an anti-aging agent (trade name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (10) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salted out. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (10)).
The obtained copolymer (10) had a weight average molecular weight of 4.4 million, and the content ratio of a structural unit derived from acrylonitrile (a structural unit derived from an unsaturated nitrile monomer) was 15% by mass. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 1% by mass.

(Synthesis Example 11)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the resulting aqueous solution, a monomer component comprising 20 parts of 2-methoxyethylethyl acrylate, 64 parts of butyl acrylate, 15 parts of acrylonitrile, 1 part of dicyclopentenyloxyethyl acrylate, and t-dodecyl as a molecular weight regulator. Mercaptan (0.18 part) and a redox catalyst were charged into a reactor and the temperature was adjusted to 15 ° C., and 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction, thereby obtaining a polymer latex (11).
Thereafter, 1 part of an anti-aging agent (trade name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (11) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salting out is performed. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (11)).
The obtained copolymer (11) had a weight average molecular weight of 3,670,000, and the content ratio of structural units derived from acrylonitrile (structural units derived from unsaturated nitrile monomers) was 15% by mass. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 1% by mass.

(Synthesis Example 12)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the resulting aqueous solution, a monomer component consisting of 84 parts of butyl acrylate, 15 parts of acrylonitrile, 1 part of dicyclopentenyloxyethyl acrylate, 0.18 part of t-dodecyl mercaptan as a molecular weight regulator, redox After the catalyst was charged into the reactor and the temperature was adjusted to 15 ° C., 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction to obtain a polymer latex (12).
Thereafter, 1 part of an anti-aging agent (trade name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (12) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salting out is performed. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (12)).
The obtained copolymer (12) had a weight average molecular weight of 6,450,000, and the content ratio of a structural unit derived from acrylonitrile (a structural unit derived from an unsaturated nitrile monomer) was 15% by mass. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 1% by mass.

(Synthesis Example 13)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the obtained aqueous solution, a monomer component consisting of 42 parts of ethyl acrylate, 42 parts of butyl acrylate, 15 parts of acrylonitrile, and 1 part of dicyclopentenyloxyethyl acrylate, and t-dodecyl mercaptan as a molecular weight regulator, 18 parts and a redox catalyst were charged into a reactor and the temperature was adjusted to 15 ° C., and 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction to obtain a polymer latex (13).
Thereafter, 1 part of an anti-aging agent (trade name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (13) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salting out is performed. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (13)).
The obtained copolymer (13) had a weight average molecular weight of 5.14 million, and the content ratio of the structural unit derived from acrylonitrile (the structural unit derived from the unsaturated nitrile monomer) was 15% by mass. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 1% by mass.

(Synthesis Example 14)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the obtained aqueous solution, a monomer component consisting of 84 parts of ethyl acrylate, 15 parts of acrylonitrile, 1 part of dicyclopentenyloxyethyl acrylate, 0.35 part of t-dodecyl mercaptan as a molecular weight regulator, redox catalyst Were adjusted to 15 ° C., and 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction to obtain a polymer latex (9).
Thereafter, 1 part of an anti-aging agent (trade name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (14) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salting out is performed. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (14)).
The obtained copolymer (14) had a weight average molecular weight of 740,000, and the content ratio of a structural unit derived from acrylonitrile (a structural unit derived from an unsaturated nitrile monomer) was 15% by mass. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 1% by mass.

(Synthesis Example 15)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the resulting aqueous solution, a monomer component comprising 96 parts of ethyl acrylate, 3 parts of acrylonitrile, 1 part of dicyclopentenyloxyethyl acrylate, 0.05 part of t-dodecyl mercaptan as a molecular weight regulator, a redox catalyst Were adjusted to 15 ° C., and 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction, thereby obtaining a polymer latex (15).
Then, 1 part of an anti-aging agent (trade name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (15) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salting out is performed. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (15)).
The obtained copolymer (15) had a weight average molecular weight of 4.4 million, and the content ratio of a structural unit derived from acrylonitrile (a structural unit derived from an unsaturated nitrile monomer) was 3% by mass. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 1% by mass.

(Synthesis Example 16)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the resulting aqueous solution, a monomer component consisting of 96 parts of ethyl acrylate, 3 parts of acrylonitrile, 1 part of dicyclopentenyloxyethyl acrylate, 0.20 part of t-dodecyl mercaptan as a molecular weight regulator, redox catalyst Were adjusted to 15 ° C., and 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction, thereby obtaining a polymer latex (16).
Thereafter, 1 part of an anti-aging agent (trade name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (16) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salting out is performed. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (16)).
The obtained copolymer (16) had a weight average molecular weight of 1,150,000, and the content ratio of structural units derived from acrylonitrile (structural units derived from unsaturated nitrile monomers) was 3% by mass. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 1% by mass.

(Synthesis Example 17)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the obtained aqueous solution, a monomer component consisting of 96 parts of ethyl acrylate, 3 parts of acrylonitrile, 1 part of dicyclopentenyloxyethyl acrylate, 0.30 part of t-dodecyl mercaptan as a molecular weight regulator, a redox catalyst Were adjusted to 15 ° C., and 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction to obtain a polymer latex (17).
Thereafter, 1 part of an anti-aging agent (trade name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (17) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salted out. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (17)).
The obtained copolymer (17) had a weight average molecular weight of 520,000, and the content ratio of structural units derived from acrylonitrile (structural units derived from unsaturated nitrile monomers) was 3%. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 1% by mass.

(Synthesis Example 18)
First, an aqueous solution in which 7 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier was dissolved in 250 parts of water was obtained. Next, the obtained aqueous solution, a monomer component consisting of 94 parts of ethyl acrylate, 3 parts of acrylonitrile, 3 parts of allyl glycidyl ether, and a redox catalyst were charged into the reactor, the temperature was adjusted to 15 ° C., and polymerization was started. As an agent, 0.02 part of paramentane hydroperoxide was added. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction, thereby obtaining a polymer latex (18).
Thereafter, 1 part of an anti-aging agent (product name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (18) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salting out is performed. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (18)).
The obtained copolymer (18) had a weight average molecular weight of 910,000, and the content ratio of structural units derived from acrylonitrile (structural units derived from unsaturated nitrile monomers) was 3%. The content ratio of the structural unit derived from allyl glycidyl ether is 3% by mass.

(Synthesis Example 19)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the resulting aqueous solution, a monomer component consisting of 51 parts ethyl acrylate, 45 parts acrylonitrile, 4 parts dicyclopentenyloxyethyl acrylate, 0.53 parts t-dodecyl mercaptan as a molecular weight regulator, redox catalyst Were adjusted to 15 ° C., and 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction, thereby obtaining a polymer latex (19).
Thereafter, 1 part of an anti-aging agent (trade name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (19) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salting out is performed. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (19)).
The obtained copolymer (19) had a weight average molecular weight of 24.55 million, and the content ratio of the structural unit derived from acrylonitrile (the structural unit derived from the unsaturated nitrile monomer) was 45% by mass. It was. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 4% by mass.

(Synthesis Example 20)
First, an aqueous solution obtained by dissolving 6 parts of sodium alkyldiphenyl ether disulfonate (trade name: Perex SS-L, manufactured by Kao Corporation) as an emulsifier in 250 parts of water was obtained. Next, the obtained aqueous solution, a monomer component composed of 70 parts of ethyl acrylate, 15 parts of acrylonitrile, 15 parts of dicyclopentenyloxyethyl acrylate, 0.53 part of t-dodecyl mercaptan as a molecular weight regulator, redox catalyst Were adjusted to 15 ° C., and 0.02 part of paramentane hydroperoxide was added as a polymerization initiator. Thereafter, emulsion polymerization was carried out to a polymerization conversion rate of 95%. Next, 0.1 part of N, N′-diethylhydroxylamine was added as a reaction terminator to terminate the polymerization reaction to obtain a polymer latex (20).
Thereafter, 1 part of an anti-aging agent (trade name: Antage SP, manufactured by Kawaguchi Chemical Industry Co., Ltd.) and polymer latex (2) are added to 50 ° C. water in which 0.5% of the coagulant is dissolved, and salting out is performed. Went. Thereafter, the precipitate was washed with water, dehydrated, and dried with an air dryer set at 90 ° C. to obtain a rubbery copolymer (copolymer (20)).
The obtained copolymer (2) had a weight average molecular weight of 35.23 million, and the content ratio of structural units derived from acrylonitrile (structural units derived from unsaturated nitrile monomers) was 15% by mass. It was. The content ratio of the structural unit derived from dicyclopentenyloxyethyl acrylate is 1% by mass.

[Method for producing heat conductive sheet]
Example 1
40 parts by mass of the copolymer (1) obtained in Synthesis Example 1 and 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type) at 180 ° C. and 16 MPa, the filling rate of the thermally conductive filler (ratio of alumina particles when the total amount of copolymer (1) and alumina particles is 100% by volume) is A heat conductive sheet of 76.5% by volume was obtained. The above-described evaluation was performed on this heat conductive sheet.

(Example 2)
40 parts by mass of the copolymer (2) obtained in Synthesis Example 2, 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

(Example 3)
40 parts by mass of the copolymer (3) obtained in Synthesis Example 3, 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatechs Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

Example 4
40 parts by mass of the copolymer (4) obtained in Synthesis Example 4, 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

(Example 5)
40 parts by mass of the copolymer (5) obtained in Synthesis Example 5, 60 parts by mass of a phosphoric ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

(Example 6)
40 parts by mass of the copolymer (6) obtained in Synthesis Example 6, 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

(Example 7)
40 parts by mass of the copolymer (7) obtained in Synthesis Example 7 and 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

(Example 8)
40 parts by mass of the copolymer (8) obtained in Synthesis Example 8, 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

Example 9
40 parts by mass of the copolymer (9) obtained in Synthesis Example 9 and 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

(Example 10)
40 parts by mass of the copolymer (10) obtained in Synthesis Example 10 and 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

(Example 11)
40 parts by mass of the copolymer (11) obtained in Synthesis Example 11 and 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

(Example 12)
40 parts by mass of the copolymer (12) obtained in Synthesis Example 12 and 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

(Example 13)
40 parts by mass of the copolymer (13) obtained in Synthesis Example 13 and 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

(Comparative Example 1)
40 parts by mass of the copolymer (14) obtained in Synthesis Example 14 and 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

(Comparative Example 2)
40 parts by mass of the copolymer (15) obtained in Synthesis Example 15 and 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

(Comparative Example 3)
40 parts by mass of the copolymer (16) obtained in Synthesis Example 16 and 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

(Comparative Example 4)
40 parts by mass of the copolymer (17) obtained in Synthesis Example 17 and 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

(Comparative Example 5)
40 parts by mass of the copolymer (18) obtained in Synthesis Example 18 and 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

(Comparative Example 6)
40 parts by mass of the copolymer (19) obtained in Synthesis Example 19 and 60 parts by mass of a phosphoric ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

(Comparative Example 7)
40 parts by mass of the copolymer (20) obtained in Synthesis Example 20, 60 parts by mass of a phosphate ester (CR-741: manufactured by Daihachi Chemical Industry Co., Ltd.) and alumina particles (AO-509: manufactured by Admatex Co., Ltd.) 1000 parts by mass of an average particle diameter of 10 μm was kneaded at 150 ° C. and 60 rpm with a Laboplast mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a composition for a heat conductive sheet. Manufactured by AT-37 type), a heat conductive sheet having a filling rate of 76.5% by volume of the heat conductive filler was obtained at 180 ° C. and 16 MPa. The above-described evaluation was performed on this heat conductive sheet.

DESCRIPTION OF SYMBOLS 1 Sheet laminated body 2,3 Protective sheet 4 Thermal conductive sheet 2a, 3a Release-treated surface 4a, 4b Surface of thermal conductive sheet

Claims (6)

(A) an acrylic rubber having a weight average molecular weight of 2 million to 20,000,000 and a content of structural units derived from unsaturated nitrile monomers of 5 to 40% by mass; and
(B) a thermally conductive filler,
The composition for heat conductive sheets containing this.   The composition for heat conductive sheets according to claim 1, wherein the volume ratio ((A) / (B)) of the acrylic rubber (A) and the heat conductive filler (B) is 15/85 to 85/15. .   The thermally conductive filler (B) is made of at least one selected from the group consisting of metal, metal oxide, metal hydroxide, carbon, boron nitride, aluminum nitride, silicon nitride, silicon carbide, and silica. The composition for heat conductive sheets of 1 or 2.   The composition for heat conductive sheets of any one of Claims 1-3 containing a flame retardant (C).   The heat conductive sheet formed by hardening | curing the composition for heat conductive sheets of any one of Claims 1-4.   A sheet laminate comprising the thermally conductive sheet according to claim 5 and a protective sheet laminated on each of both surfaces of the thermally conductive sheet.

Images