JP7362340B2 - Resin compositions, TIM and electronic devices - Google Patents

Description

The present invention relates to a resin composition, a TIM, and an electronic device.

In recent years, electronic devices have become more sophisticated and smaller, and electronic components are becoming more densely packed. For this reason, controlling the heat generated by devices and components has become a major issue in order to ensure their normal operation and longevity. As one measure to address this issue, methods have been developed to dissipate heat to the outside of electronic devices, and many electronic devices incorporate heat dissipation members such as heat sinks, heat spreaders, heat pipes, and cooling fans. Furthermore, some small devices such as mobile phones are designed so that the casing itself functions as a heat dissipation member to dissipate heat to the outside. In these electronic devices, a member called Thermal Interface Material (hereinafter also referred to as "TIM") is used for the purpose of improving heat conduction between a heating element and a heat radiating member or between heat radiating members.

TIM is roughly divided into two components. One is a filler that ensures heat conduction. For this purpose, metal oxides, metal nitrides, metal hydroxides, metal carbides, metal powders, etc. with high thermal conductivity are used. Another component is a binder that holds the filler and keeps the TIM in shape. As the binder, various organic materials such as curable resins such as silicone and acrylic, thermoplastic resins, elastomers, oils, and waxes are used, although they vary greatly depending on the type of TIM.

Among these, silicone compounds are often used as binders from the viewpoint of heat resistance stability of TIM itself. For example, Patent Document 1 discloses a thermal grease containing aluminum nitride, zinc oxide, and silicone oil. However, low-molecular-weight siloxane that silicone-based compounds themselves contain or that are gradually decomposed and produced from silicone-based compounds can precipitate on electronic circuits as insulating foreign substances such as silicon dioxide, causing contact failure. Non-silicone TIMs are being actively developed.

For example, Patent Document 2 discloses a thermally conductive grease containing a thermally conductive filler such as zinc oxide and a base oil made of a copolymer of an unsaturated dicarboxylic acid ester and an α-olefin. For efficient heat conduction of the TIM, it is important to minimize the contact thermal resistance at the interface between the TIM and the heat dissipation member and the thermal resistance of the TIM itself. In this respect, heat dissipating grease is widely used because it can adhere to the heat dissipating member by following the irregularities on the surface thereof and can be made thinner. However, the heat dissipating grease is in the form of a paste and has a problem of poor workability.

To solve this problem, TIM called phase change material (hereinafter also referred to as "PCM") has been developed. PCM is formed into a sheet or film shape at room temperature and is easy to handle, but after it is installed on a heat dissipation member, it melts or softens due to the heat generated by equipment operation, and does not conform to the shape and irregularities of the heat dissipation member. By making the thickness thinner, it is possible to reduce the contact thermal resistance and the thermal resistance of the TIM itself. For example, Patent Document 3 discloses a PCM containing an inorganic filler made of aluminum oxide and/or zinc oxide and aluminum nitride, and a binder made of liquid paraffin and an ethylene/vinyl acetate copolymer. .

Japanese Patent Application Publication No. 10-110179 Japanese Patent Application Publication No. 2006-188638 Japanese Patent Application Publication No. 2010-21165

However, in the PCM described in Patent Document 3, as the electronic device is used, the binder component gradually flows out from the PCM, which may lead to contamination of peripheral components and an increase in contact thermal resistance.

The present invention is a resin composition suitable for PCM, which is easy to handle among TIM used for the purpose of heat dissipation in electronic components, has excellent thermal conductivity, and has a binder component when softened and melted. An object of the present invention is to provide a resin composition from which a TIM that is difficult to separate and flow out and has excellent heat resistance stability can be obtained.

The present inventors have made extensive studies to solve the above problems. As a result, it was discovered that the above-mentioned problems could be solved by the following configuration example, and the present invention was completed. A configuration example of the present invention is as follows.

[1] A resin composition containing 100 parts by mass of the following binder (B) and 100 to 1000 parts by mass of filler (A).
・Binder (B):
One or more types selected from a graft modified product (Y) of an α-olefin (co)polymer and an α-olefin (co)polymer (X) that satisfies the following requirements (x-1) to (x-3) Component (P) containing 10 to 70% by mass based on 100% by mass of the binder (B), and
Contains one or more compounds (Q) selected from olefin resins, styrene thermoplastic elastomers, and waxes (excluding component (P)) (x-1) Methyl group index measured from ¹ H-NMR is 25 to 60%. [Here, the methyl group index is determined by dissolving the α-olefin (co)polymer (X) in deuterated chloroform and measuring ¹ H-NMR. When the solvent peak based on CHCl ₃ (7.24 ppm) is used as a reference, the integral value of the peak in the range of 0.50 to 2.20 ppm is compared to the integral value of the peak in the range of 0.50 to 1.15 ppm. It refers to the ratio of the integral value. ]
(x-2) The kinematic viscosity at 100°C is 400 to 10,000 mm ² /s (x-3) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 5,000 to 25, It is 000

[2] The α-olefin (co)polymer (X) is included, and the (co)polymer (X) has a kinematic viscosity of 500 to 4,000 mm ² /s at 100°C, described in [1]. resin composition.

[3] Contains the graft modified product (Y), where the graft modified product (Y) is made of one or more selected from unsaturated carboxylic acid compounds and unsaturated carboxylic acid derivatives of α-olefin (co)polymers. The resin composition according to [1] or [2], which is a modified product.
[4] Contains the graft modified product (Y), where the graft modified product (Y) is a modified product of an α-olefin (co)polymer with one or more selected from maleic acid and maleic anhydride. , the resin composition according to any one of [1] to [3].

[5] The filler (A) is made of aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, aluminum nitride, boron nitride, silicon dioxide, carbon black, carbon nanofibers, carbon nanotubes, silicon carbide, and silicon nitride. The resin composition according to any one of [1] to [4], which contains one or more selected fillers.

[6] The graft modified product (Y) according to any one of [1] to [5], wherein the graft modified product (Y) satisfies the following requirements (y-1) to (y-3). Resin composition.
(y-1) Acid value is 10 to 150 mgKOH/g (y-2) Apparent viscosity at 150°C is 50 to 1,500 mPa・s (y-3) Determined by gel permeation chromatography (GPC) The weight average molecular weight (Mw) is 3,000 to 25,000.

[7] A TIM (Thermal Interface Material) which is a molded article of the resin composition according to any one of [1] to [6].
[8] The TIM according to [7], which is a phase change material (PCM).
[9] An electronic device including the TIM according to [7] or [8].

According to the present invention, it is possible to provide a resin composition that has excellent thermal conductivity, binder components are difficult to separate and flow out during softening and melting, and can yield TIM that has excellent heat resistance stability. . Furthermore, according to the present invention, binder components, foreign substances, and the like are unlikely to flow out even in an environment where the electronic component is used at a high temperature (eg, 150° C.), so it is possible to obtain an electronic component that is less prone to contact failure.
Therefore, the resin composition according to the present invention is suitably used for heat dissipation of electronic components that generate heat, and specifically, it is suitably used as a TIM, particularly as a PCM.

The present invention will be explained in detail below.
In this specification, "~" indicating a numerical range, for example, in the case of "M~N", means "M or more and N or less" unless otherwise specified.
In this specification, the term "(co)polymer" is used as a concept encompassing both homopolymers and copolymers.
In this specification, when the olefin constituting a certain (co)polymer is M, the expression "constituent unit derived from M" may be used, but this refers to "constituent unit corresponding to M". In other words, it refers to a structural unit having a pair of bonds formed by opening the π bond constituting the double bond of M.
In this specification, the term "vinyl compound" refers to compounds containing a vinyl group such as α-olefins and carboxylic acid vinyl esters, as well as compounds having a vinylidene moiety such as methacrylic acid derivatives, internal olefins such as maleic acid derivatives, It is also used as a concept to encompass compounds with carbon-carbon double bonds, such as diene compounds such as butadiene and 5-ethylidene-2-norbornene.
In this specification, the term "(meth)acrylic" is used as a concept encompassing acrylic, methacrylic, or both acrylic and methacrylic.

≪Resin composition≫
The resin composition according to the present invention (hereinafter also referred to as "the present composition") contains a filler (A) and the following binder (B).

<Filler (A)>
The filler (A) is preferably a component that can improve the thermal conductivity of the present composition. Examples of such fillers (A) include thermally conductive fillers, and specific examples include metals, metal oxides, metal nitrides, metal hydroxides, metal carbides, metal fluorides, and carbon. It will be done.
The number of fillers (A) contained in the present composition may be one, or two or more.

More specifically, the filler (A) includes, for example, aluminum, copper, silver, magnesium oxide, aluminum oxide, zinc oxide, iron oxide, silicon dioxide, beryllium oxide, tin oxide, boron nitride, aluminum nitride, and nitride. Examples include silicon, magnesium hydroxide, aluminum hydroxide, boron carbide, silicon carbide, aluminum fluoride, calcium fluoride, carbon black, carbon nanofibers, carbon nanotubes, diamond, fullerene, and graphite.
Among these, aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, aluminum nitride, boron nitride, silicon dioxide, carbon black, carbon nano It is preferable to use one or more fillers selected from fibers, carbon nanotubes, silicon carbide, and silicon nitride.

The average particle size of the filler (A) is not particularly limited, but is preferably 0.1 to 30 μm, more preferably 0.2 to 20 μm. When the average particle size is within the above range, a resin composition with a high filling rate of the filler (A) and excellent thermal conductivity can be easily obtained, and the resin composition can be made thinner and the thermal resistance can be sufficiently reduced. TIM can be easily obtained.
If the average particle size is larger than the above upper limit, it tends to be difficult to reduce the thickness of the TIM, so it may not be possible to sufficiently reduce the thermal resistance of the TIM. Moreover, if the average particle size is smaller than the lower limit, the filling rate of the filler (A) cannot be increased, and thermal conductivity may not be sufficiently improved.
In addition, in order to increase the filling rate of the filler (A), the present composition may contain two or more types of fillers having different average particle sizes.
The average particle size can be determined by image analysis methods such as transmission electron microscopy or scanning electron microscopy, laser methods such as light scattering methods and optical diffraction methods, electrical detection zone methods, sieving methods, sedimentation methods, impact separation methods, and inertia methods. It can be measured using known methods such as an inertial method using a spectrometer, a separation method using a multistage cyclone method or a mobility analyzer, and a chromatography method.

As the filler (A), fillers having various shapes such as spherical, plate-like, polygonal, granular, and fibrous shapes can be used.
When using a filler (A) having anisotropy, the strength, thermal conductivity, etc. of the resin composition in a predetermined direction can be improved by appropriately controlling the orientation in the composition.
Note that the average particle diameter of fillers other than spherical fillers refers to the length of their longest side (eg, fiber length in the case of fibrous fillers).

The content of the filler (A) is 100 to 1000 parts by mass, preferably 100 to 700 parts by mass, more preferably 150 to 650 parts by mass, and particularly preferably is 200 to 600 parts by mass. When the content of the filler (A) is within the above range, a resin composition having excellent thermal conductivity, moldability, and mechanical properties can be easily obtained.
If the content of the filler (A) is less than the lower limit, sufficient thermal conductivity cannot be imparted to the composition, and the content of the filler (A) is higher than the upper limit. This tends to deteriorate the moldability and mechanical properties of the resin composition, making it difficult to mold it into a sheet or film.

<Binder (B)>
The binder (B) contains the following component (P) and a compound (Q) other than component (P).

<Ingredient (P)>
The component (P) is a graft modified product (Y) of an α-olefin (co)polymer (hereinafter also simply referred to as "modified product (Y)"), and the following requirements (x-1) to (x -3), preferably a modified product (Y) and a polymer Consisting of one or more types selected from combination (X).
Component (P) may contain two or more types of polymers (X), may contain two or more types of modified products (Y), and may contain two or more types of polymers (X) and two types. The above modified product (Y) may be included.

The content of component (P) based on 100% by mass of binder (B) is 10 to 70% by mass, preferably 15 to 65% by mass.
When the content of component (P) is within the above range, the fluidity of binder (B) can be appropriately controlled, and even at high temperatures, it is possible to prevent binder (B) from flowing out and increasing thermal resistance. Furthermore, the PCM can be made sufficiently thin at high temperatures and the thermal resistance can be reduced.

[Polymer (X)]
The polymer (X) is an α-olefin (co)polymer that satisfies the following requirements (x-1) to (x-3).

- Requirement (x-1): The methyl group index measured by ¹ H-NMR is 25 to 60%. The methyl group index is preferably 30 to 55%.
When the methyl group index is within the above range, it is possible to easily obtain a resin composition that has high stability against heat and suppresses an increase in thermal resistance due to outflow of the binder (B).

The polymer (X) is characterized in that the proportion of methyl groups in all protons is within a certain range. In general, protons of methyl groups have a peak observed on the high magnetic field side in ¹ H-NMR measurements (``Polymer Analysis Handbook'' (published by Asakura Shoten, pp. 163-170)). Therefore, in the present invention, the ratio of peaks on the high magnetic field side observed when measured by ¹ H-NMR is used as an index of methyl groups (referred to as "methyl group index"). Specifically, the polymer (X) was dissolved in deuterated chloroform and ¹ H-NMR was measured, and when the solvent peak appearing at 7.24 ppm based on CHCl ₃ in deuterated chloroform was used as a reference, 0.50 The ratio of the integral value of the peak within the range of 0.50 to 1.15 ppm to the integral value of the peak within the range of 2.20 ppm was taken as the methyl group index. Incidentally, as a specific method for measuring ¹ H-NMR, the method described in the following Examples can be mentioned.
Here, the peak based on the polymer (X) is almost included in the range of 0.50 to 2.20 ppm. Within this range, peaks based on methyl groups are often included within the range of 0.50 to 1.15 ppm.

The methyl group index can be controlled by selecting and polymerizing an appropriate α-olefin. For example, since an ethylene homopolymer does not have methyl groups, it is necessary to appropriately copolymerize an α-olefin having 3 to 20 carbon atoms to increase the proportion of methyl groups.

- Requirement (x-2): The kinematic viscosity at 100° C. is 400 to 10,000 mm ² /s. The kinematic viscosity is preferably 500 mm ² /s or more, more preferably 1,000 mm ² /s or more, particularly preferably is 1,500 mm ² /s or more, preferably 8,000 mm ² /s or less, more preferably 6,000 mm ² /s or less, even more preferably 4,500 mm ² /s or less, particularly preferably 4,000 mm ² /s or less.
When the kinematic viscosity is within the above range, it is possible to prevent the binder (B) from flowing out at high temperatures and increase the thermal resistance, and at the same time, the PCM can be made into a sufficiently thin film at high temperatures and the thermal resistance can be reduced.
The kinematic viscosity can be measured by the method described in JIS K2283.

- Requirement (x-3): Mw determined by GPC is 5,000 to 25,000. The Mw is preferably 6,000 to 20,000, more preferably 7,000 to 17,000. be.
When Mw is within the above range, it is possible to easily obtain a binder (B) that is excellent in compatibility with the compound (Q) and fluidity in a well-balanced manner, and when used at high temperatures, it is easy to form a thin layer. At the same time, it is possible to easily obtain a PCM in which the binder (B) is less likely to flow out, the thermal resistance is reduced, and the increase in thermal resistance over time is suppressed.

Further, the molecular weight distribution (Mw/Mn) of the polymer (X) is not particularly limited, but is usually 3 or less, preferably 2.5 or less, and more preferably 2.2 or less. Mw/Mn is usually 1.0 or more, preferably 1.2 or more.
When the Mw/Mn of the polymer (X) is within the above range, it is possible to easily obtain a binder (B) that is excellent in compatibility with the compound (Q), fluidity, and heat resistance in a well-balanced manner, and has low thermal resistance. It is possible to easily obtain a resin composition in which thermal resistance is reduced and an increase in thermal resistance over time due to outflow of the binder (B) is suppressed.

The Mw and Mw/Mn of the polymer (X) can be measured by GPC calibrated using a standard substance with a known molecular weight (monodisperse polystyrene), and specifically, by the method described in the example below. Can be measured.

-Properties of polymer (X) Polymer (X) is preferably liquid at room temperature (eg 20 to 25°C). It is preferable that the resin composition is liquid at room temperature because flexibility can be imparted to the resin composition at room temperature and the resin composition can be easily handled.

- Structure of polymer (X) Specific examples of polymer (X) include homopolymers of α-olefins having 2 to 20 carbon atoms or copolymers of two or more α-olefins. Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene. , 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, linear α-olefin such as 1-eicosene, 3-methyl-1 - α with branches such as pentene, 4-methyl-1-pentene, 8-methyl-1-nonene, 7-methyl-1-decene, 6-methyl-1-undecene, 6,8-dimethyl-1-decene, etc. - Examples include olefins. These α-olefins may be used alone or in combination of two or more.

A preferred embodiment of the polymer (X) is an ethylene/α-olefin copolymer. Examples of the α-olefin include α-olefins having 3 or more carbon atoms other than ethylene, and typical examples include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1- α with 3 to 20 carbon atoms such as decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, etc. - Examples include olefins. These α-olefins may be used alone or in combination of two or more. However, in the ethylene/α-olefin copolymer, the content of structural units derived from α-olefin having 6 to 20 carbon atoms is less than 50 mol%.

Among these α-olefins, a composition that can effectively reduce crystallinity to obtain a liquid (co)polymer, has excellent compatibility with compound (Q), and exhibits the above-mentioned desired effects is preferred. α-olefins having 3 to 10 carbon atoms are preferred, and propylene is particularly preferred, from the standpoint of being able to easily obtain products and molded bodies.

The content of structural units derived from ethylene (hereinafter also referred to as "ethylene content") in the ethylene/α-olefin copolymer is preferably 30 to 85 mol%, more preferably 40 to 80 mol%.
When the ethylene content is within the above range, a resin composition with sufficient fluidity and low thermal resistance can be easily obtained.
The ethylene content can be measured from a ¹³ C-NMR spectrum, for example, according to the method described in "Polymer Analysis Handbook" (published by Asakura Shoten, pp. 163-170).

-Method for producing polymer (X) The method for producing polymer (X) is not particularly limited, and known methods may be used. For example, ethylene and an α-olefin are combined in the presence of a catalyst consisting of a compound containing a transition metal such as vanadium, zirconium, titanium, or hafnium, and an organoaluminum compound (e.g. organoaluminumoxy compound) and/or an ionizable ionic compound. Examples include a method of copolymerizing. Examples of such methods include WO 2000/34420, JP 62-121710, WO 2004/29062, JP 2004-175707, WO 2001/27124, etc. Examples include the method described in . Among these methods, methods using a catalyst system containing a metallocene compound such as zirconocene and an organoaluminumoxy compound (aluminoxane) not only allow the production of copolymers with high polymerization activity but also reduce the chlorine content and α - More preferred because it can reduce 2,1-insertion of olefins.

[Degenerate (Y)]
The modified product (Y) is not particularly limited as long as it is a graft modified product of an α-olefin (co)polymer, but preferably a substituent other than a saturated hydrocarbon group or a polar A (co)polymer to which a group has been added, more preferably one or more α-olefin (co)polymers selected from vinyl compounds and derivatives thereof having a substituent or polar group other than a saturated hydrocarbon group. Particularly preferred is a graft modified product of an α-olefin (co)polymer using a vinyl compound containing a polar group.
Note that the grafting positions of substituents other than saturated hydrocarbon groups and polar groups in the graft modified product are not particularly limited.

The α-olefin (co)polymer before modification in the modified product (Y) may be the above polymer (X), or may be a (co)polymer other than the above polymer (X). is preferably the polymer (X).
The α-olefin (co)polymer before modification is not particularly limited, but includes homopolymers of α-olefins having 2 to 20 carbon atoms or copolymers of two or more α-olefins. Examples of the α-olefin having 2 to 20 carbon atoms include the α-olefins described in the column of the structure of the polymer (X). These α-olefins may be used alone or in combination of two or more.

A preferred embodiment of the α-olefin (co)polymer before modification is an ethylene/α-olefin copolymer. Examples of the α-olefin include the α-olefins described in the column of preferred embodiments of the polymer (X). These α-olefins may be used alone or in combination of two or more.
As the α-olefin (co)polymer before modification, an ethylene/propylene copolymer is particularly preferred for the same reason as above.

Examples of the modification method include a method using one or more graft monomers selected from vinyl compounds and derivatives thereof having substituents other than saturated hydrocarbon groups and polar groups.
Examples of substituents other than the saturated hydrocarbon group include substituents having a (hetero)aromatic ring such as a benzene ring, naphthalene ring, pyridine ring, and thiophene ring; examples of the polar group include, for example, a carboxy group , acid anhydride groups, ether bonds, ester bonds, hydroxy groups, oxygen-containing groups such as epoxy groups, amide groups, imide bonds, amino groups, nitrile groups, nitrogen-containing groups such as isocyanate groups, sulfinyl groups, sulfanyl groups, sulfonyl groups. Examples include sulfur-containing groups such as groups.

Examples of the vinyl compounds or derivatives thereof include vinyl compounds having aromatic rings such as styrene and allylbenzene, vinyl compounds having acids or acid-derived groups such as acids, acid anhydrides, esters, amides, and imides, alcohols, epoxy, ethers, etc. Examples include vinyl compounds having an oxygen-containing group, vinyl compounds having a nitrogen-containing group such as amine, nitrile, and isocyanate, and vinyl compounds having a silicon-containing group such as vinylsilane.

Among these, vinyl compounds having a polar group or derivatives thereof are preferred, vinyl compounds having an oxygen-containing group are more preferred, and specifically, unsaturated carboxylic acids and derivatives thereof, unsaturated epoxy monomers, etc. are preferred.

Examples of the unsaturated carboxylic acids include (meth)acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acid (endocys-bicyclo[2,2,1]heptate). -5-ene-2,3-dicarboxylic acid).
Examples of the derivatives of the unsaturated carboxylic acids include acid anhydrides, esters, amides, and imides of the unsaturated carboxylic acids.
Examples of the unsaturated epoxy monomer include unsaturated glycidyl ethers such as allyl glycidyl ether, unsaturated glycidyl esters such as glycidyl (meth)acrylate, monoglycidyl maleate, and diglycidyl maleate.

Examples of the unsaturated carboxylic acid ester include methyl (meth)acrylate, ethyl (meth)acrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, and monomethyl itaconate. Examples include esters, esters such as diethyl itaconate, and half esters.
Examples of the unsaturated carboxylic acid amide include (meth)acrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N,N-diethylamide, and maleic acid-N-monobutyl. Examples include amide, maleic acid-N,N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monobutylamide, and fumaric acid-N,N-dibutylamide.
Examples of the unsaturated carboxylic acid imide include maleimide, N-butylmaleimide, and N-phenylmaleimide.

Among these, unsaturated dicarboxylic acids and derivatives thereof are more preferred.
Further, maleic acid and maleic anhydride are particularly preferred because they are inexpensive, highly polar compounds, and are less likely to produce by-products such as homopolymers in the reaction for producing the modified product (Y).

The modified product (Y) preferably satisfies the following requirements (y-1) to (y-3).

- Requirement (y-1): The acid value is 10 to 150 mgKOH/g. The acid value is preferably 15 to 100 mgKOH/g.
The acid value is used as an indicator of the amount of grafting. When the acid value is within the above range, it has a well-balanced interaction with the filler (A), fluidity, and low corrosion resistance to metals, and contributes to reducing thermal resistance when using the resin composition and improving the soundness of equipment. can do.

The acid value can be adjusted by the amount of grafting. For example, in order to increase the acid value of the modified product (Y), it is preferable to increase the amount of grafting.

The acid value indicates the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of the polymer, and can be measured by a method based on JIS K2501:2003. Specifically, it is as described in Examples.

・Requirement (y-2): Apparent viscosity (Brookfield viscosity) at 150°C is 50 to 1,500 mPa·s. The apparent viscosity is measured by the method described in JIS K7117-1, and is preferably 100 to 1. ,000 mPa·s, more preferably 120 to 900 mPa·s.
When the apparent viscosity is within the above range, it is possible to prevent the binder (B) from flowing out at high temperatures and increase the thermal resistance, and at the same time, the PCM can be made into a sufficiently thin film at high temperatures and the thermal resistance can be reduced.

- Requirement (y-3): Weight average molecular weight (Mw) determined by GPC is 3,000 to 25,000. The Mw is preferably 7,000 to 20,000.
When the Mw of the modified product (Y) is within the above range, it is possible to easily obtain a binder (B) that is excellent in compatibility with the compound (Q) and fluidity in a well-balanced manner, and even at high temperatures, thinning is possible. At the same time, it is possible to easily obtain a PCM in which the binder (B) is difficult to flow out, the thermal resistance is reduced, and the increase in thermal resistance over time is suppressed.

The Mw of the modified product (Y) can be measured by GPC calibrated using a standard substance with a known molecular weight (monodisperse polystyrene), and specifically, by the method described in the Examples below.

- Method for producing modified product (Y) Modified product (Y) can be produced by various conventionally known methods, for example, methods (1) and (2) below.
(1) A method in which an α-olefin (co)polymer is charged into an extruder, a batch reactor, etc., and a graft monomer such as a vinyl compound having a polar group or its derivative is added thereto for graft copolymerization. .
(2) A method of graft copolymerization by dissolving an α-olefin (co)polymer in a solvent and adding a graft monomer such as a vinyl compound having a polar group or a derivative thereof.

In any of the above methods, in order to efficiently graft copolymerize the graft monomer, it is preferable to perform the graft copolymerization in the presence of one or more radical initiators.

Examples of the radical initiator include organic peroxides and azo compounds.
Examples of the organic peroxide include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, 2,5- Dimethyl-2,5-di(tert-butylperoxy)hexane, 1,4-bis(tert-butylperoxyisopropyl)benzene, etc. are mentioned, and the azo compounds include azobisisobutyronitrile, dimethylazoisobutyronitrile, etc. Examples include rate.
Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, 2,5-dimethyl-2,5-dimethyl Dialkyl peroxides such as (tert-butylperoxy)hexane and 1,4-bis(tert-butylperoxyisopropyl)benzene are preferably used.

The amount of the radical initiator used is usually 0.001 to 5 parts by weight, preferably 0.01 to 4 parts by weight, and more preferably 0. .05 to 3 parts by mass.

The reaction temperature during the graft copolymerization is usually 60 to 350°C, preferably 120 to 300°C.

In the graft modified product, the grafting amount of substituents other than saturated hydrocarbon groups and polar groups is usually 0.01 to 15% by mass, preferably 0.01 to 15% by mass, when the mass of the entire modified product (Y) is 100% by mass. .05 to 10% by mass.
The amount of grafting can be measured by a known method such as NMR analysis or IR analysis.

<Compound (Q)>
Compound (Q) is a compound other than component (P), and is one or more compounds selected from olefin resins, styrene thermoplastic elastomers, and waxes.
Compound (Q) has appropriate compatibility with component (P), so the fluidity of binder (B) can be appropriately controlled, and even at high temperatures, binder (B) flows out and thermal resistance is reduced. Among these, olefin resins are preferred because they can prevent the increase in heat resistance, and furthermore, can make the PCM a sufficiently thin film at high temperatures and can reduce thermal resistance.
Compound (Q) is preferably a compound that is solid at room temperature (0 to 30°C).

The content of compound (Q) based on 100% by mass of binder (B) is preferably 30 to 90% by mass, more preferably 35 to 85% by mass.
When the content of compound (Q) is within the above range, the fluidity of binder (B) can be appropriately controlled, and even at high temperatures, it is possible to prevent binder (B) from flowing out and increasing thermal resistance. Furthermore, the resin composition can be made into a sufficiently thin film at high temperatures, and the thermal resistance can be reduced.

[Olefin resin]
The olefin resin is a homopolymer or copolymer using an olefin as a monomer, and is a resin other than the polymer (X) and the modified product (Y).
The composition may contain two or more olefin resins.

Examples of olefins that can be used as the monomer include ethylene, propylene, 2-methylpropylene (isobutene, isobutylene), 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene. , 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1 -pentene, 4-methyl-1-pentene, 8-methyl-1-nonene, 7-methyl-1-decene, 6-methyl-1-undecene, and 6,8-dimethyl-1-decene. These olefins may be used alone or in combination of two or more.

As the monomer of the olefin resin, a cyclic olefin or a cyclic or chain polyene may be used. Examples of these monomers include cyclopentene, cycloheptene, norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, norbornadiene, methyltetrahydroindene, tetracyclododecene, butadiene, isoprene, chloroprene, Examples include 1,4-hexadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, and 4-ethylidene-1,7-undecadiene. These monomers may be used alone or in combination of two or more.

Furthermore, aromatic monomers, polar monomers, and polyenes can also be used as monomers for the olefin resin. Examples of these monomers include styrene, α-methylstyrene, vinyltoluene, isopropenyltoluene, and other styrene derivatives, vinyl acetate, vinyl propionate, vinyl benzoate, and other vinyl esters, (meth)acrylic acid, and (meth)acrylic acid. Methyl, (meth)acrylic acid derivatives such as ethyl (meth)acrylate, (meth)acrylic acid amide, and (meth)acrylic anhydride; Examples include diene compounds such as conjugated polyene, butadiene, and isoprene. These monomers may be used alone or in combination of two or more.

When using a polar monomer, the olefin resin may be a hydrolysis product of a resin obtained using a polar monomer, and is at least one metal salt selected from K, Na, Ca, and Zn. It may also be an ionomer.

Specific examples of the olefin resins include ethylene resins, propylene resins, other α-olefin resins, ethylene/vinyl ester copolymers, ethylene/vinyl alcohol copolymers, and ethylene/vinyl ester copolymers. Examples include partial hydrolyzate, ethylene/(meth)acrylic acid (derivative) copolymer, ethylene/α-olefin/non-conjugated polyene copolymer rubber, and butyl rubber.
Since the olefin resin has appropriate compatibility with component (P), the fluidity of binder (B) can be appropriately controlled, and even at high temperatures, binder (B) flows out and thermal resistance is reduced. Among these, ethylene-based resins and ethylene-vinyl ester copolymers are preferred because they can prevent the PCM from increasing in temperature and can also make the PCM a sufficiently thin film at high temperatures and can reduce thermal resistance.

[Ethylene resin]
The ethylene resin is a general term for ethylene homopolymers and ethylene/α-olefin copolymers in which the content of structural units derived from ethylene is 50 mol% or more and less than 100 mol%.
The composition may contain two or more ethylene resins.

The ethylene resin also includes polyethylene wax, which has a lower molecular weight than general polyethylene. As the ethylene resin, a binder (B) having a well-balanced melting point and melt viscosity can be easily obtained, and it can be used at high temperatures. In this method, it is possible to easily obtain a PCM in which the binder (B) is difficult to flow out, the thermal resistance is reduced, and the increase in thermal resistance over time is suppressed. , polyethylene wax is preferred.

When the ethylene resin is an ethylene/α-olefin copolymer, the α-olefin to be copolymerized with ethylene is not particularly limited, but α-olefins having 3 to 20 carbon atoms are preferred. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene. , 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-pentene, 4-methyl-1-pentene, 8-methyl-1-nonene, 7 -methyl-1-decene, 6-methyl-1-undecene, 6,8-dimethyl-1-decene and the like. Among these, α-olefins having 3 to 12 carbon atoms are particularly preferred. These α-olefins may be used alone or in combination of two or more.

The stereoregularity and chain structure of the ethylene/α-olefin copolymer are not particularly limited, and the ethylene/α-olefin copolymer may be a random copolymer or a block copolymer. Good too.

The ethylene resin includes low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), and high molecular weight polyethylene (HMWPE). ), various polyethylenes such as ultra-high molecular weight polyethylene (UHMWPE).

The weight average molecular weight (Mw) of the ethylene resin is preferably 500 to 5,000,000, more preferably 600 to 1,000,000, even more preferably 600 to 500,000.

The polyethylene waxes include low density polyethylene (LDPE) wax, medium density polyethylene (MDPE) wax, high density polyethylene (HDPE) wax, very low density polyethylene (VLDPE) wax, and linear low density polyethylene (LLDPE) wax. ) type waxes and various other polyethylene waxes are included.

The weight average molecular weight (Mw) of the polyethylene wax is preferably 500 to 40,000, more preferably 600 to 30,000. When Mw is within the above range, it is possible to easily obtain a binder (B) that is excellent in melting point and melt viscosity in a well-balanced manner, and at the same time, it is easy to form a thin layer at high temperatures, and at the same time, the binder (B) is difficult to flow out. A PCM with reduced thermal resistance and suppressed increase in thermal resistance over time can be easily obtained.

The Mw of the ethylene resin and polyethylene wax can be measured by GPC. Specifically, a calibration curve can be created using a standard substance with a known molecular weight (monodisperse polystyrene), and it can be determined based on the conversion method described below.
Molecular weight conversion method: polyethylene (PE) conversion/general-purpose calibration method The coefficients of the Mark-Houwink viscosity formula can be used for general-purpose calibration calculations. For the Mark-Houwink coefficients of polystyrene and polyethylene, the values described in the literature (J. Polym. Sci., Part A-2, 8, 1803 (1970), Makromol. Chem., 177, 213 (1976)) are used. be able to.

- Manufacturing method of ethylene resin The ethylene resin can be manufactured using various conventionally known methods. The method includes, for example, a known polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst containing a transition metal such as vanadium, zirconium, titanium, or hafnium, and an organoaluminum compound (e.g. organoaluminum oxy compound) and/or A method of (co)polymerization in the presence of a catalyst consisting of an ionized ionic compound, a method of radical (co)polymerization of monomers under high temperature and pressure, a method of cationic, anionic or radical (co)polymerization of monomers using an initiator. One method is to do so.
The polymerization method is not particularly limited either, and liquid phase polymerization methods such as solution polymerization method, suspension polymerization method, and bulk polymerization method, gas phase polymerization method, and other known polymerization methods can be used.
Further, the ethylene resin obtained by the above method may be thermally decomposed by a conventionally known method to reduce the molecular weight.

- Commercially available ethylene resin As the ethylene resin, commercially available products may be used, such as "Hyzex", "Neozex", "Urtozex", manufactured by Prime Polymer Co., Ltd. "Evolu", "Sumikasen" and "Excellen" manufactured by Sumitomo Chemical Co., Ltd., "Novatec LL", "Novatec C6", "Novatec HD", "Novatec LD", "Harmolex" manufactured by Japan Polyethylene Co., Ltd., Examples include "Exceed" and "Enable" manufactured by Exxon Mobil Chemical.
Commercially available polyethylene waxes include, for example, "Hiwax" and "Excelex" manufactured by Mitsui Chemicals, "Sunwax" manufactured by Sanyo Chemical Co., Ltd., and "Ceridust" manufactured by Clariant. Examples include "Licowax", "Licocene", and "AC" manufactured by Honeywell.

[Propylene resin]
The propylene-based resin includes a propylene homopolymer and a propylene/α-olefin copolymer in which the content of structural units derived from propylene is 50 mol% or more and less than 100 mol% (provided that the ethylene/α-olefin It is a general term for copolymers (other than copolymers).
The composition may contain two or more types of propylene resins.

When the propylene resin is a propylene/α-olefin copolymer, the α-olefin other than propylene to be copolymerized with propylene is not particularly limited, but α-olefins having 2 and 4 to 20 carbon atoms are preferred. Specifically, ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene. , 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-pentene, 4-methyl-1-pentene, 8-methyl-1-nonene, 7 -methyl-1-decene, 6-methyl-1-undecene, 6,8-dimethyl-1-decene and the like. Among these, α-olefins having 2 and 4 to 12 carbon atoms are particularly preferred. These α-olefins may be used alone or in combination of two or more.

The stereoregularity and chain structure of the propylene homopolymer are not particularly limited, and include propylene homopolymers having arbitrary stereoregularity and chain structure such as isotactic polypropylene, syndiotactic polypropylene, and atactic polypropylene. .
The stereoregularity and chain structure of the propylene/α-olefin copolymer are not particularly limited, and the propylene/α-olefin copolymer may be a random copolymer or a block copolymer. Good too.

The weight average molecular weight (Mw) of the propylene resin is preferably 1,000 to 5,000,000, more preferably 2,000 to 1,000,000, and even more preferably 2,000 to 500,000. .

The propylene resin also includes a polypropylene wax having a lower molecular weight than general polypropylene, and includes various polypropylene waxes such as homopolypropylene wax, block polypropylene wax, and random polypropylene wax.

The weight average molecular weight (Mw) of the polypropylene wax is preferably 1,000 to 50,000, more preferably 2,000 to 40,000. When Mw is within the above range, it is possible to easily obtain a binder (B) that is excellent in melting point and melt viscosity in a well-balanced manner, and at the same time, it is easy to form a thin layer at high temperatures, and at the same time, the binder (B) is difficult to flow out. A PCM with reduced thermal resistance and suppressed increase in thermal resistance over time can be easily obtained.

The Mw of the propylene resin and polypropylene wax can be measured by GPC. Specifically, a calibration curve can be created using a standard substance with a known molecular weight (monodisperse polystyrene), and it can be determined based on the conversion method described below.
Molecular weight conversion method: Polypropylene (PP) conversion/general-purpose calibration method The coefficients of the Mark-Houwink viscosity formula can be used for the general-purpose calibration calculation. For the Mark-Houwink coefficients of polystyrene and polypropylene, the values described in the literature (J. Polym. Sci., Part A-2, 8, 1803 (1970), Makromol. Chem., 177, 213 (1976)) are used. be able to.

-Propylene-based resin manufacturing method The propylene-based resin can be manufactured using various conventionally known methods. Examples of the method include the same methods as those described in the section on ethylene resins.

・Commercial product of propylene resin As the propylene resin, commercial products may be used. Examples of the commercial products include "Prime Polypro" manufactured by Prime Polymer Co., Ltd. and "Prime Polypro" manufactured by Nippon Polypro Co., Ltd. Examples include "Novatec PP", "Wintec", "Wellnex", "Waymax", "Nucon", and "Sumitomo Noblen", "Exelen", and "Tuffselen" manufactured by Sumitomo Chemical Co., Ltd.
Commercially available polypropylene waxes include, for example, "Hiwax" manufactured by Mitsui Chemicals, "Viscoll" manufactured by Sanyo Chemical Co., Ltd., and "Ceridust", "Licowax", and "Licocene" manufactured by Clariant. ” and “AC” manufactured by Honeywell.

[Other α-olefin resins]
The other α-olefin resins are resins other than the ethylene resins and propylene resins, and include, for example, homopolymers of α-olefins having 4 or more carbon atoms, and α-olefin resins having 4 or more carbon atoms. A copolymer of two or more types of α-olefins, a structural unit derived from one or more types selected from α-olefins having 4 or more carbon atoms, and a structural unit derived from one or more types selected from ethylene and propylene. (However, the content of structural units derived from ethylene is less than 50 mol%, and the content of structural units derived from propylene is less than 50 mol%.) It will be done. However, the other α-olefin resin is a resin other than the butyl rubber described below.
The composition may contain two or more other α-olefin resins.

The α-olefin having 4 or more carbon atoms is preferably an α-olefin having 4 to 20 carbon atoms, and examples of the α-olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1 -Octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene Linear α-olefins such as 3-methyl-1-pentene, 4-methyl-1-pentene, 8-methyl-1-nonene, 7-methyl-1-decene, 6-methyl-1-undecene, 6 , 8-dimethyl-1-decene and the like.

The stereoregularity and chain structure of the other α-olefin resins are not limited.
The other α-olefin resins include other α-olefin (co)polymer waxes (α-olefin (co)polymer waxes other than polyethylene waxes and polypropylene waxes) that have a lower molecular weight than general resins. is also included.

-Production method of other α-olefin resins The other α-olefin resins can be produced using various conventionally known methods. Examples of the method include the same methods as those described in the section on ethylene resins.

・Other commercially available α-olefin resins As the other α-olefin resins, commercially available products may be used, such as “Tafmer” manufactured by Mitsui Chemicals, DOW Examples include "ENGAGE", "AFFINITY GA", and "VERSIFY" manufactured by Chemical Company, and "Exxtral" and "Extra" manufactured by Exxon Mobil Chemical Company.

[Ethylene/vinyl ester copolymer]
The ethylene/vinyl ester copolymer is a copolymer of ethylene and one or more vinyl esters.
The stereoregularity and chain structure of the ethylene/vinyl ester copolymer are not particularly limited.
The composition may contain two or more ethylene vinyl ester copolymers.

Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl stearate.
Examples of the ethylene/vinyl ester copolymer include ethylene/vinyl acetate copolymer, ethylene/vinyl propionate copolymer, ethylene/vinyl butyrate copolymer, and ethylene/vinyl stearate copolymer. Among these, ethylene/vinyl acetate copolymer is particularly preferred.

The content of the structural units derived from ethylene in the ethylene/vinyl ester copolymer is preferably 40 to 95% by mass, and more It is preferably 42 to 93% by weight, particularly preferably 43 to 92% by weight.
When the content of the structural unit derived from ethylene is within the above range, the interaction with the filler (A) and the compatibility with the polymer (X) and/or the modified product (Y) are well-balanced. The binder (B) can be easily obtained, and a resin composition with reduced thermal resistance and suppressed increase in thermal resistance over time can be easily obtained.

- Method for producing ethylene/vinyl ester copolymer The ethylene/vinyl ester copolymer can be produced using various conventionally known methods. Examples of the method include the same methods as those described in the section on ethylene resins.

・Commercial product of ethylene/vinyl ester copolymer As the ethylene/vinyl ester copolymer, a commercial product may be used. "Flex", "Sumitate" manufactured by Sumitomo Chemical Co., Ltd., "Novatec EVA" manufactured by Nippon Polyethylene Co., Ltd., "Ultracene" manufactured by Tosoh Corporation, and "Escorene" manufactured by Exxon Mobil Chemical Company.

[Ethylene/vinyl alcohol copolymer]
Examples of the ethylene/vinyl alcohol copolymer include hydrolysates, specifically saponified products, of the ethylene/vinyl ester copolymer, and by hydrolyzing the ethylene/vinyl ester copolymer, ethylene - A vinyl alcohol copolymer can be obtained.
In this specification, the complete hydrolyzate of the ethylene/vinyl ester copolymer (with a saponification degree of 100%) is referred to as "ethylene/vinyl alcohol copolymer", and the ethylene/vinyl ester copolymer is referred to as "ethylene/vinyl alcohol copolymer". A partial hydrolyzate (having a degree of saponification greater than 0% and less than 100%) is referred to as a "partial hydrolyzate of ethylene/vinyl ester copolymer."
As the ethylene/vinyl alcohol copolymer, commercially available products may be used, and examples of the commercially available products include "Eval" manufactured by Kuraray Co., Ltd. and "Soarnol" manufactured by Mitsubishi Chemical Corporation.
The composition may contain two or more ethylene-vinyl alcohol copolymers.

[Partial hydrolyzate of ethylene/vinyl ester copolymer]
The partial hydrolyzate of the ethylene/vinyl ester copolymer is specifically a saponified product obtained by partially saponifying the ethylene/vinyl ester copolymer, and the degree of saponification is not particularly limited, but is preferably 0. % and less than 100%, more preferably more than 15% and less than 100%.
As the partial hydrolyzate of the ethylene/vinyl ester copolymer, a commercially available product may be used, and examples of the commercially available product include "Mersene H" manufactured by Tosoh Corporation.
The composition may contain a partial hydrolyzate of two or more types of ethylene/vinyl ester copolymers.

[Ethylene/(meth)acrylic acid (derivative) copolymer]
The ethylene/(meth)acrylic acid (derivative) copolymer is a copolymer of ethylene and one or more selected from (meth)acrylic acid and (meth)acrylic acid derivatives. be.
The stereoregularity and chain structure of the ethylene/(meth)acrylic acid (derivative) copolymer are not particularly limited.
The composition may contain two or more types of ethylene/(meth)acrylic acid (derivative) copolymers.

Examples of (meth)acrylic acid derivatives include (meth)acrylic anhydride, (meth)acrylic ester, (meth)acrylamide, and the like.
Examples of the (meth)acrylic ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, and (meth)acrylate. Examples include sec-butyl acrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.
Examples of the (meth)acrylamide include (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N,N -dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, N,N-diisopropyl (meth)acrylamide, and N-stearyl (meth)acrylamide.

Among these, ethylene/(meth)acrylate using methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate as (meth)acrylate esters Preferred are methyl acid copolymer, ethylene/ethyl (meth)acrylate copolymer, ethylene/propyl (meth)acrylate, and ethylene/butyl (meth)acrylate.

The ethylene/(meth)acrylic acid (derivative) copolymer may be a hydrolyzate of ethylene/(meth)acrylic acid copolymer or ethylene/(meth)acrylic acid ester copolymer, and may contain Na, An ionomer that is one or more metal salts selected from K, Ca, and Zn may also be used.

The content of the structural units derived from ethylene in the ethylene/(meth)acrylic acid (derivative) copolymer is 100% of the total structural units constituting the ethylene/ethylene/(meth)acrylic acid (derivative) copolymer. It is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass.
When the content of the structural unit derived from ethylene is within the above range, the interaction with the filler (A) and the compatibility with the polymer (X) and/or the modified product (Y) are well-balanced. The binder (B) can be easily obtained, and a resin composition with reduced thermal resistance and suppressed increase in thermal resistance over time can be easily obtained.

- Method for producing ethylene/(meth)acrylic acid (derivative) copolymer The ethylene/(meth)acrylic acid (derivative) copolymer can be produced using various conventionally known methods. Examples of the method include the same methods as those described in the section on ethylene resins.

- Commercial product of ethylene/(meth)acrylic acid (derivative) copolymer As the ethylene/(meth)acrylic acid (derivative) copolymer, a commercial product may be used, and examples of the commercial product include, for example, "Himilan", "Nucrel", "Elvaloy AC" manufactured by Mitsui-Dow Polychemicals Co., Ltd., "Acrift" and "Bond First" manufactured by Sumitomo Chemical Co., Ltd., "Lexval" manufactured by Japan Polyethylene Co., Ltd., Examples include "Escor", "Optema", "ExxonMobil EnBA copolymer resins" manufactured by Exxon Mobil Chemical, and "ACLYN" manufactured by Honeywell.

[Ethylene/α-olefin/non-conjugated polyene copolymer rubber]
The ethylene/α-olefin/non-conjugated polyene copolymer rubber is composed of a structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 or more carbon atoms, preferably 3 to 20 carbon atoms, and a non-conjugated polyene. It is a copolymer rubber containing structural units derived from the above.
The stereoregularity and chain structure of the ethylene/α-olefin/nonconjugated polyene copolymer rubber are not particularly limited. Further, in the ethylene/α-olefin/nonconjugated polyene copolymer rubber, there are no particular restrictions on the geometrical chemistry, such as cis or trans, or stereochemistry of the nonconjugated polyene.
The composition may contain two or more types of ethylene/α-olefin/nonconjugated polyene copolymer rubber.

Specifically, the α-olefin having 3 to 20 carbon atoms includes propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1- Undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 4-methyl-1-pentene, 9-methyl- Examples include 1-decene and 12-ethyl-1-tetradecene. Among these, α-olefins having 3 to 10 carbon atoms are preferred, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are more preferred, and propylene and 1-butene are particularly preferred. These α-olefins can be used alone or in combination of two or more.

Specific examples of the non-conjugated polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 4,5-hexadiene. Chain nonconjugated dienes such as dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-undecadiene, methyl Tetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclic non-conjugated dienes such as cyclopentadiene and norbornadiene, 2,3-diisopropylidene-5-norbornene, 2- Examples include trienes such as ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, and 4-ethylidene-8-methyl-1,7-nonadiene. Among these, 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, and a mixture of 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are preferred; Particularly preferred are ethylidene-2-norbornene, 5-vinyl-2-norbornene, and mixtures of 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene. These non-conjugated polyenes can be used alone or in combination of two or more.

The content of the structural units derived from ethylene in the ethylene/α-olefin/non-conjugated polyene copolymer rubber is based on the total of 100% by mass of the structural units derived from ethylene and the structural units derived from α-olefin. The content is preferably 55 to 99% by weight, more preferably 60 to 95% by weight, and even more preferably 70 to 90% by weight.

The content of the structural units derived from the non-conjugated polyene in the ethylene/α-olefin/non-conjugated polyene copolymer rubber is 100 parts by mass in total of the structural units derived from ethylene and the structural units derived from α-olefin. On the other hand, it is preferably 1 to 25 parts by weight, more preferably 1 to 20 parts by weight, and even more preferably 3 to 15 parts by weight.

・Method for producing ethylene/α-olefin/non-conjugated polyene copolymer rubber The ethylene/α-olefin/non-conjugated polyene copolymer rubber is produced using a known polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. can do. The polymerization method is not particularly limited either, and liquid phase polymerization methods such as solution polymerization method, suspension polymerization method, and bulk polymerization method, gas phase polymerization method, and other known polymerization methods can be used.

・Commercial product of ethylene/α-olefin/non-conjugated polyene copolymer rubber As the ethylene/α-olefin/non-conjugated polyene copolymer rubber, a commercial product may be used, such as Exxon Mobil. Examples include "Vistalon" manufactured by Chemical, "Esplen" manufactured by Sumitomo Chemical Co., Ltd., and "Mitsui EPT" manufactured by Mitsui Chemicals.

[Butyl rubber]
The butyl rubber is a (co)polymer containing a structural unit derived from isobutylene (isobutene, 2-methylpropylene). The butyl rubber may be a homopolymer of isobutylene or a copolymer of isobutylene and a comonomer other than isobutylene.
When the butyl rubber is a copolymer of isobutylene and a comonomer other than isobutylene, a diene compound, a styrene compound, etc. can be used as the comonomer, and one or more of these comonomers can be used. The stereoregularity and chain structure of the copolymer are not particularly limited.
The composition may contain two or more types of butyl rubber.

Examples of the diene compound include butadiene, isoprene, hexadiene, and chloroprene.
Examples of the styrene compounds include styrene, α-methylstyrene, 3-methylstyrene, and 4-methylstyrene.
Among these, isoprene and 4-methylstyrene are preferred.

The content of the structural units derived from isobutylene in the butyl-based rubber is preferably 85 to 99.8 mass% with respect to the total of 100% by mass of the structural units derived from isobutylene and the structural units derived from comonomers other than isobutylene. %, more preferably 90 to 99.5% by weight, even more preferably 92 to 99.5% by weight.

Note that halogen may be introduced into the butyl rubber. As the halogen, chlorine and bromine are preferable, and bromine is particularly preferable.
The halogen content in the halogen-containing butyl rubber is preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, based on 100% by mass of the entire butyl rubber.

Further, the butyl rubber may be a butyl rubber obtained by further secondary modification of a halogen-containing butyl rubber.
That is, the butyl rubbers include butyl rubber (isobutylene-isoprene copolymer, IIR), chlorinated butyl rubber (chlorinated product of butyl rubber, Cl-IIR), brominated butyl rubber (brominated product of butyl rubber, Br-IIR), isobutylene rubber, Contains brominated products of 4-methylstyrene copolymer.

- Method for producing butyl rubber The method for producing the butyl rubber is not particularly limited, but includes, for example, a method in which a monomer containing isobutylene is cationically polymerized in methane chloride using aluminum chloride as an initiator at a low temperature.
The method of introducing halogen into the butyl rubber is not particularly limited, and conventionally known methods such as copolymerizing a halogenated monomer or modifying a halogen-free butyl rubber and introducing a halogen can be used. Can be used. A common method is to introduce a halogen into butyl rubber using a simple halogen such as chlorine or bromine in a hydrocarbon solvent such as hexane.

- Commercial product of butyl rubber A commercial product may be used as the butyl rubber, and examples of the commercial product of the butyl rubber (IIR) include “Butyl” manufactured by Nippon Butyl Co., Ltd., and Exxon Mobil Chemical Company. Examples include "Exxon butyl rubber" manufactured by Manufacturer, Inc., and "X_Butyl RB" manufactured by Lanxees.
Examples of commercial products of the chlorinated butyl rubber (Cl-IIR) include "CHLOROBUTYL" manufactured by Nippon Butyl Co., Ltd., "Exxon chlorobutyl rubber" manufactured by Exxon Mobil Chemical, and "X_Butyl CB" manufactured by Lanxess. It will be done.
Examples of commercial products of the brominated butyl rubber (Br-IIR) include "BROMOBUTYL" manufactured by Nippon Butyl Co., Ltd., "Exxon bromobutyl rubber" manufactured by Exxon Mobil Chemical, and "X_Butyl BB" manufactured by Lanxess. It will be done.
A commercially available product of the brominated isobutylene/4-methylstyrene copolymer includes, for example, "Exxpro" manufactured by Exxon Mobil Chemical.

[Styrenic thermoplastic elastomer]
The styrenic thermoplastic elastomer is a block copolymer containing a polymer block mainly composed of structural units derived from a styrene compound and a polymer block mainly composed of structural units derived from a conjugated diene compound, and , one or more copolymers selected from these hydrogenated products.
The composition may contain two or more types of styrenic thermoplastic elastomers.

Specific examples of the styrene compounds include styrene, α-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, and 4-dodecyl. Examples include styrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, chlorostyrene, dichlorostyrene, methoxystyrene, indene, and acenaphthylene. These styrene compounds may be used alone or in combination of two or more. Among these, styrene is most preferred.

The conjugated diene compound is preferably a conjugated diene having 4 to 20 carbon atoms, and specific examples thereof include butadiene, isoprene, and hexadiene. These conjugated dienes may be used alone or in combination of two or more. Among these, butadiene and isoprene are most preferred.

The content of the polymer block mainly composed of structural units derived from a styrene compound in the styrenic thermoplastic elastomer is determined by the content of the polymer block mainly composed of structural units derived from a styrene compound and the polymer block mainly composed of structural units derived from a styrene compound and a conjugated diene compound. The amount is preferably 5 to 80 mass %, more preferably 10 to 75 mass %, and even more preferably 20 to 40 mass %, based on the total 100 mass % of the polymer block mainly composed of the structural units.

The styrenic thermoplastic elastomer has a polymer block mainly composed of a structural unit derived from at least one styrene compound in the molecule, and a polymer mainly composed of a structural unit derived from at least one conjugated diene compound. The structure is not particularly limited as long as it has a block, and the structure is not particularly limited and may be either linear or branched. Preferably, a polymer block mainly composed of structural units derived from a styrene compound, a polymer block mainly composed of structural units derived from a conjugated diene compound, and a polymer block mainly composed of structural units derived from a styrene compound. It is a type of triblock copolymer.

Specific examples of the styrene thermoplastic elastomer include styrene/butadiene/styrene block copolymer, styrene/isoprene/styrene block copolymer, and styrene/butadiene/isoprene/styrene block copolymer.
Note that, for example, the styrene-butadiene-styrene block copolymer means a block copolymer in the form of polystyrene block-polybutadiene block-polystyrene block.

The styrenic thermoplastic elastomer is a block copolymer containing a polymer block mainly composed of structural units derived from a styrene compound and a polymer block mainly composed of structural units derived from a conjugated diene compound. Additives can also be used. It is preferable to use this hydrogenated material because hydrogenation reduces aliphatic double bonds and improves heat resistance.

The hydrogenated product is preferably a copolymer in which 90 to 100% of aliphatic double bonds are hydrogenated and 0 to 10% of aromatic double bonds are hydrogenated, particularly a copolymer in which 99 to 100% of aliphatic double bonds are hydrogenated. Preferred is a copolymer in which the aliphatic double bonds are hydrogenated and 0 to 5% of the aromatic double bonds are hydrogenated.

・Method for producing a styrenic thermoplastic elastomer The method for producing the styrenic thermoplastic elastomer is not particularly limited, but for example, using a suitable polymerization initiator system, a styrene compound such as styrene and butadiene, etc. are mixed in an inert solvent. It can be produced by sequentially polymerizing the following conjugated diene compounds.

An example of the polymerization initiator system in this case is a mixed system of a Lewis acid and an organic compound that generates a cationic polymerization active species by the Lewis acid. Examples of the Lewis acid include titanium tetrachloride, tin tetrachloride, boron trichloride, aluminum chloride, etc., and examples of the organic compound include organic compounds having a functional group such as an alkoxy group, an acyloxy group, and/or a halogen, etc. , bis(2-methoxy-2-propyl)benzene, bis(2-acetoxy-2-propyl)benzene, and bis(2-chloro-2-propyl)benzene.
Furthermore, in addition to the Lewis acid and organic compound described above, for example, amides such as N,N-dimethylacetamide, and esters such as ethyl acetate may be used as a third component, if necessary.
Further, examples of the inert solvent include hexane, cyclohexane, methylcyclohexane, methyl chloride, and methylene chloride.

Linear styrenic thermoplastic elastomers are, for example,
(1) As a polymerization initiator system, a styrene compound is polymerized to form a polymer block using a Lewis acid and a compound having one functional group that generates a cationic polymerization active species, and then a conjugated diene compound is A method in which a styrene compound is added to a reaction system and polymerized to form a polymer block, and if necessary, a styrene compound is further added and polymerized to form a polymer block.
(2) As a polymerization initiator system, a compound having two functional groups that generate a Lewis acid and a cationic polymerization active species is used to first polymerize a conjugated diene compound to form a polymer block, and then the reaction system It can be produced by a method in which a styrene compound is added to polymerize to form a polymer block.

In addition, styrenic thermoplastic elastomers are produced by first polymerizing a conjugated diene compound using, for example, a Lewis acid and a compound having three or more functional groups that generate cationic polymerization active species as a polymerization initiator system. It can also be produced by a method in which a block is formed, then a styrene compound is added and polymerized to form a polymer block.

The hydrogenated product can be obtained by hydrogenating the block copolymer by a known method.
In this hydrogenation, it is preferable to use a hydrogenation catalyst, such as platinum, palladium, etc. on a carrier such as nickel, porous diatomaceous earth, Raney nickel, copper dichromate, molybdenum sulfide, or carbon. Examples include things that were supported.
Note that the hydrogenation may be carried out at any pressure (for example, atmospheric pressure to 300 atm, preferably 5 to 200 atm), at any temperature (for example, 20 to 350°C), and for any time (for example, 0.2 to 10 atm). time).

・Commercial product of styrene thermoplastic elastomer As the styrene thermoplastic elastomer, a commercial product may be used. Examples of non-hydrogenated commercial products include "D series" manufactured by Clayton Co., Ltd., and JSR Co., Ltd. ) "TR series" manufactured by Asahi Kasei Corporation, "Tuffprene" and "Asaprene".
Commercially available hydrogenated products include, for example, "Septon" and "Hybler" manufactured by Kuraray Co., Ltd., "Tuftec" manufactured by Asahi Kasei Corporation, "Dynalon" manufactured by JSR Corporation, and "Dynalon" manufactured by Clayton Polymer Co., Ltd. One example is the "G series."

[wax]
Examples of the wax include paraffin wax, microcrystalline wax, petrolatum, Fischer-Tropsch wax, fatty acid derivative wax, animal and vegetable wax, and mineral wax.
Note that the wax is a wax other than polyolefin wax (polyethylene wax, polypropylene wax, or other α-olefin (co)polymer wax).

Examples of the paraffin wax include waxes that are separated and purified from vacuum distillation distillate of petroleum and are solid at room temperature, and specific examples include waxes that are mainly composed of straight-chain alkanes (paraffins) having 20 to 60 carbon atoms. Examples include waxes containing
Examples of the microcrystalline wax include waxes that are solid at room temperature separated and purified from residual oil or heavy distillate from petroleum vacuum distillation, and specific examples include branched alkanes with 20 to 60 carbon atoms ( Examples include waxes containing as a main component a cyclic cycloalkane (isoparaffin) and/or a cyclic cycloalkane.
Examples of the petrolatum include waxes that are semi-solid at room temperature and are separated and purified from residual oil of petroleum distillation under reduced pressure.
Examples of the fatty acid derivative wax include fatty acids, fatty acid calcium salts, fatty acid methyl esters, fatty acid ethyl esters, and fatty acid amides. These fatty acids include, for example, lauric acid, myristic acid, palmitic acid, stearic acid, and arachidic acid.
Examples of the animal and plant waxes include beeswax, spermaceti, shellac wax, carnauba wax, and wood wax.
Examples of the mineral wax include montan wax, ozokerite, and ceresin.

[Other embodiments of compound (Q)]
The above-mentioned compound (Q) may be the above-mentioned compound as it is, or a modified form of the above-mentioned compound to which some substituent and polar group are added (however, it is a compound other than the above-mentioned modified form (Y)). ) may be used. Compound (Q) can be used alone or in combination of two or more of these.
The method of modification is not limited, and various conventionally known modification methods can be used. For example, oxidation reactions with oxygen or peroxides, reactions starting from carboxy group sites such as hydrolysis, saponification, esterification, and amidation, reactions with simple halogens such as chlorine and bromine, and reactions with good elimination ability (pseudo) Examples include nucleophilic substitution reactions and nucleophilic elimination reactions at halogenated alkyl moieties, and graft reactions in which a vinyl compound or the like is reacted in the presence of a radical initiator.

<Other ingredients>
The present composition may contain other components other than the filler (A) and the binder (B) as long as the object of the present invention is not impaired. The other components include oil or polymer components other than the binder (B), weathering stabilizers, heat resistant stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, antislip agents, antiblocking agents, and antifogging agents. agent, nucleating agent, lubricant, pigment, dye, anti-aging agent, hydrochloric acid absorbent, organic or inorganic blowing agent, crosslinking agent, co-crosslinking agent, crosslinking aid, adhesive, plasticizer, flame retardant, mold release agent , antibacterial agents, surfactants, crystallization aids, impact modifiers, processing aids, and the like.

Note that this composition does not substantially contain any components that may flow out from the composition at high temperatures (e.g., 150° C.) or components that generate substances that cause contact failure in electronic components. The content of this component is preferably 1% by mass or less based on 100% by mass of the present composition, and specific examples of such components include polydimethylsiloxane, polydimethyldiphenylsiloxane, Examples include silicone oil and modified silicone oil (liquid silicone) made of polydimethylhydromethylsiloxane and the like.

<Method for manufacturing resin composition>
The method for producing the present composition is not particularly limited, and the filler (A), the binder (B), and the optionally used other components may be mixed (or kneaded, hereinafter the same) in a predetermined ratio by a known method. ) can be obtained by doing. Specifically, for example, by mixing and kneading the filler (A), binder (B), and other components using a mixing/kneading means such as an extruder, Banbury mixer, mixing roll, Henschel mixer, or kneader. can be manufactured.

The filler (A) may be mixed with components other than the filler (A) constituting the present composition, and in the final stage of producing the present composition, the filler (A) constituting the present composition may be mixed with other components. It may be added to a composition containing all components other than A) and mixed. In addition, a part of the filler (A) is mixed with components other than the filler (A) constituting the present composition, and in the final stage of manufacturing the present composition, the remaining filler (A) is mixed with the remaining filler (A). may be added and mixed.
The same applies to the binder (B) and other components used as necessary.

≪TIM≫
The TIM, particularly the PCM, according to the present invention is a molded product of the present composition, and from the viewpoint of ease of handling and workability, the composition is molded into a desired shape and then used as the TIM, particularly the PCM, for electronic equipment. It is preferable to use it for etc. According to this composition, a molded article having a desired shape can be easily formed.
Since the present composition has good thermal conductivity, it is suitably used as a TIM that improves thermal conductivity between a heating element and a heat radiating member or between heat radiating members. In addition, since it can be softened or melted by the heat transmitted from the heating element, it can achieve low thermal resistance by thinning the wall, and is particularly suitable for use as PCM among TIMs.

The molding method used in the molding is not particularly limited, and any known method can be used. Specifically, for example, well-known methods such as extrusion molding, compression molding, and injection molding can be mentioned.

The shape of the TIM is not particularly limited and may be appropriately selected depending on the desired use, but the present composition is usually formed into a film (sheet) shape. The thickness of the film (sheet) may be appropriately selected depending on the desired use, but from the viewpoint of achieving a well-balanced handling property and thermal resistance, it is preferably 100 to 1,000 μm, more preferably 200 to 1,000 μm. It is 700 μm.
Note that the thickness is the thickness of the TIM before it is used in electronic equipment or the like, and the thickness may change depending on the use of the electronic equipment or the like.

≪Electronic equipment≫
An electronic device according to the present invention includes the TIM. Specifically, the TIM is placed between a heat generating element and a heat radiating member or between heat radiating members in an electronic device.
Since such a TIM, particularly a PCM, exhibits the above-mentioned effects, the TIM is suitably used in a heat dissipation system of an electronic device, and a system with excellent heat dissipation performance can be constructed. Furthermore, electronic equipment including the TIM (PCM) can efficiently release heat to the outside of the equipment, resulting in electronic equipment that operates stably over a long period of time.

Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.

<Filler (A)>
As the filler (A), the following commercially available products were used.
・"A-1": Aluminum nitride (manufactured by Tokuyama Co., Ltd. H grade, average particle size 1.2 μm)

<Production of polymer (X) and modified product (Y)>
Polymer (X) and modified product (Y) were produced according to the following synthesis examples and production examples.

[Synthesis Example 1] Synthesis of [ethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,7-di-t-butylfluorenyl)] zirconium dichloride [ethylene (η ⁵ -cyclopentadienyl) ( η ⁵ -2,7-di-t-butylfluorenyl)]zirconium dichloride was synthesized by the method described in Japanese Patent No. 4367687.

[Synthesis Example 2] Synthesis of [methylphenylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,7-di-t-butylfluorenyl)] zirconium dichloride [Methylphenylmethylene (η ⁵ -cyclopentadienyl)] (dienyl)(η ⁵ -2,7-di-t-butylfluorenyl)]zirconium dichloride was synthesized by the method described in Japanese Patent No. 6496533.

[Production Example 1] Synthesis of ethylene-propylene copolymer (X-1) 1 L of dehydrated and purified hexane was placed in a 2 L capacity continuous polymerization reactor equipped with stirring blades that was sufficiently purged with nitrogen, and 96 mmol/L was added thereto. After continuously supplying a hexane solution of prepared ethylaluminum sesquichloride (Al(C ₂ H ₅ ) _1.5 ·Cl _1.5 ) at a rate of 500 mL/h for 1 hour, VO (adjusted to 16 mmol/L) was added as a catalyst. A hexane solution of OC ₂ H ₅ )Cl ₂ was continuously supplied in an amount of 500 mL/h, and hexane was continuously supplied in an amount of 500 mL/h. On the other hand, the polymerization liquid was continuously extracted from the upper part of the reactor so that the polymerization liquid in the reactor was always 1 L.

Next, using a bubbling tube, ethylene gas was supplied in an amount of 36 L/h, propylene gas in an amount of 36 L/h, and hydrogen gas in an amount of 30 L/h. The copolymerization reaction was carried out at 35° C. by circulating a refrigerant through a jacket attached to the outside of the reactor. As a result, a polymerization solution containing an ethylene-propylene copolymer was obtained.
The obtained polymerization solution was washed three times with 500mL of 0.2 mol/L hydrochloric acid per 1L of the polymerization solution, then three times with 500mL of distilled water per 1L of the polymerization solution, and dried over magnesium sulfate. , the solvent was distilled off under reduced pressure. The obtained viscous liquid was dried at 130° C. for 24 hours under reduced pressure to obtain an ethylene-propylene copolymer (X-1).

[Production Examples 2 and 3] Synthesis of ethylene-propylene copolymers (X-2) and (X-3) In Production Example 1, the amount of ethylene gas, propylene gas, and hydrogen gas were adjusted as appropriate. By adjusting, ethylene/propylene copolymers (X-2) and (X-3) were obtained.

[Production Example 4] Synthesis of ethylene-propylene copolymer (X-4) 250 mL of heptane was charged into a glass polymerization vessel with an internal volume of 1 L that was sufficiently purged with nitrogen, and the temperature in the system was raised to 50 ° C. After that, ethylene was continuously supplied into the polymerization vessel at a flow rate of 25 L/h, propylene 75 L/h, and hydrogen 100 L/h, and the mixture was stirred at a stirring rotation speed of 600 rpm. Next, 0.2 mmol of triisobutylaluminum was charged into a polymerization vessel, and then 0.688 mmol of MMAO (manufactured by Tosoh Finechem Co., Ltd.) and [ethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2, Polymerization was started by premixing 0.00230 mmol of zirconium dichloride (7-di-t-butylfluorenyl) in toluene for 15 minutes or more and charging the mixture into a polymerization vessel. Thereafter, continuous supply of ethylene, propylene, and hydrogen was continued, and polymerization was carried out at 50° C. for 15 minutes. After the polymerization was stopped by adding a small amount of isobutyl alcohol into the system, unreacted monomers were purged. The obtained polymerization solution was washed three times with 100 mL of 0.2 mol/L hydrochloric acid, then three times with 100 mL of distilled water, dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the mixture was dried overnight at 80° C. under reduced pressure. In this way, an ethylene/propylene copolymer was obtained.

After adding 100 mL of a hexane solution of 0.5 mass % Pd/alumina catalyst and 500 mL of a 30 mass % hexane solution of the obtained ethylene propylene copolymer to a stainless steel autoclave with an internal volume of 1 L, and sealing the autoclave. , nitrogen substitution was performed. Next, the temperature was raised to 140°C with stirring, the system was replaced with hydrogen, and then the pressure was increased to 1.5 MPa with hydrogen and a hydrogenation reaction was performed for 15 minutes to produce ethylene-propylene copolymer (X-4). 1.43g was obtained.

[Production Example 5] Synthesis of modified ethylene/propylene copolymer (Y-1) (i) Synthesis of ethylene/propylene copolymer 760 mL of heptane and propylene were placed in a stainless steel autoclave with an internal volume of 2 L that was sufficiently purged with nitrogen. After charging 120 g and raising the temperature in the system to 150° C., 0.85 MPa of hydrogen and 0.19 MPa of ethylene were supplied to bring the total pressure to 3 MPaG. Next, 0.4 mmol of triisobutylaluminum, 0.0002 mmol of [methylphenylmethylene (η ⁵ -cyclopentadienyl) (η ⁵ -2,7-di-t-butylfluorenyl)]zirconium dichloride, and N , N-dimethylanilinium tetrakis(pentafluorophenyl)borate (0.002 mmol) was introduced under pressure with nitrogen, and the stirring speed was set to 400 rpm to initiate polymerization. Thereafter, the total pressure was maintained at 3 MPaG by continuously supplying only ethylene, and polymerization was carried out at 150° C. for 5 minutes. After stopping the polymerization by adding a small amount of ethanol into the system, unreacted ethylene, propylene, and hydrogen were purged. The obtained polymerization solution was washed three times with 1000 mL of 0.2 mol/L hydrochloric acid and then three times with 1000 mL of distilled water, dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the mixture was dried overnight at 80° C. under reduced pressure. As a result, an ethylene/propylene copolymer having a kinematic viscosity at 100° C. (JIS K2283) of 150 mm ² /s was obtained.

After adding 100 mL of a hexane solution of 0.5 mass % Pd/alumina catalyst and 500 mL of a 30 mass % hexane solution of the obtained ethylene propylene copolymer to a stainless steel autoclave with an internal volume of 1 L, and sealing the autoclave. , nitrogen substitution was performed. Next, the temperature was raised to 140 ° C. with stirring, the inside of the system was replaced with hydrogen, and the pressure was increased to 1.5 MPa with hydrogen and a hydrogenation reaction was performed for 15 minutes to obtain 60.9 g of ethylene propylene copolymer. Ta.

(ii) Synthesis of modified ethylene-propylene copolymer (Y-1) The product obtained in (i) was placed in a 200 mL glass reactor equipped with a stirrer equipped with a nitrogen blowing tube, a water-cooled condenser, a thermometer, and two dropping funnels. After raising the temperature, nitrogen bubbling was started at 120°C and the inside of the system was kept at 160°C. Thereafter, 6.6 g of maleic anhydride (which had been heated to around 70°C and made into a liquid) and 1.3 g of di-t-butyl peroxide, which had been charged in advance into two dropping funnels, were added to 5 The mixture was supplied to the reactor over time, and after the supply was completed, the reaction was allowed to proceed for 1 hour. Next, the temperature was raised to 175°C, and after depressurizing the system, the pressure was reduced for 1 hour while gradually introducing nitrogen using a vacuum pump to remove impurities (decomposed products of unreacted maleic anhydride and di-t-butyl peroxide). ) was removed. Through the above operations, a modified ethylene/propylene copolymer (Y-1) was obtained.

[Production Example 6] Synthesis of modified product (Y-2) of ethylene-propylene copolymer (X-1) The copolymer obtained in Production Example 5 (i) was combined with the copolymer obtained in Production Example 1. Production example except that the mixture was changed to compound (X-1), and the amounts of maleic anhydride and di-t-butyl peroxide were changed to 2.8 g and 0.6 g, respectively, and were fed to the reactor over 2 hours. A modified ethylene-propylene copolymer (Y-2) was obtained in the same manner as in 5-(ii).

[Production Example 7] Synthesis of modified product (Y-3) of ethylene-propylene copolymer (X-2) The copolymer obtained in Production Example 5 (i) was combined with the copolymer obtained in Production Example 2. Production example except that the mixture was changed to compound (X-2), and the amounts of maleic anhydride and di-t-butyl peroxide were changed to 3.8 g and 0.8 g, respectively, and were fed to the reactor over 3 hours. A modified ethylene-propylene copolymer (Y-3) was obtained in the same manner as in 5-(ii).

<Commercially available oil>
In the comparative examples below, the following commercially available oils were used.
・“Z-1”: Paraffinic mineral oil (manufactured by Idemitsu Kosan Co., Ltd., Diana Process Oil PW-380)
・“Z-2”: Silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-96H-10,000cs)
・“Q-3”: Poly α-olefin (manufactured by Exxon Mobil Chemical, SpectraSyn100)
・“Q-4”: Liquid polyisobutylene (manufactured by JXTG Energy Corporation, Nisseki Polybutene HV-1900)

Copolymers (X-1) to (X-4) obtained in Production Examples 1 to 4, commercially available oils (Z-1) to (Z-2) and (Q-3) to (Q-4 ), the physical properties of the modified products (Y-1) to (Y-3) were measured by the following methods. The results of these analyzes are shown in Table 1 or Table 2.

[Methyl group index]
Using an AVANCE III cryo-500 nuclear magnetic resonance apparatus manufactured by Bruker Biospin, deuterium chloroform was used as the solvent, the sample concentration was 20 mg/0.6 mL, the measurement temperature was 50°C, the observation nucleus was ¹ H (500 MHz), and the sequence was is a single pulse, pulse width is 5.00 μs (45° pulse), repetition time is 7.0 seconds, number of integration is 64 times, and the reference value of chemical shift is the solvent peak based on CHCl ₃ in deuterated chloroform (7.24 ppm). ), the ¹ H-NMR spectrum was measured.
In the ¹ H-NMR spectrum measured in this way, the ratio of the integral value of the peak within the range of 0.50 to 1.15 ppm to the integral value of the peak within the range of 0.50 to 2.20 ppm was used as the methyl group index.

[Kinematic viscosity at 100°C]
The kinematic viscosity at 100°C (100°C kinematic viscosity) was measured and calculated by the method described in JIS K2283.

[Molecular weight (Mw)]
Mw was measured using the following high-speed GPC measuring device.
High-speed GPC measurement device: HLC8320GPC manufactured by Tosoh Corporation
Mobile phase: THF (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., stabilizer-free, liquid chromatography grade)
Column: Two TSKgel Super Multipore HZ-M manufactured by Tosoh Corporation connected in series Sample concentration: 5 mg/mL
Mobile phase flow rate: 0.35 mL/min Measurement temperature: 40°C
Standard sample for calibration curve: Tosoh Corporation, PStQuick MP-M

[Acid value]
The acid value was measured and calculated by the method described in JIS K2501:2003.

[Viscosity at 150°C]
The apparent viscosity at 150°C (150°C Brookfield viscosity (150°C BF viscosity)) was measured and calculated by the method described in JIS K7117-1.

<Compound (Q)>
As compound (Q), the following commercially available products were used.
・"Q-1": Polyethylene wax (manufactured by Mitsui Chemicals, Inc., Hiwax 4202E, does not meet the above requirement (x-1), is not a graft modified product)
・“Q-2”: Ethylene/vinyl acetate copolymer (manufactured by Mitsui Dow Polychemical Co., Ltd., Evaflex EV150)

[Examples 1 to 8 and Comparative Examples 1 to 7 ]
Using a mixing stirrer heated to 120° C., the components listed in the composition column of Tables 3 and 4 below were mixed for 5 minutes at the numerical values (mass ratio) listed in the column to prepare a resin composition.

<Measurement of physical properties of resin composition>
The respective resin compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 7 were heated using a manual heat press machine (manufactured by Shinto Metal Industry Co., Ltd.) at 100°C for 2 minutes at 4 MPa. Compression molding was performed using a mold to create a sheet of 65 mm x 65 mm x (thickness) 1 mm. Using this sheet, the physical properties of the resin composition were measured according to the following method. The results are shown in Tables 3 and 4.

[Sheet formability]
When eight sheets were produced, the number of sheets in which cracks or breaks were visually observed was counted and evaluated at the end of sheet molding or after the sheet was taken out from the mold. Tables 3 and 4 show the number of sheets on which cracks and cracks were confirmed.

〔Thermal resistance〕
After the sheet was cut into a size of 1.5 cm x 1.5 cm, it was sandwiched between a copper jig in which a heater was embedded and an aluminum jig, and a load of 2 kg was applied. Here, a power of 24 W was applied to the heater, and the thermal resistance was determined from the temperature of each of the copper jig and the aluminum jig using the following formula when the temperatures reached a constant equilibrium state.
(Thermal resistance) = (T _Cu - T _Al )/24
Here, T _Cu is the temperature of the copper jig in an equilibrium state, and T _Al is the temperature of the aluminum jig in an equilibrium state.

[Appearance evaluation after heat aging test]
The sheet was placed on a glass Petri dish, placed in an air oven, and left standing at 150° C. for 168 hours to perform a heat aging test. The petri dish was taken out from the oven, the inside of the petri dish after the test was photographed from directly above, and the photograph was printed. The area where the sheet of the printed photo is visible is the area where the filler (A) can be seen (opaque [white to light yellow] area), and the area where the filler (A) cannot be seen but the binder (B) component can be seen. The area was divided into clear areas (transparent [colorless to pale yellow] areas), and the weights of the photographs representing each area were defined as W _A and W _B , respectively. Based on the value of W _B /W _A at this time, the appearance after the heat aging test was evaluated according to the following criteria.

(Evaluation criteria)
2:0≦W _B /W _A <0.1.
1:0.1≦W _B /W _A <0.3.
0:0.3≦W _B / _WA .

[Mass change rate before and after heat aging test]
From the mass of the sheet before being placed in the air oven and the mass of the sheet after the heat aging test, the mass change rate before and after the heat aging test was calculated using the following formula, and evaluated based on the following criteria.
(Sheet mass change rate before and after heat aging test)=100×(W-W ₀ )/W ₀
Here, W is the mass of the sheet after the heat aging test, and W ₀ is the mass of the sheet before the heat aging test.

(Evaluation criteria)
3: The absolute value of the mass change rate is less than 0.5% 2: The absolute value of the mass change rate is 0.5% or more and less than 1% 1: The absolute value of the mass change rate is 1% or more 1.5 0: The absolute value of the mass change rate is 1.5% or more

Claims (9)

A resin composition containing 100 parts by mass of the following binder (B) and 100 to 1000 parts by mass of filler (A).
・Binder (B):
A graft modified product (Y) of an α-olefin (co)polymer that satisfies the following requirements (y-1) to (y-4) , and an α- that satisfies the following requirements (x-1) to (x- 4 ) Contains a component (P) containing one or more types selected from olefin (co)polymers (X) in an amount of 10 to 70% by mass based on 100% by mass of the binder (B), and
Contains one or more compounds (Q) selected from olefin resin, styrene thermoplastic elastomer, and wax (excluding component (P)) (x-1) Methyl group index measured from ¹ H-NMR is 25 to 55 %. [Here, the methyl group index is determined by dissolving the α-olefin (co)polymer (X) in deuterated chloroform and measuring ¹ H-NMR. When the solvent peak based on CHCl ₃ (7.24 ppm) is used as a reference, the integral value of the peak in the range of 0.50 to 2.20 ppm is compared to the integral value of the peak in the range of 0.50 to 1.15 ppm. It refers to the ratio of the integral value. ]
(x-2) The kinematic viscosity at 100°C is 400 to 10,000 mm ² /s. (x-3) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 5,000 to 25, It is 000
(x-4) α-olefin (co)polymer (X) is an ethylene/propylene copolymer
(y-1) Acid value is 10 to 150 mgKOH/g
(y-2) Apparent viscosity at 150°C is 50 to 1,500 mPa・s
(y-3) Weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 3,000 to 25,000
(y-4) The α-olefin (co)polymer before graft modification is an ethylene/α-olefin copolymer, and the content of structural units derived from ethylene in the ethylene/α-olefin copolymer is 30 to 85 mol% The resin composition according to claim 1, which contains the α-olefin (co)polymer (X) and has a kinematic viscosity at 100° C. of 500 to 4,000 mm ² /s. thing. The graft modified product (Y) is a modified product of an α-olefin (co)polymer with one or more selected from unsaturated carboxylic acid compounds and unsaturated carboxylic acid derivatives. The resin composition according to claim 1 or 2. The graft modified product (Y) is a modified product of an α-olefin (co)polymer with one or more selected from maleic acid and maleic anhydride. The resin composition according to any one of items 1 to 3. The filler (A) is selected from aluminum oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, aluminum nitride, boron nitride, silicon dioxide, carbon black, carbon nanofibers, carbon nanotubes, silicon carbide, and silicon nitride. The resin composition according to any one of claims 1 to 4, comprising one or more fillers. The resin composition according to any one of claims 1 to 5, comprising the graft modified product (Y). A TIM (Thermal Interface Material) which is a molded article of the resin composition according to any one of claims 1 to 6. 8. The TIM of claim 7, which is a phase change material (PCM). An electronic device comprising the TIM according to claim 7 or 8.