KR101956370B1 - A resin composition using heat padiating sheet having phase change material of electrically insulative - Google Patents

Abstract

According to the present invention, a resin composition for a heat radiation sheet including an insulating phase change material uses an aluminum oxide unlike the phase change material used in a resin for a conventional insulation sheet, so that heat generated from electrical and electronic products can be effectively emitted without adjusting the thickness of the heat radiation sheet and complicating the structure, and simultaneously sufficient insulation can be ensured.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a resin composition for a heat-

The present invention relates to a resin composition for a heat-radiating sheet containing an insulating phase-change material, and more particularly to a resin composition for a heat- The present invention also relates to a resin composition for a heat-radiating sheet comprising an insulating phase-change material that can satisfy both insulation and thermal conductivity.

In recent years, electronic devices used in automobiles, electric and electronic fields have been pursued to be lighter, thinner, smaller, and multifunctional. As these electronic devices become more highly integrated, more heat is generated. This heat dissipation not only degrades the function of the device but also causes malfunction of the peripheral device and deterioration of the substrate. Therefore, . Particularly, the material of the high heat radiation circuit board can utilize the thermal conductivity of the base metal substrate, so that it is advantageous for manufacturing high power consuming parts such as power devices and LED modules and generating heat, so that interest in research and development is being amplified. For example, about 85% of LEDs are converted to losses, and the temperature of the junction increases continuously due to the high temperature of the emitted heat, which causes the lifetime of the LED semiconductor to deteriorate. The average time for a malfunction to occur is known to be twice as long as the element operating temperature increases by 10 ° C. In order to prevent this, high power LEDs use high heat dissipation substrates, and the demand for high heat dissipation materials is rapidly increasing.

Here, as the size and weight of electronic devices and parts are reduced, the degree of integration of circuits mounted on the electronic devices and parts is increasing. As the amount of generated electromagnetic waves increases, electromagnetic interference and electromagnetic interference threats are increasing. As a result, the heat generated by the electric devices operating on the basis of electric energy is rising, and the heat problem is highlighted. Therefore, it is necessary to develop a technology capable of simultaneously realizing heat dissipation characteristics that effectively dissipate heat generated from the electric device and dissipate heat, and effectively shield and absorb electromagnetic waves that cause malfunction of the electric device and adversely affect the human body.

Accordingly, there is a problem in that products having two or more sheets, in particular, sheets obtained by laminating a sheet having heat conductive property and a sheet having electromagnetic wave absorbing property are studied, but the processability is poor due to a multilayered structure, In addition, in order to realize the thermal conductivity and the electromagnetic wave absorbing property to the extent required in recent electronic apparatuses, the thickness has to be thickened due to the characteristics of multilayer, which is a problem in that it is not suitable for recent electronic devices seeking miniaturization and weight saving.

Particularly, the material of the high heat radiation circuit board can utilize the thermal conductivity of the base metal substrate, and thus it is advantageous for the production of parts with high power consumption and heat generation such as power devices and LED modules. About 85% of the LEDs are converted to losses and the junction temperature is continuously increased due to the high heat emission heat, which causes the lifetime of the LED semiconductor to decrease. The average time for a malfunction to occur is known to be twice as long as the element operating temperature increases by 10 ° C. In order to prevent this, high power LEDs use high heat dissipation substrates, and the demand for high heat dissipation materials is rapidly increasing.

Phase change material (PCM), on the other hand, can absorb or release much heat (latent heat) as the phase changes without changing the temperature at a specific temperature, Emitting material. Such latent heat has an energy storage and discharge ability tens or hundreds of times higher than sensible heat, so it has superior functions than energy storage materials using existing sensible heat.

These phase change materials, due to their excellent properties, are used in the energy industry and environmentally friendly housing systems (interior materials, air conditioning, air conditioning systems, solar thermal systems, low cost energy utilization systems), sports apparel and accessories (hiking, mountaineering backpacks, , Sleeping bag), functional clothing (special military uniform), footwear (shoes, shoes, specialization, specialization, work), military industrial facilities and munitions, automobile industry (interior materials, seat) It is an energy-saving eco-friendly material that can be applied to various industries such as beds for preventing pressure ulcers (long-term hospitalized patients, blood transport system).

As for the material composition of the heat-radiating material including the phase change material, most of the composite material is a mixture of a high thermal conductive filler material such as a carbon material or a ceramic material and a polymer material. Thermally conductive polymers can impart properties of metals and ceramics while retaining the advantages of conventional polymer materials, such as easy processability, low cost, light weight, and variety of product form. The reason for using the composite material is that the high thermal conductivity inorganic filler material is excellent in thermal conductivity but has no adhesive force, and the polymer material has good adhesion, but low thermal conductivity. However, in order to achieve a high thermal conductivity of a polymer composite, a large amount of filler is contained. In such a case, the processing conditions are complicated and the physical properties of the product are impaired. In many cases, the electrical conductivity is high due to the characteristics of the heat- It has a disadvantage that the dislocations can not be used between two different surfaces.

Korean Patent No. 10-0949786 (Mar. 19, 2010)

SUMMARY OF THE INVENTION The present invention has been devised to solve the above-mentioned problems, and it is an object of the present invention to provide a phase change material which is excellent in insulation performance and thermal conductivity The present invention also relates to a resin composition for a heat-radiating sheet comprising an insulating phase-change material that can be satisfactorily satisfactory.

Another object of the present invention is to provide a resin composition for a heat-radiating sheet comprising an insulating phase-change material to which a dispersion auxiliary agent and an ionomer are further added in order to further improve heat radiation characteristics of the phase-change material.

The present invention relates to a resin composition for a heat radiation sheet comprising an insulating phase change material.

One aspect of the present invention relates to a composition comprising a base resin; And a heat accumulating capsule dispersed in the base resin, wherein the heat accumulating capsule comprises a filler containing a phase change material and a coating layer containing the filler, ≪ / RTI >

The phase change material in the present invention, _{Fe 2 O 3 *? * 3} *? * 2 O, NaNH 4 SO 4 *? * 2 O, NaNH 4 HPO 4 *? * 2 O, FeCl 3 *? * 2 O, Na ₂ PO ₄ * ₂ O, Na ₂ SiO ₃ * ₂ O, Ca (NO ₃ ) ₂ *? ₂ O, K ₂ HPO ₄ *? ₂ O, Na ₂ SiO ₃ *? _{2 O, Fe (NO 3) 3} *? * 2 O, K 3 PO 4 *? * 2 O, NaHPO 4 *? * 2 O, CaCl 2 *? * 2 O, Na 2 SO 4 *? * 2 O, Na ₂ SO ₄ *? ₂ O + Na ₂ B ₄ O ₇ · ₂ O, CaCl ₂ *? ₂ O + BaO and Na (CH ₃ COO) *? ₂ O, paraffin wax, n -Cyclohexanoic acid, eicosanoic acid, n-octadecane, n-triacotan, hexadecane, nonadecane, eicosane, hexoic acid, docosane, tricoic acid, tetracholic acid, pentacosanoic acid, polyethylene glycol, , Capric acid, isopropyl stearate, butyl stearate, palmitic acid, myristic acid and vinyl stearic acid, and the like.

Wherein the base resin is selected from the group consisting of polydimethylsiloxane resin, epoxy resin, acrylate resin, organopolysiloxane resin, polyimide resin, fluorocarbon resin, benzocyclobutene resin, fluorinated polyallyl ether resin, polyamide resin, An ester resin, a phenol resol resin, an aromatic polyester resin, a polyphenylene ether resin, a bismaleimide triazine resin, and a fluororesin.

The composition may further comprise one or more fillers selected from carbon nanotubes, graphene, graphite, fullerene, aluminum oxide, copper oxide, silver oxide, gold oxide, palladium oxide, platinum oxide, nickel oxide, And more particularly, aluminum oxide and acid whiten are mixed in a ratio of 60 to 80: 20 to 40 by weight.

The composition may further comprise a polyallyl amine derivative as a dispersion aid, and the phase change material may further comprise aluminum oxide nanoparticles.

The resin composition for a heat-radiating sheet containing an insulating phase-change material according to the present invention is different from a phase change material used for a conventional resin for an insulating sheet, It is possible to effectively release heat generated from the electric and electronic products without complicated formation, and at the same time ensure sufficient insulation.

The high heat-radiating carbon sheet according to the present invention can further improve the service life of electronic parts and devices included in automobile interior materials, batteries, displays and the like owing to the above-mentioned characteristics, and the consumers can directly contact portable electronic devices such as mobile devices It is possible to relieve the feeling of resistance to the fever that can be felt and to secure the insulation property compared with the conventional simple lamination or the technique using graphene, and to suppress the discharge phenomenon such as corona, partial discharge, flashover and the like.

The insulating silicone heat-radiating sheet according to the present invention can be applied to a product which is causing a heating problem due to the thinness of smart phones, LED TVs and automobile parts owing to the above characteristics, It is applicable to the functional composite material field.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view illustrating an insulated phase change material manufactured according to an embodiment of the present invention; FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a resin composition for a heat-radiating sheet containing an insulating phase-change material according to the present invention will be described in detail with reference to specific examples. The following specific embodiments are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention.

Therefore, the present invention is not limited to the embodiments shown below, but may be embodied in other forms. The embodiments shown below are only for clarifying the spirit of the present invention, and the present invention is not limited thereto.

Here, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. In the following description, the gist of the present invention is unnecessarily blurred And a description of the known function and configuration will be omitted.

In addition, the following drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention is not limited to the following drawings, but may be embodied in other forms, and the drawings presented below may be exaggerated in order to clarify the spirit of the present invention. Also, throughout the specification, like reference numerals designate like elements.

Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise.

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."

The resin composition for a heat radiation sheet containing an insulating phase change material according to the present invention may comprise a base resin and a heat storage capsule dispersed in the base resin.

In the present invention, the resin composition provides EMI-shielding (Electro-Magnetic Interference Shielding) as a resin or emulsion, such as a pressure-sensitive adhesive, and enhances the thermal performance of a device to which the composition is applied.

The composition may also function as an endothermic film, such as a transfer tape format, so that it can be applied at any location on the apparatus requiring cooling. The application position may act as a heat spreader on or between the substrates.

The composition may be used with a power source, such as a battery module, to dissipate the heat generated by the power source during operation. The operating temperature is not limited in the present invention, but may be as high as about 40 占 폚. In this embodiment, a housing comprising at least one substrate having an inner surface and an outer surface is provided on or against the product and on its inwardly facing surface, and the spreading of the generated heat, A composition comprising a plurality of encapsulated phase change material storage capsule particles dispersed in a matrix disposed on a substrate capable of providing a thermal conductivity to facilitate is disposed on at least a portion of the inner surface of the at least one substrate. In one aspect, the encapsulated phase change material particles may have a layer of conductive material disposed on at least a portion of a surface of the particle. The conductive coating should be a metal such as Ag, Cu or Ni to provide an EMI shielding effect.

In the present invention, the base resin is a receptacle for receiving a heat accumulation capsule therein, and is a substrate directly applied to a heat source.

In the present invention, the base resin has ductility and is easily adhered to a heat source, has excellent workability, and is excellent in heat resistance, so that even if the continuous heat is supplied, deformation does not occur in the resin, It is preferable to use a substance having

Examples of the base resin in the present invention include polydimethylsiloxane resin, epoxy resin, acrylate resin, organopolysiloxane resin, polyimide resin, fluorocarbon resin, benzocyclobutene resin, fluorinated polyallyl ether resin, polyamide resin, Amide resins, cyanate ester resins, phenol resole resins, aromatic polyester resins, polyphenylene ether resins, bismaleimide triazine resins, fluororesins, or mixtures thereof. The polymer can be thermoplastic or thermoset and can be selected according to the desired final properties (e.g., viscosity, modulus and elasticity). Suitable examples of curable thermosetting matrices include, but are not limited to, acrylate resins, epoxy resins and polydimethylsiloxane resins, as well as free radical polymerization, atom transfer, radical polymerization ring opening polymerization, ring opening metathesis polymerization, anionic polymerization, cationic polymerization, Other organic functional polysiloxane resins that can form crosslinked networks through other methods of the invention. In the case of a non-curable polymer, the resulting thermal interface material may be formulated as a gel, grease, or phase change material that can maintain heat transfer during operation while holding the components together during manufacture.

Specifically, the polymer matrix may be a polysiloxane resin such as an addition curable silicone rubber composition. Such compositions may include one or more organopolysiloxane components (e. G., An organopolysiloxane containing an average of at least two silicon-bonded alkenyl groups per molecule), one or more organohydrogenpolysiloxanes that serve as crosslinkers (e. G., Two or more silicon- (For example, ruthenium, rhodium, platinum or palladium complex), and optionally at least one catalyst inhibitor (used to modify the curing profile and improve shelf life) and 1 Or more adhesion promoters.

The polymer matrix may further comprise various additives to achieve the desired overall properties of the thermal interface material. For example, when combined with a filler, a reactive organic diluent may be added to reduce the viscosity of the polymer matrix. Non-reactive diluents may also be added to reduce the viscosity of the formulation. It may also comprise one or more pigments or pigments mixed with a carrier liquid. In the case of epoxy resins, various known hardeners, hardeners and / or other optional reagents may be used with the curing catalyst.

For example, a dispersing agent such as fatty acid, fish oil, polydiallyldimethylammonium chloride, polyacrylic acid, and polystyrene sulfonate may be further added to disperse the filler or the fibrous heat conductor, and polyvinyl alcohol, polyvinyl butyral, A binder such as wax may be mixed.

In the present invention, the base resin is preferably added in an amount of 60 to 85% by weight based on 100% by weight of the total composition. If less than 60% by weight is added, the content of the substrate is small and it is difficult to adhere well to the heat source. If the content exceeds 85% by weight, the content of the other components may be decreased and the thermal conductivity may be greatly decreased.

In the present invention, the thermal storage capsule comprises a filler material 100 containing a phase change material and a coating layer 200 for containing the filler material as shown in FIG. 1, and the filling material contained in the coating material, Thereby absorbing or releasing a large amount of heat generated from the heat source to maintain the temperature uniformly.

The heat storage capsule may be formed in various shapes such as spherical and elliptical shapes, and the coating layer may be formed to have a predetermined thickness and surround the filler. For example, the coating layer may be formed to a thickness of about 10 to 200 nm, but it is not limited thereto and may have various thicknesses depending on the shape of the heat storage capsule, the kind of the component forming the coating layer, .

In the present invention, the coating layer protects the filler containing the phase change material from external impact, and blocks the mixing with other components due to the phase change material in which the phase change occurs depending on the temperature, It plays a role.

In the present invention, the component constituting the coating layer is not particularly limited as long as it is a polymer capable of providing excellent mechanical strength. Examples of the polymer include polyurea, polyurethane, polyester, polyamide, melamine resin, gelatin, And one or more of these may be used in combination.

As the material for forming the coating layer, more specifically, a monomer capable of causing condensation polymerization, preferably a compound containing two or more isocyanate groups is preferable.

The compound containing two or more isocyanate groups may be selected from the group consisting of toluene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, etc., Two or more species can be used.

In the present invention, the filler may include a phase change material. The phase change material may be an organic or inorganic material. Examples of the organic phase change material include paraffin wax, n-eicosane, n-octadecane, n-triacontane, hexadecane, But are not limited to, hexadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, polyethylene glycol, But are not limited to, lauric acid, propyl palmitate, capric acid, isopropyl stearate, butyl stearate, palmitic acid, Petrolatum, myristic acid, vinyl stearic acid, and the like.

Examples of the inorganic phase change materials include Fe ₂ O ₃ * ₃ *? * ₂ O, NaNH ₄ SO ₄ *? * ₂ O, NaNH ₄ HPO ₄ *? ₂ O, FeCl ₃ *? * ₂ O, Na ₃ PO ₄ *? * ₂ O, Na ₂ SiO ₃ *? ₂ O, Ca (NO ₃ ) ₂ *? ₂ O, K ₂ HPO ₄ *? * ₂ O, Na ₂ SiO ₃ *? _{* 2 O, Fe (NO 3} ) 3 *? * 2 O, K 3 PO 4 *? * 2 O, NaHPO 4 *? * 2 O, CaCl 2 *? * 2 O, Na 2 SO 4 *? * 2 O, Na ₂ SO ₄ *? ₂ O + Na ₂ B ₄ O ₇ · ₂ O, CaCl ₂ *? ₂ O + BaO and Na (CH ₃ COO) *? ₂ O.

These phase change materials may be used singly or in combination of two or more kinds depending on the use, and organic and inorganic systems may be mixed. At this time, the blending ratio can be freely carried out within a range that does not impair the object of the present invention. For example, when paraffin and petrolatum are mixed, it is preferable to mix them in a weight ratio of 1 to 3: 1 to satisfy softness and shrinkage.

The phase change material and the polymer monomer constituting the coating layer are preferably mixed in a weight ratio of 1: 5: 1. The physical strength of the heat storage capsule can be firmly manufactured within the above content range.

The heat storage capsule does not limit the production method. For example, the emulsion may be prepared by mixing the phase change material and the coating layer polymer, homogenizing the mixture to a nanometer size, mixing the homogenized mixture with an emulsifier, and emulsifying the mixture by forced emulsification.

The step of homogenizing the composition may be performed by using a physical device such as a homogenizer to crush the droplet to a nanometer size. Any separation method commonly used in the art may be used for this purpose. Do.

The homogenization can be carried out by stirring at 5,000 to 20,000 rpm for 5 to 30 minutes, but it is not particularly limited.

The emulsion can be prepared by mixing a mixed solution of a phase transition material and a polymer monomer crushed to a nanometer size, a dispersing solution of an emulsifier and a polymer.

The emulsifier can be used for the polymerization reaction with the monomer, emulsify the phase transition material to produce stable liquid droplets of small size, and for the chemical bonding with the reactor of the polymer monomer for the polymerization reaction.

The emulsifier can be used without limitation as long as it is a reactive group having reactivity with a reactor of a polymer monomer, preferably a compound having a hydroxy group. For example, a poly (styrene sulfonic acid comoleic acid) or a styrene-maleic anhydride copolymer may be used alone or in combination of two or more.

The emulsifier is preferably contained in an amount of 0.2 to 1 part by weight based on 100 parts by weight of the emulsion. When the content is within the above range, the produced nanocomposite capsules have the highest dispersion stability.

The emulsion may have a nanocapsule structure in which a polymer shell encapsulates the phase change material through condensation polymerization at 60 to 80 ° C for 3 to 12 hours in combination with a chain extender.

Examples of the compound include ethylenediamine, propanediamine, hexanediamine, phenylenediamine, pentaerythritol, and the like. Examples of the compound having at least two amine groups at the terminal thereof include ethylenediamine, propanediamine, hexanediamine, Or polyoxyethylene bisamine may be used alone or in combination of two or more.

The chain extender may be included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the emulsion. When the content is within the above range, the physical strength of the polymer coating layer is maintained.

Preferably, the heat storage capsules are added in an amount of 15 to 40% by weight based on 100% by weight of the total composition. When it is added in an amount of less than 15% by weight, the thermal conductivity may be considerably lowered. When it is added in an amount of more than 40% by weight, the content of the substrate may be too small.

The composition may further include one or more fillers to further improve mechanical properties such as heat resistance, adhesiveness, durability and the like.

The filler is added to improve the thermal conductivity or the chargeability in addition to the mechanical properties as described above. The filler has high thermal conductivity and can easily receive heat from the heat source and release it to the graphite sheet layer or the outside Any material that can be used can be used regardless of the type.

The filler is generally composed of a metal oxide having excellent thermal conductivity such as aluminum oxide, copper oxide, silver oxide, palladium oxide, platinum oxide, nickel oxide and acid whitanium, carbon nanotubes, graphene, graphite, Fullerene, and the like. In addition to the above materials, ceramic nanoparticles such as dry silica, fused silica, quartz powder, amorphous silica, aluminum nitride (AlN) or boron nitride (BN) may be added.

In the present invention, as the filler, more specifically, it is preferable to use a mixture of aluminum oxide and whitening acid. The aluminum oxide has high thermal conductivity, electrical resistance and mechanical strength, and is used as a heat-radiating material due to its low dielectric constant, which is further amplified when mixed with acid whiten.

In the present invention, the mixing ratio of the aluminum oxide to the acid whitanium is preferably 60 to 80: 20 to 40 by weight. In particular, when the acid whiten is added in an amount exceeding the above range, the heat radiation characteristic of the adhesive layer due to the thermal conductivity drop of the aluminum oxide may be deteriorated.

In the present invention, the filler is preferably added in an amount of 5 to 30 parts by weight based on 100 parts by weight of the total composition. If it is added in an amount of less than 5 parts by weight, the effect of improving thermal conductivity and mechanical properties is insufficient. If it is added in an amount of more than 30 parts by weight, the insulating property of the composition is deteriorated due to excessive addition of a metallic material.

The filler may further include aluminum oxide nanoparticles to further increase the insulating property.

The aluminum oxide (Al ₂ O ₃ ) has a high thermal conductivity and mechanical strength and exhibits excellent insulation characteristics, but is inexpensive and is widely used as a typical ceramic substrate material. The filler according to the present invention is characterized by satisfying the insulating property by further adding aluminum oxide to the composition.

The aluminum oxide does not limit the production method. For example, water can be prepared by reacting aluminum nitrate (Al (NO ₃ ) ₃ ) with ammonium hydroxide (NH ₄ OH) in the presence of laponite as a reaction medium and a dispersing agent.

The aluminum oxide is not limited in size and shape but may be spherical particles having a diameter of 1 to 50 nm in order to satisfy heat radiation characteristics and insulation characteristics of the composition. The addition amount is not limited, but the addition of 0.1 to 5 parts by weight based on 100 parts by weight of the total composition may satisfy excellent heat and insulation properties without impairing the mechanical properties of the composition.

The composition according to the present invention may further include a dispersing aid to further increase the dispersibility of the inorganic material such as a filler and the heat dissipation property.

In the present invention, the dispersion aid is intended to further increase the dispersibility of the filler in the composition, And a polyallylamine derivative as a main component.

In the present invention, the polyallylamine derivative can be obtained by first polymerizing allylamine in the presence of an initiator and a chain transfer catalyst to prepare a polyallylamine, and then reacting the polyester, the polyamide and the polyester amide. The polyallylamine derivative prepared by the above method may have an acidity of 2.5 to 50 mg and a weight average molecular weight of 2,000 to 100,000.

In the present invention, the dispersion aid is preferably added in an amount of 1 to 10 parts by weight based on 100 parts by weight of the total composition. If it is less than 1 part by weight, the fibrous heat conductor may not migrate sufficiently during charging, and the thermal conductivity may be greatly deteriorated. If it is added in an amount exceeding 10 parts by weight, moldability may be deteriorated due to an increase in flowability of the adhesive layer composition.

In addition, the composition may further include one or more ionomers to further increase the insulating properties and adhesion properties with the heat source.

The ionomer means an ion conductive polymer having a fixed ion attached to a polymer chain or a side chain by a covalent bond. In order to further increase the insulating property, the ionomer is an alkyl group of at least one monomer constituting a general aliphatic hydrocarbon or aromatic hydrocarbon, , A partially fluorinated ionomer in which a part of the hydrogen of the aromatic group is substituted with a fluorine atom is preferably used.

In the present invention, the partially fluorinated ionomer is a sulfonated poly (arylene ether sulfone-co-vinylidene fluoride), a sulfonated tri-fluoro styrene-graft-poly (tetrafluoroethylene) (PTFE- , Copolymers containing fluorinated or partially fluorinated monomers such as styrene-grafted sulfonated polyvinylidene fluoride (PVDFg-PSSA), dicarfluorobiphenyl or hexafluorobenzene (eg HQSH-6F Block copolymers), and the like, and it is also possible to use one or a mixture thereof.

The ionomer is not limited in shape, but preferably has an average particle size of 0.01 nm to 600 nm, and its content is 0.1 to 5 parts by weight in 100 parts by weight of the total composition, .

In addition, the adhesive layer may further include at least one additive in preparing the composition within the range not impairing the object of the present invention. Examples of the additives include plasticizers, crosslinking agents, antioxidants, crosslinking aids, curing accelerators, scorch retarders, processing aids, coupling agents, ultraviolet stabilizers (including UV absorbers), antistatic agents, , Viscosity modifiers, tackifiers, antiblocking agents, surfactants, extender oils, antacids, flame retardants, adhesion promoters, and metal deactivators.

Examples of such plasticizers in the present invention include, but are not limited to, phthalic acid diesters (also known as "phthalates") such as di-isononyl phthalate (DINP), diallyl phthalate (DAP), di- ), Dioctyl phthalate (DOP) and diisodecyl phthalate (DIDP); Trimellitates such as trimethyltrimellitate, n-octyltrimellitate, and tri- (2-ethylhexyl) trimellitate; Adipate plasticizers such as bis (2-ethylhexyl) adipate, dimethyl adipate and dioctyl adipate; Sebacate plasticizers, such as dibutyl sebacate; Maleates such as dibutyl maleate; Benzoate; Sulfonamides such as N-ethyltoluenesulfonamide; Organophosphate; Polybutene; Glycols / polyethers such as triethylene glycol dihexanoate; Paraffinic process oils such as SUNPAR 2280 (Sunoco Corp.); Special hydrocarbon fluids, and polymer modifiers; And those derived from renewable sources such as epoxidized grains (e.g., soy, corn, etc.) oils (i.e., biochemical plasticizers).

Examples of the curing agent in the present invention include (1) a free radical initiator (for example, an organic peroxide or an azo compound), (2) a silane functional group generally activated by moisture (for example, a vinylalkoxysilane or a vinylalkoxy (3) a sulfur-containing curing agent to facilitate vulcanization, and / or (4) a polymeric material selected from the group consisting of electromagnetic radiation (e.g., infrared (IR), ultraviolet (UV), visible, gamma , Etc.) to accelerate crosslinking of the composition.

Examples of the scorch retarder in the present invention include 2,2,6,6-tetramethylpiperidinoxyl (TEMPO) and 4-hydroxy-2,2,6,6-tetramethylpiperidinoxyl Roxy TEMPO).

Examples of the ultraviolet stabilizer in the present invention include hindered amine light stabilizers (HALS) and ultraviolet absorber (UVA) additives. Representative UVA additives include benzotriazole type, such as Tinuvin 326 and Tinuvin 328, commercially available from Ciba, Inc. A blend of HAL and UVA additives is also effective. Examples of antioxidants include hindered phenols such as tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane; (2-methyl-6-tert-butylphenol), 4,4'-thiobis (4-hydroxybenzyl) , 4'-thiobis (2-tert-butyl-5-methylphenol), 2,2'-thiobis -tert-butyl-4-hydroxy) -hydrocinnamate; Phosphites and phosphonites such as tris (2,4-di-tert-butylphenyl) phosphite and di-tert-butylphenyl-phosphonite; Thio compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate; Various siloxanes; Polymerized 2,2,4-trimethyl-1,2-dihydroquinoline, n, n'-bis (1,4-dimethylpentyl-p-phenylenediamine), alkylated diphenylamine, Bis (alpha, alpha-dimethylbenzyl) diphenylamine, diphenyl-p-phenylenediamine, mixed di-aryl-p-phenylenediamine, and other hindered amine anti-dispersants or stabilizers .

Examples of processing aids include, but are not limited to, metal salts of carboxylic acids, such as zinc stearate or calcium stearate; Fatty acids such as stearic acid, oleic acid, or erucic acid; Fatty amides such as stearamide, oleamide, erucamide, or N, N'-ethylene bis-stearamide; Polyethylene wax; Oxidized polyethylene wax; Polymers of ethylene oxide; Copolymers of ethylene oxide and propylene oxide; Vegetable wax; Petroleum wax; Non-ionic surfactants; Silicone fluids and polysiloxanes.

The resin composition for a heat-radiating sheet according to the present invention may be formed into a sheet form through a curing step, and then adhered to a heat source. At this time, the release film may be removed after being adhered to the heat source in a state of being laminated with the release film to facilitate adhesion of the composition. The release film may be a polyolefin-based base film commonly used in the art in which a release coating layer composed of a silicone type, a long chain alkyl type, a fluorine type, or the like is coated.

In the present invention, the method of preparing the pressure sensitive adhesive sheet containing the composition is not particularly limited, but a method of applying the composition to a release film in a thickness of 10 to 500 탆 and irradiating ultraviolet rays to cure the adhesive sheet is cited. At this time, the irradiation dose of ultraviolet rays may vary depending on the type of resin constituting the composition, but it is preferably 500 to 5,000 mJ / cm 2.

Examples of the coater used when applying the composition include, but are not limited to, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, .

The resin composition for a heat-radiating sheet of the present invention may be protected by a release film (separator) until use. Specifically, the resin composition for a heat-radiating sheet may be protected by being sandwiched between two release films or may be rolled up and protected by a single release film on both sides of the release film.

The resin composition for a heat-radiating sheet according to the present invention can be used for attaching an LED light source and a heat-radiating material (heat sink, graphite sheet, etc.) with the above characteristics, an electronic part such as a CPU or an AP, It can be used for electric parts and so on.

Hereinafter, the resin composition for a heat-radiating sheet including the insulating phase-change material according to the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples and comparative examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following examples and comparative examples.

The physical properties of the specimens prepared through the following examples and comparative examples were measured as follows.

(Electrical insulation)

Measurement was carried out in accordance with JIS-K-6911 using a resistivity meter (Hiresta UP MCP-HT450 type, manufactured by Mitsubishi Kagaku Kagaku Co., Ltd.) in an atmosphere of a temperature of 23 캜 and a humidity of 50% RH. The measured results were assigned to the following criteria.

Electrical Insulation ⊚: 1.0 × 10 ¹⁴ Ω / □ or more

Electrical Insulation ◯: 1.0 × 10 ¹² Ω / □ or more and 1.0 × 10 ¹⁴ Ω / □ or less

Electrical insulation?: 1.0 x 10 ⁹ ? /? Or more 1.0 x 10 ¹² ? /?

Electrical insulation x: Less than 1.0 x 10 ⁹ ? /?

(Thermal conductivity)

The thermal conductivity in the thickness direction was measured using a LFA 457 micro flash measuring instrument (NES cooking, Germany).

(Temperature falling width)

The specimen was attached to the heating element, and the temperature was measured with a non-contact thermometer. The temperature was measured with the same thermometer 30 minutes later.

(Adhesive property)

The prepared specimens were cut into a size of 100 mm long × 25 mm long and specimens were laminated on a test plate including SUS304. Then, the test piece and the rectangular sheet were attached to each other by making one round of a 2-kg rubber roller (width: about 50 mm), and the bonded test plates and the rectangular sheet were allowed to stand for 24 hours under conditions of 23 ° C and 50% RH. Thereafter, in accordance with JIS Z 0237, a tensile test in the direction of 180 占 was carried out at a peeling speed of 300 mm / min, and the adhesive force (N / 25 mm) of the rectangular sheet to the test plate was measured.

(Example 1)

First, 3 g of a toluene diisocyanate (Sigma-Aldrich, USA) which can be polymerized as an encapsulating material by condensation polymerization to make a thermal storage capsule, a paraffin as a capsule core material [Sigma-Aldrich ], And 5 g of acetone (Duksan, Korea) were added to 80 g of water and stirred at 8000 rpm for about 10 minutes using a homogenizer [T25 basic ULTRA-TURAX, IKA, Germany] A first solution was prepared.

Then, a second solution obtained by dispersing 0.6 g of polystyrene sulfonic acid-co-maleic acid (Sigma-Aldrich, USA) in 60 g of water was stirred at 600 rpm, The first emulsified solution was mixed with the second stirring solution to prepare a third solution.

, 0.005 g of polystyrene sulfonic acid-co-maleic acid (poly (styrene sulfonic acid-co-maleic acid)), 5 g of ethyldiamine (Junsei Chemical, Japan) and 5 g of water was added to the third solution The mixture was gradually mixed and reacted for 4 hours at 60 ° C with stirring at 600 rpm to prepare a heat storage capsule (particle diameter: 100 to 600 nm, see FIGS. 2 to 4).

Separately, a composition was prepared by mixing 30 parts by weight of the heat-storage capsules prepared in 100 parts by weight of an acrylate resin (Vinil (registered trademark) PSA SV-6805 solid content 47 mass% by Showa Denko K.K.) as a base resin , A peel-treated PET film (trade name: E7006, thickness: 25 mu m, manufactured by TOYOBO CO., LTD.) Was applied by a doctor blade and the solvent was dried to form a pressure-sensitive adhesive layer having a thickness of 10 mu m. The properties of the prepared specimens were measured and are shown in Table 1 below.

(Example 2)

A specimen was prepared in the same manner as in Example 1, except that 15 parts by weight of a filler mixed with aluminum oxide and whitening acid in a weight ratio of 70:30 was added to 100 parts by weight of the base resin. The properties of the prepared specimens were measured and are shown in Table 1 below.

(Example 3)

A specimen was prepared in the same manner as in Example 1, except that 5 parts by weight of polyallylamine derivative (Mw: 10,000) was further mixed as a dispersing aid in the preparation of the composition. The properties of the prepared specimens were measured and are shown in Table 1 below.

(Example 4)

A specimen was prepared in the same manner as in Example 1, except that 1.0 g of aluminum oxide nanoparticles having an average particle size of 50 nm was added during the preparation of the second solution. The properties of the prepared specimens were measured and are shown in Table 1 below.

(Example 5)

A specimen was prepared in the same manner as in Example 1, except that 1 part by weight of poly (arylene ether sulfone-co-vinylidene fluoride) having an average particle diameter of 300 nm was added during the preparation of the composition. The properties of the prepared specimens were measured and are shown in Table 1 below.

[Table 1]

As shown in Table 1, the resin composition for a heat-radiating sheet including the insulating phase-change material according to the present invention exhibits excellent thermal conductivity, temperature falling width, electrical insulation, and adhesive property. Particularly, Example 2 using a mixture of aluminum oxide and acid whiten with a filler exhibited a further excellent thermal diffusion effect. In Example 3 in which a dispersion auxiliary agent was further added, the thermal conductivity and the temperature lowering width were further improved. In Example 4 in which aluminum oxide nanoparticles were further added to the filler, the best electrical insulation, thermal conductivity, have. It can be seen that Example 5 in which an ionomer was further added showed improved adhesion properties while maintaining electrical insulation and thermal properties.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention as defined by the following claims. It will be understood that the invention may be modified and varied without departing from the scope of the invention.

100: filler
200:

Claims (8)

Base resin;
A filler in which aluminum oxide and yttria are mixed at a weight ratio of 60 to 80: 20 to 40;
A dispersion aid comprising a polyallylamine derivative;
An ionomer having an average particle diameter of 0.01 to 600 nm; And
A heat storage capsule dispersed in the base resin;
, Wherein the heat storage capsule
A resin composition for a heat radiation sheet, comprising a filler containing a phase change material and a coating layer containing the filler.
The method according to claim 1,
The phase change material is selected from the group consisting of Fe ₂ O _{3 .4} SO ₃ .9H ₂ O, NaNH ₄ SO ₄ .2H ₂ O, NaNH ₄ HPO ₄ .4H ₂ O, FeCl ₃ .2H ₂ O, Na ₃ PO ₄ .12H ₂ O _{, Na 2 SiO 3 · 5H 2} O, Ca (NO 3) 2 · 3H 2 O, K 2 HPO 4 · 3H 2 O, Na 2 SiO 3 · 9H 2 O, Fe (NO 3) 3 · 9H 2 O, One or more selected from K ₃ PO ₄揃 7H ₂ O, NaHPO ₄揃 12H ₂ O, CaCl ₂揃 6H ₂ O, Na ₂ SO ₄揃 10H ₂ O, and Na (CH ₃ COO) 揃 3H ₂ O Wherein the thermosetting resin is a thermosetting resin.
The method according to claim 1,
Wherein the phase change material is selected from the group consisting of paraffin wax, n-octanoic acid, n-octadecane, n-triacotane, hexadecane, nonadecane, eicosane, hexenoic acid, docosanoic acid, tricoic acid, tetracosanic acid, Wherein the insulating phase change material is at least one selected from the group consisting of glycol, lauric acid, propyl palmitate, capric acid, isopropyl stearate, butyl stearate, palmitic acid, myristic acid and vinyl stearic acid. And a thermosetting resin.
The method according to claim 1,
Wherein the base resin is selected from the group consisting of polydimethylsiloxane resin, epoxy resin, acrylate resin, organopolysiloxane resin, polyimide resin, fluorocarbon resin, benzocyclobutene resin, fluorinated polyallyl ether resin, polyamide resin, A heat-releasing sheet containing an insulating phase-change material, which is selected from the group consisting of an ester resin, a phenol resin resin, an aromatic polyester resin, a polyphenylene ether resin, a bismaleimide triazine resin and a fluororesin Resin composition.
delete delete delete The method according to claim 1,
Wherein the phase change material further comprises aluminum oxide nanoparticles. ≪ RTI ID = 0.0 > 11. < / RTI >

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