KR20200046356A - (meth)acrylic heat-conductive sheet, heat-radiating film and method of manufacturing heat-radiating film - Google Patents

Abstract

This specification provides a (meth) acrylate-based thermal conductive sheet, a heat dissipation film, and a method for manufacturing the heat dissipation film.

Description

Manufacturing method of (meth) acrylate thermal conductive sheet, heat dissipation film and heat dissipation film {(METH) ACRYLIC HEAT-CONDUCTIVE SHEET, HEAT-RADIATING FILM AND METHOD OF MANUFACTURING HEAT-RADIATING FILM}

The present invention relates to a (meth) acrylate-based thermal conductive sheet, a heat radiation film, and a method for manufacturing the heat radiation film.

2. Description of the Related Art Recently, as electronic devices used in automobiles, electrical and electronic fields have been improved in performance and miniaturization, electronic components mounted therein are undergoing large-capacity and high integration. The higher the integration of electronic components, the more heat is generated when the device is used. The generated heat causes malfunction of peripheral components and deterioration of the substrate, leading to deterioration of product functions. Accordingly, in order to dissipate heat from electronic products to the outside, thermal conductive sheets are introduced into electronic products.

Patent Publication No. 10-2004-0076072

The present invention is to provide a heat dissipation film that can easily separate the release film and the thermal conductive sheet even with a low peeling force, and easily obtain a thermal conductive sheet without deformation of the thermal conductive sheet.

In addition, it is intended to provide a thermally conductive sheet that can be separated without damaging the surface of an electronic product after being used in an electronic product because the adhesive strength with the surface of an electronic product such as stainless steel sheet or aluminum does not significantly increase over time. .

In order to solve the above problems, the present applicant has included uncured silicone in a release layer of a release film, and produced a (meth) acrylate-based thermal conductive sheet using the release film.

An exemplary embodiment of the present specification is a (meth) acrylate-based thermal conductive sheet; And a release film provided on one surface of the (meth) acrylate-based thermal conductive sheet, wherein the release film includes a base film; And a release layer provided on one surface of the base film and provided in contact with the (meth) acrylate-based thermal conductive sheet, wherein the release layer includes an uncured silicone compound.

An exemplary embodiment of the present invention is a (meth) acrylate-based thermal conductive sheet in which an uncurable silicone compound is present on a part of the surface, wherein the uncured silicone compound is a compound represented by Chemical Formula 3 below. do.

[Formula 3]

In Chemical Formula 3, c1 is an integer from 1 to 1000.

An exemplary embodiment of the present invention comprises the steps of forming a release layer on one surface of the base film to produce a release film; And forming a (meth) acrylate-based thermal conductive sheet on one surface of the release layer of the release film.

In the heat dissipation film according to an exemplary embodiment of the present invention, the release film can be separated from the (meth) acrylate-based thermal conductive sheet with a low peel force, and thus workability is easy, and deformation of the thermal conductive sheet can be prevented during peeling.

The (meth) acrylate-based thermal conductive sheet according to an exemplary embodiment of the present invention has low adhesion to the surface of an electronic product such as a battery module case or an aluminum cooling plate, so it is easy to rework at the time of initial attachment, and even if the electronic product passes over time It is possible to separate the thermally conductive sheet without damaging it.

1 and 2 illustrate a laminated structure of a heat dissipation film according to an exemplary embodiment of the present application.

Hereinafter, preferred embodiments of the present application will be described. However, embodiments of the present application may be modified differently from the following description, and the scope of the present application is not limited to the following description. Embodiments of the present application are provided to explain the present application in detail to those of ordinary skill in the art.

Among the physical properties mentioned in the present specification, when temperature affects the physical properties, the physical properties may be physical properties measured at room temperature unless otherwise specified. In the above, normal temperature may be, for example, any one of 15 ° C to 35 ° C, or any one of 20 ° C to 30 ° C, preferably any one of 20 ° C to 25 ° C.

In one embodiment of the present specification, the viscosity of the compound may be measured using a viscoelasticity meter (Brookfield, DV2T Viscometer). In the present specification, viscosity means a viscosity measured at 25 ° C unless otherwise indicated.

In one embodiment of the present specification, the weight average molecular weight may mean a converted value for polystyrene measured using GPC (Gel Permeation Chromatography) or the like. In the present specification, unless otherwise specified, 'molecular weight' means a weight average molecular weight.

In the present specification, solid content means a component excluding a solvent among components constituting the composition. In an exemplary embodiment, the solid content may mean remaining components when the composition is dried in an oven to remove all of the solvent.

In the present specification, the cured product means a material in which a component capable of participating in the curing reaction is cured or crosslinked through the curing reaction.

In this specification, unless otherwise specified, the weight ratio between compounds is a comparison of the weight of the solid content of each compound.

In the present specification, the thermosetting composition is a composition in which curing is induced by application of heat, and the photocurable composition is a composition in which curing is induced by electromagnetic waves. Here, the electromagnetic waves include microwaves, infrared rays (IR), ultraviolet rays (UV), X-rays, gamma rays, and particle beams.

Hereinafter, the present invention will be described in more detail.

An exemplary embodiment of the present specification is a (meth) acrylate-based thermal conductive sheet; And a release film provided on one surface of the (meth) acrylate-based thermal conductive sheet, wherein the release film includes a base film; And a release layer provided on one surface of the base film and provided in contact with the (meth) acrylate-based thermal conductive sheet, wherein the release layer includes an uncured silicone compound.

In one embodiment, the heat dissipation film may be used in the following form. After removing the release film from one side of the heat dissipation film, attach the surface of the heat conductive sheet from which the release film is removed to the electronic product, remove the release film provided on the opposite side of the heat conductive sheet to which the electronic product is attached, and then remove the release film Attach other electronic products to it.

In one embodiment, a heat generating component may be attached to one surface of the thermal conductive sheet, and a cooling component may be attached to the other surface.

In one embodiment, the heat-conducting sheet can be used inside a vehicle. In one embodiment, one surface of the heat-conducting sheet may be attached to an aluminum cooling plate, and a battery module may be attached to the other surface of the heat-conducting sheet.

The present invention is characterized in that, in one embodiment of the heat dissipation film, the release film can be removed from one surface of the heat dissipation film without deformation of the (meth) acrylate-based thermal conductive sheet.

The thermal conductive sheet may be peeled off for rework in the electronic product manufacturing process, or may be peeled off for recycling of the electronic product at a later time. The present invention is characterized in that, in one embodiment of the (meth) acrylate-based thermal conductive sheet, the adhesive strength with electronic products does not increase significantly over time, and peeling is easy after use of the thermal conductive sheet.

The above-described effect is realized on the heat dissipation film and the (meth) acrylate-based thermal conductive sheet according to an exemplary embodiment of the present invention is that the release layer contains an uncurable silicone compound.

The uncurable silicone compound does not participate in the curing reaction of the release layer composition. Accordingly, when the curing reaction of the release layer is finished, a part of the uncured silicone compound is a cured product of an organopolysiloxane compound containing an alkenyl group and an organopolysiloxane compound containing a hydrosilyl group (hereinafter simply referred to as a 'release layer cured product') (Hereinafter referred to as "), some uncured silicone compounds are present on the surface of the release layer.

When the heat conductive sheet is formed on the release layer in which the uncured silicone compound is present on the surface, when the release film is peeled off the heat conductive sheet, it can be transferred to the surface of the heat conductive sheet of the uncured silicone compound present on the surface of the release layer.

In the present specification, 'transfer' of the uncured silicone may mean that a part of the uncured silicone compound on the surface of the release film moves to the surface of the thermal conductive sheet. The transferred uncured silicone compound is present in physical contact with the surface of the thermal conductive sheet. The transferred uncured silicone compound modifies the surface of the thermally conductive sheet, thereby realizing the desired effect of the present invention.

In one embodiment, the release layer further includes a cured product of the release layer composition.

In one embodiment, the cured product of the release layer composition may be a cured product of an organopolysiloxane compound containing an alkenyl group and an organopolysiloxane compound containing a hydrosilyl group. In one embodiment, the release layer further comprises a cured product of an organopolysiloxane compound containing an alkenyl group and an organopolysiloxane compound containing a hydrosilyl group.

In one embodiment, the release layer composition is an organopolysiloxane compound containing an alkenyl group; Organopolysiloxane compounds containing a hydrosilyl group; And uncured silicone compounds.

In one embodiment, the organopolysiloxane containing the alkenyl group is specifically dimethylpolysiloxane blocked with dimethylvinylsiloxy groups at both ends of the molecular chain, dimethylsiloxane-methylvinyl blocked with dimethylvinylsiloxy groups at both ends of the molecular chain. Siloxane copolymer, dimethylsiloxane-methylphenylsiloxane copolymer with dimethylvinylsiloxy groups blocked at both ends of the molecular chain, methylvinylpolysiloxane with trimethylsiloxy groups blocked at both ends of the molecular chain, and trimethylsiloxy groups sealed at both ends of the molecular chain Dimethylsiloxane-methylvinylsiloxane copolymer, dimethylsiloxane-methyl (5-hexenyl) siloxane copolymer with trimethylsiloxy groups blocked at both ends of the molecular chain, dimethylsiloxane-methyl with dimethylvinylsiloxy groups blocked at both ends of the molecular chain Vinylsiloxane-methylphenylsiloxane copolymer, dimethyl at both ends of the molecular chain The hydroxysiloxy group may be blocked, such as methylvinylpolysiloxane or a dimethylsiloxane-methylvinylsiloxane copolymer in which dimethylhydroxysiloxy groups are blocked at both ends of the molecular chain, but is not limited thereto.

The organopolysiloxane compound containing the alkenyl group may be included in one kind or two or more kinds, and when two or more kinds are used, the mixing ratio of the compounds may be appropriately selected.

In one embodiment, the organopolysiloxane compound containing the alkenyl group may be a compound represented by Formula 1 below.

 [Formula 1]

In Formula 1, a1 is an integer of 1 or more, and a2 is an integer of 1 or more.

In one embodiment, a1 is an integer from 1 to 500.

In one embodiment, a2 is an integer from 1 to 500.

In one embodiment, the weight average molecular weight of the organopolysiloxane compound containing the alkenyl group is 500 g / mol to 1,000 g / mol.

In one embodiment, the organopolysiloxane compound containing the hydrosilyl group may be a compound represented by Formula 2 below.

[Formula 2]

In Chemical Formula 2,

R ₁ to R ₉ are the same as or different from each other, and each independently an alkyl group, and b1 and b2 are each independently an integer of 1 or more.

In one embodiment, the R ₁ to R ₉ are the same as or different from each other, and each independently a C1-C10 alkyl group; C1-C8 alkyl group; Or it is a C1-C4 alkyl group.

In one embodiment, b1 is an integer from 1 to 200.

In one embodiment, b2 is an integer from 1 to 400.

In one embodiment, the alkyl group of R ₁ to R ₉ is a methyl group; Ethyl group; n-propyl group; Isopropyl group; n-butyl group; Isobutyl group; sec-butyl group; t-butyl group; n-pentyl group; sec-pentyl group; Isopentyl group; n-hexyl group, and the like, but is not limited thereto.

In one embodiment, the Chemical Formula 2 is represented by the following Chemical Formula 2-1.

[Formula 2-1]

In Formula 2-1, b1 is an integer of 1 or more, and b2 is an integer of 1 or more.

In one embodiment, the weight average molecular weight of the organopolysiloxane compound containing the hydrosilyl group is 400 g / mol to 100,000 g / mol.

In one embodiment, the organopolysiloxane compound containing the hydrosilyl group is 0.1 part to 10 parts by weight compared to 100 parts by weight of the organopolysiloxane compound containing the alkenyl group; Or 0.5 to 5 parts by weight. When the compound containing the hydrosilyl group is included below the above range, curing may be insignificant, and when it is included above the above range, there may be problems such as overcuring and rapid curing.

In one embodiment, the release layer composition further comprises a solvent.

The solvent may be used without limitation as long as it dissolves an organopolysiloxane compound containing an alkenyl group and an organopolysiloxane compound containing a hydrosilyl group.

In one embodiment, the solvent may be toluene, isopropyl alcohol (IPA), acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), xylene, and the like, but is not limited thereto.

In one embodiment, the release layer composition solids concentration is 1% to 50% by weight. The concentration of the solid content of the release layer composition means (weight of the solid content of the release layer composition) / (weight of the release layer composition) * 100.

In one embodiment, the release layer composition is one or two selected from the group consisting of a catalyst, a curing delay agent, a reaction delay agent, an antistatic agent, an antioxidant, an antifouling coating agent, a peel force control agent, a coupling agent, and a curing initiator. The additive may be further included.

In one embodiment, the release layer composition may further include a catalyst to control the crosslinking density.

In one embodiment, the catalyst may be a platinum-based catalyst.

As the platinum-based catalyst, platinum-based compounds such as chloroplatinic acid, an alcoholic solution of chloroplatinic acid, a complex of chloroplatinic acid and olefin, a chloroplatinic acid-alkenylsiloxane complex, platinum black, platinum-supported silica, platinum-supported activated carbon, and the like can be used. However, it is not limited thereto.

In one embodiment, the concentration of the platinum-based catalyst is 1,000ppm to 10,000ppm compared to the solid content of the release layer composition; 2,000 ppm to 9,000 ppm; 3,000 to 8,000 ppm; Or 4,000 ppm to 5,000 ppm.

In one embodiment, the release layer composition may further include a curing retarder. In one embodiment, as the curing retarder, a compound having a carbon-carbon double bond or a carbon-carbon triple bond may be used.

The curing retarder is 1-ethynyl-1-cyclohexanol, 3-methyl-1-penten-3-ol, 2-methyl-3-butyn-2-ol, 3-phenyl-3-butyn-2- All, 1-phenyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 1,5-hexadiine, 1,6-heptadine, 3,5-dimethyl- 1-hexine, 2-ethyl-3-butyne, 2-phenyl-3-butyne, 1,3-divinyltetramethyldisiloxane, 1,3,5,7-tetravinyl-1,3,5,7- It may be one or two or more selected from the group consisting of tetramethylcyclotetrasiloxane and 1,3-divinyl-1,3-diphenyldimethyldisiloxane, but is not limited thereto.

The release layer composition includes an uncurable silicone compound.

In one embodiment, the uncurable silicone compound may be a compound represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3, c1 is an integer from 1 to 1000.

The release layer composition may include a thermosetting release layer composition; Or it is a photocurable release layer composition.

The curing reaction of the release layer composition will be described using heat curing as an example. In the curing process of the silicone release coating composition, an alkenyl group of an organopolysiloxane compound containing an alkenyl group and a hydrosilyl group of an organopolysiloxane compound containing a hydrosilyl group react with each other.

In the present specification, uncured means a property that does not participate in the curing reaction. In one embodiment, the uncurable silicone compound may mean a compound that does not participate in a curing reaction between an alkenyl group and a hydrosilyl group.

Since the uncured silicone compound has a smaller density than the curable compound included in the release layer composition, a part of the uncured silicone compound may be present on the surface of the release layer composition after the curing reaction of the release layer composition.

In one embodiment, the content of the alkenyl and hydrosilyl groups of the uncurable silicone compound is 0% by weight, respectively.

In one embodiment, the uncurable silicone compound is 1 part by weight to 20 parts by weight based on 100 parts by weight of the organopolysiloxane compound containing the alkenyl group; 3 parts by weight to 20 parts by weight; Or 5 to 15 parts by weight. When the uncured silicone compound is included below the above range, the surface modification of the heat conducting sheet may be insufficient, and when it is included above the above range, the adhesive force between the release film and the (meth) acrylate-based heat conducting sheet is severely lowered so that the release film is a heat conducting sheet. Since it is not attached to the surface, the handleability of the thermal conductive sheet may be deteriorated.

In one embodiment, the viscosity at 25 ° C. of the release layer composition having a solid content concentration of 5 wt% may be 20 cps to 30 cps. When the viscosity of the release layer composition is less than the above range, the workability is lowered during application and drying of the composition, and when it exceeds the above range, the surface of the release layer is not flat, which may lead to a defect in the thermal conductive sheet.

The heat conductive sheet is a layer attached to a heating element such as an electronic product when removing the release film from the heat dissipation film.

In one embodiment, the (meth) acrylate-based thermal conductive sheet may be formed by applying and curing a (meth) acrylate-based thermal conductive sheet composition on one surface of a release layer. The (meth) acrylate-based thermal conductive sheet includes a cured product of the (meth) acrylate-based thermal conductive sheet composition.

In one embodiment, the (meth) acrylate-based thermal conductive sheet composition comprises (meth) acrylate-based resin; filler; And plasticizers.

The (meth) acrylate-based resin may be an acrylic polymer including one or two or more alkyl (meth) acrylates as a monomer component. The (meth) acrylate-based resin may be a homopolymer or a copolymer. In the present specification, the (meth) acrylate means acrylate and / or methacrylate.

In the alkyl (meth) acrylate, the alkyl group may be a linear or branched alkyl group having 1 to 20 carbon atoms. The alkyl (meth) acrylate is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylic Rate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-octyl (Meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, tetradecyl (meth) acrylate, and the like, but are not limited thereto. The alkyl (meth) acrylate monomer may be included in 50% to 100% by weight relative to 100% by weight of the total monomer component constituting the (meth) acrylate-based resin.

The (meth) acrylate-based resin may further include other monomer units polymerizable with the alkyl (meth) acrylate. Examples of the other monomer units include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; Acid anhydride monomers such as maleic anhydride and itaconic anhydride; Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxydecyl (meth) ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl ( Hydroxy group-containing monomers such as meth) acrylates; Contains sulfonic acid groups such as styrenesulfonic acid, allylsulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidepropanesulfonic acid, sulfopropyl (meth) acrylate, and (meth) acryloyloxynaphthalenesulfonic acid Monomer; Amide systems such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, and N-methylolpropane (meth) acrylamide Monomer; Amino group-containing monomers such as dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; Alkoxyalkyl group-containing monomers such as methoxyethyl (meth) acrylamide and ethoxyethyl (meth) acrylamide; N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide, N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide , Imide group-containing monomers such as N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itaconimide, and N- lauryl itaconimide; N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide, etc. Succinimide-based monomer; Vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinyl Vinyl monomers such as morpholine, N-vinylcarboxylic acid amides, styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, and N-vinyl caprolactam; Cyano group-containing monomers such as acrylonitrile and methacrylonitrile; Epoxy resin-containing monomers such as (meth) acrylic acid glycidyl; Glycol-based (meth) acrylate monomers such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate; Ester-based (meth) acrylate monomers having fluorine, silicone, halogen, silicon, and the like; Hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylic Polyfunctional monomers such as acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, and urethane acrylate; Olefin monomers such as isoprene, butadiene, and isobutylene; And it may include one or two or more selected from the group consisting of vinyl ether monomers such as vinyl ether, but is not limited thereto. Other monomer units polymerizable with the alkyl (meth) acrylate may be included in an amount of 0% to 50% by weight with respect to 100% by weight of the total monomer components constituting the (meth) acrylate-based resin.

The (meth) acrylate-based resin is a conventional polymerization method, for example, solution polymerization, photopolymerization, bulk polymerization, suspension polymerization or emulsion polymerization. ) And the like.

In one embodiment, the filler is aluminum (Al), nickel (Ni), copper (Cu), tin (Sn), zinc (Zn), tungsten (W), iron (Fe), silver (Ag), etc. Ceramic powders such as metal powder, calcium carbonate (CaCO ₃ ), aluminum oxide (Al ₂ O ₃ ), magnesium oxide, aluminum hydroxide (Al (OH) ₃ ), silicon carbide (SiC), boron nitride (BN) and aluminum nitride It may include one or two or more selected from, but is not limited thereto. In one embodiment, it is preferable to use aluminum hydroxide, aluminum oxide, magnesium oxide or the like as the filler in view of realizing good insulating properties.

In one embodiment, the filler may be spherical. Here, the spherical shape means that it is close to the spherical shape, and is not limited as long as it is rounded.

In one embodiment, the average particle diameter of the filler is more than 0㎛ 200㎛. Here, the average particle diameter means the average value of the longest length of the diameter of the filler.

In one embodiment, the filler may be one or two or more. When two or more fillers are used, the content ratio of the fillers can be appropriately selected.

In one embodiment, the filler has a filler having a particle diameter of more than 0㎛ 10㎛; And it may include a filler having a particle diameter of more than 10㎛ 200㎛.

In one embodiment, the filler is included in 350 parts by weight to 450 parts by weight based on 100 parts by weight of the (meth) acrylate resin. When the content of the filler is less than the above range, the thermal conductivity of the thermally conductive sheet may be lowered, and if it is more than the above range, the heat dissipation effect of the thermally conductive sheet may be lowered.

In one embodiment, the thermal conductive sheet composition includes a plasticizer.

As the plasticizer, a conventional plasticizer can be used.

In one embodiment, the plasticizer is a citrate-based plasticizer; Trimellitic acid ester plasticizers; Pyromellitic acid ester plasticizers; Phosphate plasticizers; Phthalate plasticizers; And one or two or more selected from the group consisting of an adipate plasticizer, but is not limited thereto.

The citrate plasticizer may be triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate (ATBC) or acetyl trioctyl citrate, but is not limited thereto.

The trimellitic acid ester plasticizer is trimellitic acid tri (n-octyl), trimellitic acid tri (2-ethylhexyl), trimellitic acid triisooctyl, trimellitic acid triisononyl, trimellitic acid triisodecyl, etc. Trimellitic acid trialkyl ester, and the like, but is not limited thereto.

The pyromellitic acid ester plasticizer may be a pyromellitic acid tetraalkyl ester such as tetra (n-octyl) pyromellitate or tetra (2-ethylhexyl) pyromellitate, but is not limited thereto.

The phosphate-based plasticizer may be tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, isodecyldiphenyl phosphate, 2-ethylhexyl-diphenyl phosphate, bis- (2-ethylhexyl) phenyl phosphate, etc., It is not limited to this.

The phthalate plasticizer is dioctyl phthalate, dibutyl phthalate, dimethyl phthalate, diethyl phthalate, diheptyl phthalate, dinonyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, butylbenzyl phthalate, butyllauryl Phthalate, and the like, but is not limited thereto.

The adipate plasticizer may be dioctyl adipate, diisononyl adipate, diisodecyl adipate, etc., but is not limited thereto.

In one embodiment, the plasticizer is 30 parts by weight to 150 parts by weight based on 100 parts by weight of the (meth) acrylate-based resin; Or 30 parts by weight to 100 parts by weight. When the content of the plasticizer is less than the above range, it is difficult to form a thermal conductive sheet, and a bleed out phenomenon in which the plasticizer migrates to the surface of the thermal conductive sheet and precipitates is liable to occur.

The thermal conductive sheet composition is of a solvent-free type. Here, the solvent-free type means that the composition does not contain a solvent.

The thermal conductive sheet composition is one selected from the group consisting of a photoinitiator, a curing agent, a crosslinking agent, a UV stabilizer, an antioxidant, a reinforcing agent, a filler, an antifoaming agent, a surfactant, a plasticizer, and combinations thereof, in a range that does not degrade the properties of the thermal conductive sheet, or It may further include two or more additives.

In one embodiment, the thermal conductive sheet composition is a photocurable composition, and may further include a photoinitiator. The photoinitiator is a material that initiates a photocuring reaction by light irradiation, and the type is not particularly limited, but is not limited to triazine compounds, biimidazole compounds, acetophenone compounds, O-acyloxime compounds, thioxanthone compounds, It may include one or two or more selected from the group consisting of phosphine oxide compounds, coumarin compounds and benzophenone compounds.

In one embodiment, the photoinitiator is 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6 -Triazine, 2,4-trichloromethyl- (fiflonil) -6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6-triazine, 3- {4- [2,4-bis (trichloromethyl) -s-triazine-6-yl] phenylthio} propanoic acid, 2,4-trichloromethyl- (4'-ethylbiphenyl) -6-tri Triazine-based compounds such as azine or 2,4-trichloromethyl- (4'-methylbiphenyl) -6-triazine; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole or 2,2'-bis (2,3-dichlorophenyl) -4,4', 5 Biimidazole-based compounds such as, 5'-tetraphenylbiimidazole; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxye Thoxy) -phenyl (2-hydroxy) propyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2-methyl- (4-methylthiophenyl) -2-mol Acetopes such as polyno-1-propan-1-one (Irgacure-907) or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure-369) Non-based compounds; O-acyloxime compounds such as Irgacure OXE 01 and Irgacure OXE 02 manufactured by Ciba Geigy; Benzophenone compounds such as 4,4'-bis (dimethylamino) benzophenone or 4,4'-bis (diethylamino) benzophenone; Thioxanthone-based compounds such as 2,4-diethyl thioxanthone, 2-chloro thioxanthone, isopropyl thioxanthone or diisopropyl thioxanthone; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide or bis (2,6-dichlorobenzoyl) propyl phosphine oxide Phosphine oxide compounds such as; 3,3'-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin and 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-Cl] -Benzopyrano [6,7,8-ij] -quinolinazine-11-one may be one or two or more selected from the group consisting of, but is not limited thereto.

In one embodiment, the photoinitiator is 0.05 parts by weight to 5 parts by weight based on 100 parts by weight of the (meth) acrylate-based resin; Or 0.1 part by weight to 3 parts by weight.

In one embodiment, the thermal conductive sheet composition may further include a coupling agent. The coupling agent may use a known coupling agent, in one embodiment, the coupling agent is a silane coupling agent; Titanate-based coupling agents; And a zirconium-based coupling agent.

The silane coupling agent is 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyl (dimethoxy) methylsilane, 2- (3,4 -Epoxy silane coupling agents such as epoxycyclohexyl) ethyl trimethoxysilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 11-mercaptoundecyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethoxymethylsilane, 3-ureidpropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Methyl diethoxysilane, p-styryl trimethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-isocyanatepropyl trimethoxysilane, bis (triethoxysilyl Propyl) disulfide, bis (triethoxysilylpropyl) tetrasulfide, phenyltrimethox Silane, methacryloxypropyl trimethoxy silane, or the like, but imidazole silane, triazine jinsilran, and the like.

The titanate-based coupling agent is poly-n-butyl-titanate, tetra-n-butyl titanate, tetraisopropyl titanate, tetraethylhexyl titanate, isopropyl trioleic titanate, isopropyl triisosteroyl Titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl) titanate, isostearyl titanate, tetraoctylbis (ditridecylphosphate) titanate, bis (dioctylpyro Phosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, and the like, but is not limited thereto.

The zirconium-based coupling agent may be, but is not limited to, tetra normal-propyl zirconate, tetra normal-butyl zirconate, triethanol amine zirconate, hexafluoro zirconate, and the like.

In an exemplary embodiment, when a titanate-based coupling agent is used as the coupling agent, handleability of the thermal conductive sheet composition is improved, and workability in manufacturing the thermal conductive sheet can be improved.

In one embodiment, the coupling agent is 0.001 parts by weight to 10 parts by weight based on 100 parts by weight of the filler; Or 0.001 part to 5 parts by weight.

In one embodiment, the thermal conductive sheet composition may further include an antioxidant.

The antioxidant may include one or two or more selected from the group consisting of phenol-based antioxidants, aromatic amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants, but is not limited thereto.

The phenolic antioxidant is 2,6-di-tertiary-butyl-4-methyl-phenol (BHT), thiodiethylene bis 2- (3,5-di-t-butyl-4-hydroxyphenyl) pro Cypionate (Songnox 1035), Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionate] methane, pentaerythritol tetrakis [-3- [3,5-di-t-butyl-4-hydroxypentyl]] propionate, and the like, but is not limited thereto. Does not work.

The aromatic amine antioxidants are phenylnaphthylamine, 4,4 '-(α, α-dimethylbenzyl) diphenylamine, and N, N'-di-2-naphthyl-p-phenylenediamine, 4, It can be 4'-dioctyldiphenylamine, N, N'-diphenyl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-P-phenylenamine, N-benzylethylenediamine, alkyldiphenylamine, etc. However, it is not limited thereto.

The phosphorus antioxidant is tris (2,4-di-tertiary-butylphenyl) phosphite, tris (nonylphenyl) phosphite (TNPP), di- (2,4-di-tertiary-butylphenyl) pentaerythritol Diphosphide, and the like, but is not limited thereto.

The sulfur-based antioxidant may be, but is not limited to, distearyl thiodipropionate, ditridecylthiodipropionate, dilauryl thiodipropionate, and the like.

In one embodiment, the antioxidant is 0.001 to 2 parts by weight based on 100 parts by weight of the (meth) acrylate-based resin; Or 0.005 to 1 part by weight.

In one embodiment, the thickness of the thermal conductive sheet is 0.1mm to 10mm; 0.1 mm to 5 mm; It is preferably 0.5 mm to 2 mm. When the thickness of the thermally conductive sheet is less than the above range, handleability is deteriorated, and if it is above the above range, workability may be problematic.

In one embodiment, a portion of the uncurable silicone compound is present on the surface of the release layer in contact with the (meth) acrylate-based thermal conductive sheet.

In one embodiment, when the release film in the heat dissipation film is peeled at a peel angle of 180 ° and a peel rate of 1.8 m / min, at least a part of the surface of the (meth) acrylate-based thermal conductive sheet is the uncured silicone The compound is present.

In one embodiment, when the release film in the heat dissipation film is peeled at a peel angle of 180 ° and a peel rate of 1.8 m / min, at least a part of the surface of the (meth) acrylate-based thermal conductive sheet is the uncured silicone The compound is present in physical contact with the surface of the (meth) acrylate-based thermal conductive sheet.

In one embodiment of the present specification, the release film may be removed from the heat dissipation film to form a thermal conductive sheet.

An exemplary embodiment of the present specification provides a method for manufacturing a (meth) acrylate-based thermal conductive sheet comprising the step of removing the release film from the heat dissipation film.

In the present specification, unless otherwise specified, physical properties are values measured under a temperature of 25 ° C. and a relative humidity of 50%.

In one embodiment, the peel force (F1) measured at a peel angle of 180 ° and a peel speed of 1.8 m / min with respect to the (meth) acrylate-based thermal conductive sheet of the release film is 0.5 gf / in to 15 gf / in; 0.5gf / in to 12gf / in; 0.5 gf / in to 10 gf / in; Or 0.5gf / in to 8gf / in.

In one embodiment, the peel force (F1) can be measured using a peel strength (AR-1000, Chem Instrument).

In one embodiment, in the heat dissipation film, the release film is peeled at a peel angle of 180 ° and a peel rate of 1.8 m / min, and one surface of the (meth) acrylate-based thermal conductive sheet is made of stainless steel sheet (JIS SUS 304). In accordance with JIS Z 0.27, attached with a 2 kg roller, and stored for 24 hours under a temperature of 25 ° C. and 50% relative humidity, 180 ° to the stainless steel sheet of the (meth) acrylate-based thermal conductive sheet The peeling force (F2) measured at a peeling angle of 0.3 m / min and a peeling speed of 30 gf / in or less; 1gf / in to 30gf / in; 1 gf / in to 27 gf / in; Or 1 gf / in to 25 gf / in.

In one embodiment, in the heat dissipation film, the release film is peeled at a peel angle of 180 ° and a peel rate of 1.8 m / min, and one surface of the (meth) acrylate-based thermal conductive sheet is attached to an aluminum substrate (KS D6759). Attached with a 2 kg roller according to JIS Z 0.27, and stored for 24 hours under a temperature of 25 ° C and a relative humidity of 50%, 180 ° of the (meth) acrylate-based thermal conductive sheet to the aluminum substrate Peeling force (F3) measured at a peeling angle and a peeling rate of 0.3 m / min was 35 gf / in or less; 1 gf / in to 35 gf / in; 1 gf / in to 32 gf / in; 1gf / in to 30gf / in; Or 1gf / in to 28gf / in.

In one embodiment, in the heat dissipation film, the release film is peeled at a peeling angle of 180 ° and a peeling rate of 1.8 m / min, and the (meth) acrylate-based thermal conductive sheet is coated on a stainless steel sheet (JIS SUS 304) JIS Attached with a 2 kg roller according to Z 0.27, and stored for 24 hours at a temperature of 25 ° C. and 50% relative humidity, maintaining a pressing time of 0.01 second under a load of 800 g of the (meth) acrylate-based thermal conductive sheet, The measured tack force was 80 gfin or less; 1 gf / in to 75 gf / in; 1 gf / in to 70 gf / in; Or 1gf / in to 66gf / in.

In one embodiment, the tack force measured by maintaining the pressing time of 0.01 second under the load of 800 g of the (meth) acrylate-based thermal conductive sheet is a peel force measured at a temperature of 25 ° C. and a relative humidity of 50%. Power.

In one embodiment, When the release film is peeled from the heat dissipation film at a peeling angle of 180 ° and a peeling rate of 1.8 m / min, the length of the (meth) acrylate-based thermal conductive sheet in the peeling direction is less than 1%.

In one embodiment, the adhesive strength increase rate of the (meth) acrylate-based thermal conductive sheet is 10% or less; 9% or less; 8% or less; 7% or less; 6% or less; Or 5.5% or less.

The adhesion increase rate is calculated by the following equation (1),

[Equation 1]

Adhesion increase rate (%) = (F6-F2) / (F2) * 100

In Equation 1,

F6 peels the release film from the heat dissipation film at a peel angle of 180 ° and a peel rate of 1.8 m / min, and one surface of the (meth) acrylate-based thermal conductive sheet is stainless steel sheet (JIS SUS 304) JIS J Attached with a 2 kg roller based on 0.27, and stored for 7 days at a temperature of 60 ° C., the (meth) acrylate-based thermal conductive sheet was peeled at 180 ° with respect to the stainless steel sheet and at an angle of 0.3 m / min. Peeling force at the time of peeling at the peeling speed,

F2 peels the release film from the heat dissipation film at a peel angle of 180 ° and a peel rate of 1.8 m / min, and one surface of the (meth) acrylate-based thermal conductive sheet is coated on a stainless steel sheet (JIS SUS 304) with JIS Z 0.27. Attached with a 2 kg roller according to the above, and stored for 24 hours under a temperature of 25 ° C. and a relative humidity of 50%, the (meth) acrylate-based thermal conductive sheet was peeled at an angle of 180 ° with respect to the stainless steel sheet and It is the peeling force at the time of peeling measured at the peeling speed of 0.3 m / min.

In an exemplary embodiment, a tesa 7475 tape having a width of 25 mm and a length of 300 nm is attached to the release layer of the release film, and is passed through a 4 kg / cm ² pressing roll twice with an automatic reciprocating roller, followed by pressing for 5 hours under a load of 5 kg. When pre-treatment at room temperature and fixing release paper on a grip using a peel strength (AR-1000, Chem Instrument), when the release film is peeled at a 0.3 m / min speed and a peel angle of 180 ° The peel force (F4) of 10gf / in or less; 1gf / in to 10gf / in; 1 gf / in to 8 gf / in; Or 1gf / in to 6gf / in.

In one embodiment, in the measurement of the F2, F3, F4, and F5, the (meth) acrylate-based thermal conductive sheet with respect to the stainless steel sheet with a peeling angle of 180 ° and a peeling rate of 0.3m / min The force F2 is the peel force measured under a temperature of 25 ° C and a relative humidity of 50%.

In one embodiment, in the measurement of F6, the relative humidity when stored at a temperature of 60 ° C for 7 days is 90%.

In one embodiment, the vertical thermal conductivity of the (meth) acrylate-based thermal conductive sheet is 1W / mK to 2W / mK; 1.2W / mK to 2W / mK; Or 1.4W / mK to 2W / mK. Here, the vertical thermal conductivity means a thermal conductivity in a direction perpendicular to a plane parallel to the layered surface of the thermal conductive sheet.

In the present specification, the thermal conductivity of the thermal conductive sheet may be measured by a thermal interface material meter (Analysis Tech, TIM TESTER 1300) based on ASTM D5470 measurement standard.

One embodiment of the present specification, forming a release layer on one surface of the base film to prepare a release film; And forming a (meth) acrylate-based thermal conductive sheet on one surface of the release layer of the release film.

In one embodiment, the manufacturing of the release film may include coating a release layer composition on one surface of the base film; And curing the coated release layer composition.

In one embodiment, the step of forming the (meth) acrylate-based thermal conductive sheet may include applying a (meth) acrylate-based thermal conductive sheet composition to one surface of the release layer; And curing the coated (meth) acrylate-based thermal conductive sheet composition.

The release film is a film that is removed from the heat dissipation film when the (meth) acrylate-based thermal conductive sheet is attached to a heating element such as an electronic product.

The release film is a base film; And a release layer provided on one surface of the base film.

The type of the base film is not particularly limited and may be appropriately selected.

The base film is, for example, polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polybutene film, polybutadiene film, vinyl chloride copolymer film, polyurethane film, ethylene-vinyl acetate film , Ethylene-propylene copolymer film, ethylene-acrylic acid ethyl copolymer film, ethylene-acrylic acid methyl copolymer film or polyimide film, but is not limited thereto.

In one embodiment, the base film may be a polyethylene terephthalate (PET) film.

The thickness of the base film may be appropriately selected in consideration of the purpose of the present application. For example, the thickness of the base film may be 25 μm or more and 150 μm or less, 50 μm or more and 125 μm or less, or 75 μm or more and 100 μm or less. When the range of the base film is less than the above-mentioned thickness range, when the (meth) acrylate-based thermal conductive sheet is produced, sagging occurs in the release film, and the thickness of the (meth) acrylate-based thermal conductive sheet may be non-uniform, and when the range is more than the above range, cost increases There is a problem and the winding of the film can be difficult.

For the base film, for example, appropriate treatment such as corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, or sputter etching treatment may be performed.

In one embodiment, the thickness of the release layer is 30nm to 500nm; 30 nm to 400 nm; It is preferably 30 nm to 300 nm. When the thickness of the release layer is less than the above-mentioned range, the releasability decreases.

In one embodiment of the present specification, the method of coating the release layer composition on one surface of the base film is a gravure coating method, a kiss coating method, a die coating method, a lip coating method, a comma coating method, a blade coating method, a roll coating method, A knife coating method, a spray coating method, a bar coating method, a spin coating method or a dip coating method may be used, but is not limited thereto.

The method of applying the (meth) acrylate-based thermal conductive sheet composition to one surface of the release layer is not limited, and a coating method used when forming a conventional thermal conductive sheet can be used. In one embodiment, as a method of applying the (meth) acrylate-based thermal conductive sheet composition, a die coating method, a lip coating method, a comma coating method, a blade coating method, a roll coating method, a knife coating method, etc. may be used. It is not limited to this.

In one embodiment, the step of preparing the release film may further include drying the applied release layer composition after the applying step of the release layer composition in order to remove the solvent of the applied release layer composition.

In one embodiment, drying of the coated release layer composition may be performed at a temperature of 120 ° C to 180 ° C for a time of 30 seconds to 2 minutes.

In one embodiment of the present specification, the method of curing the applied release layer composition and the applied (meth) acrylate-based thermal conductive sheet composition is heat treatment; Plasma treatment; And one or more of ultraviolet irradiation treatment methods, but is not limited thereto.

In one embodiment of the present specification, the coated release layer composition is cured through heat treatment. In one embodiment, the coated release layer composition is heat cured at a temperature of 120 ° C to 180 ° C for a period of 30 seconds to 2 minutes.

In one embodiment of the present specification, the applied (meth) acrylate-based thermal conductive sheet composition is cured through ultraviolet irradiation. In one embodiment, curing of the coated (meth) acrylate-based thermal conductive sheet composition is irradiated with 0.1 mW / cm ² to 10 mW / cm ² of ultraviolet light at a temperature of 20 ° C. to 50 ° C. for 5 to 20 minutes. Can be achieved. In one embodiment, the ultraviolet light source may include a mercury arc lamp, a low pressure mercury wrap, a medium pressure mercury wrap, a high pressure mercury lamp, and a metal halide lamp, but is not limited thereto.

Hereinafter, the present invention will be described in more detail through examples according to the present invention and comparative examples not according to the present invention, but the scope of the present invention is not limited by the examples given below.

Example 1

100 parts by weight of polysiloxane containing alkenyl group (Evoik, VS5000) 5 parts by weight of polysiloxane containing hydrosilyl group (Evoik, Crosslinker 200), 5 parts by weight of an uncured silicone compound (Dow Corning, PMX-200), epoxy 0.05 parts by weight of silane, 50 ppm of platinum chelate catalyst (Evonik, catalyst 500) and 0.1 parts by weight of curing retarder (Evonik, Inhibitor 200) were diluted in a solvent mixed with methyl ethyl ketone, toluene, hexane and heptane, and solid content concentration was 5 wt% A release layer composition was formed.

The release layer composition was applied to one surface of a corona-treated 75 μm-thick polyester base film (SKC, SG00), dried at 170 ° C. for 1 minute, and 150 nm thick. A release film on which a release layer was formed was prepared.

100 parts by weight of 2-ethylhexyl acrylate (2-EHA), 0.6 parts by weight of 1,6-hexanediol diacrylate (HDDA), 50 parts by weight of plasticizer (diisononyl adipate), photoinitiator (2,2-dimethoxy) 2 parts by weight of -2-phenyl acetophenone, 6.6 parts by weight of coupling agent (isostearyl titanate), 0.05 parts by weight of antioxidant (pentaerythritol tetrakis [3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionate), 530 parts by weight of aluminum hydroxide with a particle diameter of 17 µm and 130 parts by weight of aluminum hydroxide with a particle diameter of 1.5 µm were supplied to a planetary mixer (a co-rotating mixer), kneaded for 1 hour to degas and mix to prepare a thermal conductive sheet composition. The heat conductive sheet composition was applied to the release layer of the release film, and irradiated with 1 mW / cm ² of ultraviolet light for 10 minutes to prepare a heat dissipation film including a heat conductive sheet having a thickness of 2 mm.

Example 2

A release film of Example 2 was prepared in the same manner as in Example 1, except that the uncured silicone compound was mixed in 10 parts by weight instead of 5 parts by weight.

Comparative Example 1

A release film of Comparative Example 1 was prepared in the same manner as in Example 1, except that the uncured silicone compound was not used.

Comparative Example 2

A corona-treated 75 μm-thick polyester base film (SKC, SG00) having no release layer was used as a heat dissipation film.

How to measure the release force (F4) of the release film

An adhesive tape (tesa 7475 tape) having a width of 25 mm and a length of 300 nm was attached to the release layer of the release film, and then passed through a 4 kg / cm ² pressure roll twice with an automatic reciprocating roller, followed by compression, followed by pretreatment at room temperature for 24 hours under a load of 5 kg. Then, using a peel strength (AR-1000, Chem Instrument, Inc.) to fix the adhesive tape to the grip (grip) and then peeling force (F4) when peeling at a peel angle of 0.3m / min speed and 180 ° It was measured.

Method for measuring peeling force (F1) between release film and thermally conductive sheet

In the prepared heat dissipation film, the peel strength when peeling the release film at a peel angle of 180 ° and a peel speed of 1.8 m / min using a peel strength (AR-1000, Chem Instrument) was measured.

Method for measuring peel force (F2) between stainless steel sheet and thermal conductive sheet

In the produced heat dissipation film, the release film is peeled at a peeling angle of 180 ° and a peeling rate of 1.8 m / min, and then one surface of the heat-conducting sheet is rolled on a stainless steel sheet (JIS SUS 304) surface according to JIS Z 0.27 with a 2 kg roller Attach with. After storage for 24 hours at a temperature of 25 ° C and a relative humidity of 50%, the heat conducting sheet was peeled using a tensile tester (Texture analyzer) at a peel angle of 180 ° and a peel rate of 0.3 m / min. Peeling force (F2) was measured.

Method for measuring peeling force (F3) between an aluminum substrate and a thermally conductive sheet

In the produced heat dissipation film, the release film is peeled at a peeling angle of 180 ° and a peeling rate of 1.8 m / min, and then one surface of the heat-conducting sheet is a roller of 2 kg according to JIS Z 0.27 on the surface of the aluminum (KS D6759) substrate. Attach with. After storage for 24 hours at a temperature of 25 ° C and a relative humidity of 50%, the heat conducting sheet was peeled using a tensile tester (Texture analyzer) at a peel angle of 180 ° and a peel rate of 0.3 m / min. Peeling force (F3) was measured.

How to measure tack force (F5)

After peeling the release film from the prepared heat dissipation film at a peel angle of 180 ° and a peel speed of 1.8 m / min, the heat conductive sheet is attached to a stainless steel sheet (JIS SUS 304) with a 2 kg roller according to JIS Z 0.27. After storing at a temperature of 25 ° C. and 50% relative humidity for 24 hours, a tack force (F5) was measured by maintaining a pressing time of 0.01 sec under a load of 800 g using a tensile analyzer (texture analyzer).

Deformation measurement during release of release film

When the release film in the produced heat dissipation film is peeled at a peeling angle of 180 ° and a peeling rate of 1.8 m / min, the degree of deformation is indicated by X when the length of the thermal conductive sheet in the peeling direction increases to less than 1%, When stretched to 1% or more, the degree of deformation was denoted by O.

Measurement of increase in adhesive strength of thermal conductive sheets

In the produced heat dissipation film, the release film is peeled at a peeling angle of 180 ° and a peeling rate of 1.8 m / min, and then one surface of the heat-conducting sheet is rolled on a stainless steel sheet (JIS SUS 304) surface according to JIS Z 0.27 with a 2 kg roller Attach with. After storing for 7 days in an oven at 60 ° C., the peeling force (F6) when peeling a thermally conductive sheet using a tensile tester (Texture analyzer) at a peel angle of 180 ° and a peel rate of 0.3 m / min is measured. Did.

The rate of increase in the adhesion rate was calculated as follows.

Adhesion rate increase rate (%) = (F6-F2) / (F2) * 100

F4
(gf / in) F1
(gf / in) F2
(gf / in) F3
(gf / in) F5
(gf / in) Deformation degree adhesiveness
Growth rate (%) Example 1 5 14.3 23 27.6 65.8 X 5.1 Example 2 5 12.8 18.2 21.9 64 X 5.3 Comparative Example 1 5 30.8 41.2 64.3 97.8 O 20 Comparative Example 2 2500 128.1 40.8 60 99.8 O 20.1

In Table 1, when the (meth) acrylate-based thermal conductive sheet is prepared using the release film of the present invention, it can be seen that the tack force (F5) of the prepared thermal conductive sheet is lowered. Accordingly, the release film can be peeled from the (meth) acrylate resin with a lower peeling force (F1), so that when the release film is removed from the heat dissipation film, deformation of the thermal conductive sheet is small, and the stainless steel sheet (F2) of the thermal conductive sheet or It was confirmed that the peeling force to the aluminum substrate (F3) was lowered.

In addition, it was confirmed that the adhesive strength of the (meth) acrylate-based thermal conductive sheet of the present invention was not significantly increased even in a high temperature environment.

Residual adhesion rate measurement

The residual adhesive force was calculated by the following equation, and the results are shown in Table 2.

Residual adhesion rate (%) = (F7) / (F8) * 100

An adhesive tape (Tesa tape 7475) is placed on the release layer of the release film prepared above, and is pressed for 30 minutes after being compressed with a 2 kg compression roller. The adhesive tape is peeled from the release layer at a peel angle of 180 ° and a peel speed of 0.3 m / min. The adhesive tape was attached to a stainless steel sheet (JIS SUS 304), and the peel force when peeling at a peel angle of 180 ° and a peel rate of 0.3 m / min was measured, and the peel force was referred to as F7.

The peel force at the time of peeling at a peeling angle of 0.3 m / min and a peeling angle of 180 ° to a stainless steel sheet (JIS SUS 304) of an adhesive tape (Tesa tape 7475) that has never been used was measured, and the peeling force was F8. It was called.

In Table 2, the content of uncured silicone refers to parts by weight based on 100 parts by weight of a polysiloxane compound containing an alkenyl group.

Uncured silicone content (wt%) Residual adhesion rate (%) Example 1 5 76 Example 2 10 70 Comparative Example 1 - 87

In Table 2, it can be seen that Examples 1 and 2 in which the release layer contained an uncured silicone compound had a lower residual adhesion rate than Comparative Example 1. That is, it can be confirmed that uncured silicon is present on the surface of the release layer.

1: release film
1a: release layer
1b: base film
2: Thermal conductive sheet

Claims (14)

(Meth) acrylate-based thermal conductive sheet; And a release film provided on one surface of the (meth) acrylate-based thermal conductive sheet,
The release film is a base film; And a release layer provided on one side of the base film and provided in contact with the (meth) acrylate-based thermal conductive sheet,
The release layer is a heat-radiating film comprising an uncurable silicone compound. The method according to claim 1, wherein the uncured silicone compound is a heat dissipation film that is a compound represented by the formula (3):
[Formula 3]

In Chemical Formula 3, c1 is an integer from 1 to 1000. The method according to claim 1, Part of the uncured silicone compound is a heat radiation film that is present on the surface of the surface of the release layer in contact with the (meth) acrylate-based thermal conductive sheet. The method according to claim 1, The release layer is a heat radiation film further comprising a cured product of an organopolysiloxane compound containing an alkenyl group and an organopolysiloxane compound containing a hydrosilyl group. The method according to claim 1, wherein the release force of the release film measured at a peeling angle of 180 ° and a peeling rate of 1.8 m / min with respect to the (meth) acrylate-based thermal conductive sheet is less than 0.5gf / in 15gf / in Heat resistant film. The method according to claim 1, In the heat dissipation film, the release film is peeled at a peel angle of 180 ° and a peel rate of 1.8 m / min, and one surface of the (meth) acrylate-based thermal conductive sheet is applied to a stainless steel sheet (JIS SUS 304). According to JIS Z 0.27, attached with a 2 kg roller, and stored for 24 hours under a temperature of 25 ° C. and 50% relative humidity, the (meth) acrylate-based thermal conductive sheet of 180 ° to the stainless steel sheet A heat dissipation film having a peeling force of 30 gf / in or less measured at a peeling angle and a peeling rate of 0.3 m / min. The method according to claim 1, wherein the release film is released from the heat dissipation film at a peeling angle of 180 ° and a peeling rate of 1.8 m / min, and one surface of the (meth) acrylate-based thermal conductive sheet is attached to an aluminum substrate (KS D6759) by JIS Z. Attached with a 2 kg roller according to 0.27, and stored for 24 hours at a temperature of 25 ° C. and 50% relative humidity, the peeling angle of 180 ° to the aluminum substrate of the (meth) acrylate-based thermal conductive sheet And a peeling force measured at a peeling rate of 0.3 m / min is 35 gf / in or less. The method according to claim 1, when the release film in the heat dissipation film at a peeling angle of 180 ° and a peeling rate of 1.8 m / min, the length of the (meth) acrylate-based thermal conductive sheet in the direction of peeling is 1 Heat dissipation film which is less than%. The method according to claim 1, In the heat dissipation film, the release film is peeled at a peeling angle of 180 ° and a peeling rate of 1.8 m / min, and the (meth) acrylate-based thermal conductive sheet is applied to a stainless steel sheet (JIS SUS 304) by JIS Z. Attached with a 2 kg roller based on 0.27, stored for 24 hours at a temperature of 25 ° C. and 50% relative humidity, and measured by maintaining a pressing time of 0.01 sec under a load of 800 g of the (meth) acrylate-based thermal conductive sheet A heat dissipation film having a tack force of 80 gf / in or less. The method according to claim 1, The (meth) acrylate-based thermal conductive sheet has an adhesive strength increase rate of 10% or less of the heat dissipation film:
The adhesion increase rate is calculated by the following equation (1),
[Equation 1]
Adhesion increase rate (%) = (F6-F2) / (F2) * 100
In Equation 1,
F6 peels the release film from the heat dissipation film at a peel angle of 180 ° and a peel rate of 1.8 m / min, and one surface of the (meth) acrylate-based thermal conductive sheet is stainless steel sheet (JIS SUS 304) JIS J Attached with a 2 kg roller based on 0.27, and stored for 7 days at a temperature of 60 ° C., the (meth) acrylate-based thermal conductive sheet was peeled at 180 ° with respect to the stainless steel sheet and at an angle of 0.3 m / min. Peeling force at the time of peeling at the peeling speed,
F2 peels the release film from the heat dissipation film at a peel angle of 180 ° and a peel rate of 1.8 m / min, and one surface of the (meth) acrylate-based thermal conductive sheet is coated on a stainless steel sheet (JIS SUS 304) with JIS Z 0.27. Attached with a 2 kg roller according to the above, and stored for 24 hours under a temperature of 25 ° C. and a relative humidity of 50%, the (meth) acrylate-based thermal conductive sheet was peeled at an angle of 180 ° with respect to the stainless steel sheet and It is the peeling force at the time of peeling measured at the peeling speed of 0.3 m / min. A (meth) acrylate-based thermal conductive sheet in which an uncurable silicone compound is present on a part of the surface,
The uncurable silicone compound is a thermal conductive sheet that is a compound represented by the following formula (3):
[Formula 3]

In Chemical Formula 3, c1 is an integer from 1 to 1000. Forming a release layer on one surface of the base film to produce a release film; And forming a (meth) acrylate-based thermal conductive sheet on one surface of the release layer of the release film. The method of claim 12, wherein the manufacturing of the release film comprises: coating a release layer composition on one surface of the base film; And curing the coated release layer composition. The method of claim 12, wherein the forming of the (meth) acrylate-based thermal conductive sheet comprises: applying a (meth) acrylate-based thermal conductive sheet composition to one surface of the release layer; And curing the coated (meth) acrylate-based thermal conductive sheet composition.

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