Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/44—Polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
  • C09K5/08—Materials not undergoing a change of physical state when used
  • C09K5/14—Solid materials, e.g. powdery or granular

Definitions

• the present disclosure relates to a thermally conductive resin composition, a cured product thereof, a thermally conductive sheet, and a method for manufacturing the same.
• heat dissipating members are sometimes required to have excellent flame retardancy, and also to have excellent heat resistance so that they can withstand use under high temperature conditions.
• An object of the present disclosure is to provide a thermally conductive resin composition capable of obtaining a cured product having excellent thermal conductivity and flexibility, as well as excellent flame retardancy and heat resistance, and a thermally conductive sheet containing the same. There is a particular thing.
• the thermally conductive resin composition of the present disclosure includes a polycarbonate polyol compound (A) having a hydroxyl equivalent of 200 g/eq or more and 800 g/eq or less, a polyisocyanate compound (B), and a metal hydroxide filler (C1), It may contain a plasticizer (D).
• the equivalent ratio of the isocyanate groups in the polyisocyanate compound (B) to the hydroxyl groups in the polycarbonate polyol compound (A) (isocyanate group/hydroxyl group) is 0.27 or more and 0.39 or less. It is.
• the metal hydroxide filler (C1) is contained based on 100 parts by mass of the total amount of the polycarbonate polyol compound (A), the polyisocyanate compound (B), and the plasticizer (D). The amount is 30 parts by mass or more and 500 parts by mass or less.
• the thermally conductive resin composition of the present disclosure includes a plasticizer (D), the solubility parameter (SP value) of the plasticizer (D) is 9.0 (cal/cm 3 ) 1/2 or more,
• the content of the plasticizer (D) is 50 parts by mass or less with respect to 100 parts by mass of the total amount of the polycarbonate polyol compound (A), the polyisocyanate compound (B), and the plasticizer (D).
• thermally conductive resin composition of the present disclosure it is possible to provide a cured product that has excellent thermal conductivity and flexibility, as well as excellent flame retardancy and heat resistance, and a thermally conductive sheet containing the same.
• the thermally conductive resin composition of the present embodiment includes a polycarbonate polyol compound (A), a polyisocyanate compound (B), and a metal hydroxide filler (C1 ) and may also contain a plasticizer (D).
• the present composition contains a plasticizer (D)
• the solubility parameter (SP value) of the plasticizer (D) is 9.0 (cal/cm 3 ) 1/2 or more.
• the present composition may further contain an inorganic filler (C2) other than the metal hydroxide filler (C1), and may further contain a polycarbonate polyol compound (A), a polyisocyanate compound (B), a metal hydroxide filler. (C1), the inorganic filler (C2), and one or more other components other than the plasticizer (D) may be included.
• Polycarbonate polyol compound (A) The present composition includes a polycarbonate polyol compound (A) (hereinafter sometimes referred to as "polyol compound (A)").
• the hydroxyl equivalent of the polyol compound (A) is 200 g/eq or more and 800 g/eq or less.
• the number of polyol compounds (A) contained in this composition may be one, or two or more.
• the polyol compound (A) is a compound that has two or more hydroxyl groups in one molecule and has a polycarbonate structure in the molecule.
• the hydroxyl group contained in the polyol compound (A) forms a urethane bond by reacting with the isocyanate group contained in the polyisocyanate compound (B).
• a crosslinked structure can be introduced into the cured product of the present composition, so that the cured product obtained using the present composition can have excellent electrical insulation properties and excellent heat resistance.
• the number of hydroxyl groups contained in the polyol compound (A) is not particularly limited as long as it is 2 or more per molecule, but it is preferably 2.
• the number of hydroxyl groups per molecule contained in the polyol compound (A) increases, the crosslinking density of the cured product of the present composition tends to increase, the hardness of the cured product increases, and the flexibility of the cured product tends to decrease. It is in.
• the number of hydroxyl groups per molecule contained in the polyol compound (A) decreases, the crosslinking reaction between the hydroxyl groups and isocyanate groups becomes difficult to proceed, and the present composition tends to be difficult to cure sufficiently.
• Hardness in this specification refers to Asker C hardness.
• the hydroxyl equivalent of the polyol compound (A) is 200 g/eq or more and 800 g/eq or less, preferably 300 g/eq or more and 700 g/eq or less, and may be 350 g/eq or more and 650 g/eq or less.
• the hydroxyl equivalent of the polyol compound (A) decreases, the crosslinking density of the cured product of the composition tends to increase, the hardness of the cured product increases, and the flexibility of the cured product tends to decrease.
• the hydroxyl equivalent of the polyol compound (A) becomes large, the crosslinking reaction between the hydroxyl group and the isocyanate group becomes difficult to proceed, and it tends to become difficult to sufficiently cure the present composition.
• the hydroxyl equivalent of the polyol compound (A) can be measured by the method described in the Examples below.
• the polycarbonate structure contained in the polyol compound (A) is a structure having polymer chains bonded via carbonate bonds.
• the polycarbonate structure contained in the polyol compound (A) is preferably contained in the main chain structure of the polyol compound (A), and more preferably the main chain structure is a polycarbonate structure. Since the polyol compound (A) has a polycarbonate structure in the molecule, excellent heat resistance can be imparted to the cured product obtained using the present composition.
• a known compound can be used as the polyol compound (A), for example, a reaction product of a compound having two or more hydroxyl groups in one molecule and at least one of a carbonate ester and phosgene can be used.
• Examples of compounds having two or more hydroxyl groups in one molecule include ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3 -propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,7-heptanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol
• carbonic esters examples include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, dibenzyl carbonate, and the like.
• the content of the polyol compound (A) in the present composition can be adjusted depending on the types of the polyol compound (A) and the polyisocyanate compound (B) contained in the present composition.
• the content of the polyol compound (A) in the present composition is, for example, 40 parts by mass or more with respect to 100 parts by mass of the total amount of the polyol compound (A), the polyisocyanate compound (B), and the plasticizer (D).
• the content may be 50 parts by mass or more and 90 parts by mass or less, or 55 parts by mass or more and 80 parts by mass or less.
• the content of the polyol compounds (A) refers to the total content of the two or more types of polyol compounds (A).
• Polyisocyanate compound (B) This composition contains a polyisocyanate compound (B).
• the polyisocyanate compound (B) is a compound having two or more isocyanate groups in one molecule.
• the number of polyisocyanate compounds (B) contained in this composition may be one, or two or more.
• the isocyanate group contained in the polyisocyanate compound (B) forms a urethane bond by reacting with the hydroxyl group contained in the polyol compound (A).
• a crosslinked structure can be introduced into the cured product of the present composition, so that the cured product can have excellent electrical insulation properties and excellent heat resistance.
• the number of isocyanate groups contained in the polyisocyanate compound (B) is not particularly limited as long as it is 2 or more per molecule, but it is preferably 3.
• the number of isocyanate groups per molecule contained in the polyisocyanate compound (B) increases, the crosslinking density of the cured product of this composition tends to increase, so the hardness of the cured product increases and the flexibility of the cured product decreases. It is on a declining trend.
• the number of isocyanate groups per molecule contained in the polyisocyanate compound (B) decreases, the crosslinking reaction between hydroxyl groups and isocyanate groups becomes difficult to proceed, and the present composition tends to be difficult to cure sufficiently.
• polyisocyanate compound (B) can be used as the polyisocyanate compound (B), and examples thereof include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic polyisocyanate compounds, isocyanurate-type polyisocyanate compounds, and the like.
• the polyisocyanate compound (B) is preferably an isocyanurate type polyisocyanate compound.
• the isocyanate group equivalent of the polyisocyanate compound (B) may be, for example, 54 g/eq or more and 312 g/eq or less, 60 g/eq or more and 300 g/eq or less, or 80 g/eq or more and 250 g/eq or less. It may be 100 g/eq or more and 200 g/eq or less.
• the isocyanate group equivalent of the polyisocyanate compound (B) can be measured by the method described in the Examples below.
• the content of the polyisocyanate compound (B) in the present composition can be adjusted depending on the types of the polyol compound (A) and the polyisocyanate compound (B) contained in the present composition.
• the content of the polyol compound (A) in the present composition is, for example, 1 part by mass or more and 25 parts by mass or more based on 100 parts by mass of the total amount of the polyol compound (A), the polyisocyanate compound (B), and the plasticizer (D).
• the amount may be 3 parts by mass or more and 20 parts by mass or less, or 5 parts by mass or more and 15 parts by mass or less.
• the content of the polyisocyanate compounds (B) refers to the total content of the two or more types of polyol compounds (A).
• composition of polyol compound (A) and polyisocyanate compound (B) The content of the polyol compound (A) and the polyisocyanate compound (B) in the present composition is determined by the equivalent ratio of the isocyanate group in the polyisocyanate compound (B) to the hydroxyl group in the polyol compound (A) (isocyanate group/hydroxyl group). , is adjusted to be 0.27 or more and 0.39 or less.
• the above equivalent ratio may be 0.28 or more and 0.38 or less, or may be 0.29 or more and 0.37 or less.
• the water contained in the metal hydroxide filler (C1) reacts with the polyisocyanate compound (B) and may be a cause of inhibiting curing of the present composition, but by adjusting the equivalent ratio to the above range, It is possible to suppress curing inhibition and obtain a cured product with excellent flexibility.
• the content of the metal hydroxide filler (C1) in the present composition is increased in order to improve thermal conductivity, by adjusting the equivalent ratio to the above range, the hardness of the cured product can be increased.
• the present composition includes a metal hydroxide filler (C1) (hereinafter sometimes referred to as "filler (C1)").
• the content of the filler (C1) in the present composition is 30 parts by mass or more and 500 parts by mass or less, based on 100 parts by mass of the total amount of the polyol compound (A), polyisocyanate compound (B), and plasticizer (D). It is.
• the number of fillers (C1) contained in the present composition may be one, or two or more.
• the filler (C1) is composed of metal hydroxide, it has electrical insulation, excellent thermal conductivity, and excellent flame retardancy. Therefore, a cured product obtained using the present composition containing the filler (C1) can have excellent thermal conductivity, excellent electrical insulation, and excellent flame retardancy.
• the filler (C1) is not particularly limited as long as it is a metal hydroxide, but is preferably at least one of aluminum hydroxide and magnesium hydroxide.
• the content of the filler (C1) in the present composition is 30 parts by mass or more and 500 parts by mass or less, based on 100 parts by mass of the total amount of the polyol compound (A), polyisocyanate compound (B), and plasticizer (D).
• the content may be 35 parts by mass or more and 450 parts by mass or less, or 40 parts by mass or more and 400 parts by mass or less.
• the content of fillers (C1) refers to the total content of the two or more types of fillers (C1).
• the cured product obtained using the present composition can have excellent thermal conductivity, excellent electrical insulation, and excellent flame retardancy. can.
• the thermal conductivity and flame retardance of the cured product tend to decrease.
• the filler (C1) content increases, it becomes difficult to uniformly disperse the filler (C1) in the composition, and even when it is uniformly dispersed, the hardness of the cured product becomes large and the cured product becomes soft. There is a tendency for hardening to be inhibited due to moisture contained in the filler (C1). Alternatively, it tends to be difficult to fill all the filler (C1) into a cured product formed into a sheet.
• the average particle diameter of the filler (C1) is not particularly limited.
• the average particle diameter of the filler (C1) may be, for example, 1 ⁇ m or more and 200 ⁇ m or less, 5 ⁇ m or more and 150 ⁇ m or less, 40 ⁇ m or more and 100 ⁇ m or less, 50 ⁇ m or more and 80 ⁇ m or less, and 60 ⁇ m or more. It may be 80 ⁇ m or less, 5 ⁇ m or more and 20 ⁇ m or less, or 5 ⁇ m or more and 10 ⁇ m or less.
• the present composition may contain two or more types of fillers (C1) having different average particle diameters. The average particle diameter can be measured by the method described in Examples below.
• the filler (C1) may be surface-treated.
• the surface treatment include a treatment in which the surface of the metal hydroxide filler is modified using a titanate coupling agent; a silane coupling agent; a surfactant; an organic acid such as oleic acid and stearic acid.
• the present composition may contain an inorganic filler (C2) other than the filler (C1).
• the number of inorganic fillers (C2) contained in this composition may be one, or two or more.
• the inorganic filler (C2) include one or more inorganic fillers selected from the group consisting of metal oxides, metal nitrides, metal carbonates, and silicon compounds.
• the inorganic filler (C2) is preferably a spherical alumina filler from the viewpoint of improving filler filling properties.
• a cured product obtained using the present composition containing an inorganic filler (C2) in addition to the filler (C1) can have better thermal conductivity and better electrical insulation.
• the filler (C1) and the inorganic filler (C2) are preferably 100 parts by mass or more and 900 parts by mass or less, may be 150 parts by mass or more and 800 parts by mass or less, and may be 230 parts by mass or more and 750 parts by mass or less.
• the content of the inorganic filler (C2) is based on 100 parts by mass of the total amount of the polycarbonate polyol compound (A), the polyisocyanate compound (B), and the plasticizer (D).
• the present composition may be 70 parts by mass or more and 700 parts by mass or less, 150 parts by mass or more and 600 parts by mass or less, or 200 parts by mass or more and 500 parts by mass or less.
• the content of the inorganic fillers (C2) refers to the total content of the two or more types of inorganic fillers (C2).
• the cured product obtained using the present composition is It can have excellent thermal conductivity and excellent electrical insulation.
• the average particle diameter of the inorganic filler (C2) is not particularly limited. When the present composition contains two or more types of inorganic fillers (C2), it may contain two or more types of inorganic fillers (C2) having different average particle diameters.
• the average particle diameter of the inorganic filler (C2) can be in the same range as the range of the average particle diameter explained for the filler (C1).
• the inorganic filler (C2) may be surface-treated.
• Examples of the surface treatment include the surface treatment described for filler (C1).
• the present composition may or may not contain a plasticizer (D), but preferably contains a plasticizer (D).
• the plasticizer (D) has a solubility parameter (hereinafter sometimes referred to as "SP value") of 9.0 (cal/cm 3 ) 1/2 or more. and is preferably 9.3 (cal/cm 3 ) 1/2 or more.
• SP value of the plasticizer (D) may be 9.0 (cal/cm 3 ) 1/2 or more and 9.9 (cal/cm 3 ) 1/2 or less, and may be 9.3 (cal/cm 3 ) 1/2 or less.
• the SP value can be measured by the method described in Examples below.
• the composition preferably does not contain a plasticizer with an SP value of less than 9.0 (cal/cm 3 ) 1/2 .
• the number of plasticizers (D) contained in this composition may be one, or two or more.
• the present composition contains the plasticizer (D) having an SP value within the above range, a cured product with low hardness and excellent flexibility can be easily obtained.
• the content of the plasticizer (D) in the present composition is 100% of the total amount of the polyol compound (A), the polyisocyanate compound (B), and the plasticizer (D).
• 50 parts by mass or less may be more than 0 parts by mass and less than 50 parts by mass, may be 10 parts by mass or more and 40 parts by mass or less, and 20 parts by mass or more and 35 parts by mass or less. It's okay.
• the content of plasticizers (D) refers to the total content of all plasticizers (D) contained in the present composition.
• the content of the plasticizer (D) whose SP value is in the above range is increased, the reactivity between the polyol compound (A) and the polyisocyanate compound (B) is reduced, and the composition is It tends to be difficult to harden.
• the plasticizer (D) contained in the present composition is preferably at least one of a phthalic acid plasticizer and an ester plasticizer.
• the present composition may contain other components other than the polyol compound (A), the polyisocyanate compound (B), the metal hydroxide filler (C1), the inorganic filler (C2), and the plasticizer (D).
• Other ingredients include curing accelerators, flame retardants, flame retardant aids, colorants, antioxidants, ultraviolet absorbers, heat stabilizers, crystal accelerators, dispersants, surface conditioners, antifoaming agents, and adhesion. Examples include imparting agents, solvents such as organic solvents, and the like.
• the composition may contain one or more other components.
• the present composition may also contain hindered amine additives as other ingredients.
• hindered amine additive those having an N-alkoxy hindered amine (NOR) structure are preferred.
• the present composition can be prepared by mixing a polyol compound (A), a metal hydroxide filler (C1), and, if necessary, an inorganic filler (C2) and other components, removing water, and then adding a polyisocyanate to the mixture. It can be produced by mixing compound (B).
• the mixing device for mixing these components is not particularly limited, and kneaders such as mixing rolls, kneaders, Banbury mixers, and planetary mixers; vacuum defoaming stirrers, etc. can be used.
• a mixing device it is preferable to use a planetary mixer or a vacuum stirrer that can suppress the inclusion of air bubbles, and it is more preferable to use a rotation-revolution type vacuum stirrer or a planetary mixer under vacuum conditions. preferable.
• Embodiment 2 The cured product of this embodiment is obtained by curing the present composition described in Embodiment 1.
• the present composition can be cured by various methods, such as a method in which the present composition is thermally polymerized by heating it, a method in which the present composition is polymerized at room temperature, and the like. Since the present composition can be cured at low temperatures, the environmental burden when obtaining a cured product obtained using the present composition can be reduced.
• the heating temperature is, for example, 70°C or higher and 100°C or lower, and may be 70°C or higher and 90°C or lower.
• the heating time is, for example, 0.05 hours or more and 72 hours or less, and may be 0.1 hours or more and 10 hours or less.
• the temperature of the room temperature can be 15° C. or more and 40° C. or less, and the time for curing at room temperature is preferably 12 hours or more and 72 hours or less.
• the curing treatment of the present composition may be performed in an air atmosphere, in a nitrogen atmosphere, in an argon atmosphere, or under vacuum conditions.
• the shape of the cured product is not particularly limited.
• the cured product may be shaped into a film, sheet, plate, cylinder, prism, etc., and may be shaped by applying the present composition to a desired position. It may also have an irregular shape.
• the cured product contains the present composition, it has excellent thermal conductivity and flexibility, as well as excellent flame retardancy and heat resistance. Therefore, the cured product can be used in electronic products and electrical products, for example, as a thermally conductive sheet for promoting heat transfer between a heat generating member and a cooling member such as a heat sinker included in these products. and heat dissipation spacers; can be used for sealing parts of electronic products and electrical products, etc.
• the Asker C hardness of the cured product is preferably 1 or more and 40 or less, may be 1 or more and less than 40, may be 5 or more and 37 or less, or may be 10 or more and 35 or less.
• a cured product having an Asker C hardness within the above range has good flexibility and has low compressive stress when the cured product is compressed. This makes it easier to bring the cured product into close contact with the member to be attached, so that thermal resistance can be reduced.
• the Asker C hardness of the cured product increases, a large compressive stress is required to compress the cured product, making it difficult to compress the cured product when attaching it to a member to be attached. This increases the reaction force to the peripheral members, making the peripheral members more likely to suffer from the above-mentioned problems, thereby reducing the ease of handling the cured product.
• Asker C hardness can be measured by the method described in Examples below.
• thermoly conductive sheet of this embodiment includes the cured product described in Embodiment 2, and may be composed only of the cured product.
• the thermally conductive sheet can be obtained, for example, by molding the present composition described in Embodiment 1 into a sheet shape and curing it.
• the thermally conductive sheet contains the cured product of the present composition, it has excellent thermal conductivity and flexibility, as well as excellent flame retardancy and heat resistance.
• the equivalent ratio is within the above range. Therefore, it is possible to suppress the hardness of the thermally conductive sheet from increasing. The lower the hardness of the thermally conductive sheet, the better the flexibility the thermally conductive sheet has, and the more compressive stress can be reduced.
• the thermally conductive sheet can be deformed to follow the unevenness of the surface of the attached member, such as a heat generating member and a cooling member, to which the thermally conductive sheet is attached, so that it can be closely attached to the attached member.
• This can prevent air from being trapped between the thermally conductive sheet and the attached member, reducing thermal conductivity and increasing thermal resistance. can promote heat transfer between
• the thermally conductive sheet is easily compressed, which may cause warping or distortion of peripheral components such as the board around the attached component to which the thermally conductive sheet is attached. It is possible to suppress the occurrence of problems such as
• the thermal conductivity of the thermally conductive sheet is preferably 0.5 W/(m ⁇ K) or more and 5.0 W/(m ⁇ K) or less, and 0.7 W/(m ⁇ K) or more and 4.0 W/ (m ⁇ K) or less, or 1.0 W/(m ⁇ K) or more and 3.0 W/(m ⁇ K) or less.
• a thermally conductive sheet having a thermal conductivity within the above range has excellent thermal conductivity, and therefore can exhibit good thermal conductivity when attached to a member to be attached.
• the thermally conductive sheet has Asker C hardness within the range described above, it is possible to improve the adhesion to the attached member, so the thermal conductivity when the thermally conductive sheet is attached to the attached member It is possible to further improve performance.
• Thermal conductivity can be measured by the method described in Examples below.
• the flame retardancy of the thermally conductive sheet is preferably V-2, V-1, or V-0, and preferably V-1 or V-0, according to the flame retardant UL (Underwriters Laboratories) 94 standard. More preferably, it is V-0. Evaluation according to the UL94 flame retardant standard can be performed by the method described in the Examples described below.
• the thickness of the thermally conductive sheet is not particularly limited.
• the thickness of the thermally conductive sheet is preferably 0.1 mm or more and 10 mm or less, more preferably 0.3 mm or more and 5 mm or less.
• the handleability of the thermally conductive sheet may decrease, and when the thickness of the thermally conductive sheet increases, the thermal resistance tends to increase and the thermal conductivity tends to decrease.
• Embodiment 4 (Method for manufacturing thermally conductive sheet)
• the method for manufacturing a thermally conductive sheet according to the present embodiment includes a step of obtaining a sheet-like molded product by molding the present composition into a sheet-like shape as described in Embodiment 1, and a step of curing the sheet-like molded product by heating. ,including.
• the method for producing a thermally conductive sheet includes a step of curing the cured sheet-like molded product, and adjusting at least one of the shape and size of the thermally conductive sheet, if necessary after the curing step. In order to do this, the method may include a step of cutting out a thermally conductive sheet from the cured sheet-like molded product. According to the method for manufacturing a thermally conductive sheet of this embodiment, the thermally conductive sheet described in Embodiment 3 can be suitably manufactured.
• the step of obtaining the sheet-like molded product can be performed by any method that can mold the present composition into a sheet, and the method is not particularly limited.
• methods for molding the present composition into a sheet include press molding; roll molding; bar coater molding; From the viewpoint of properties, the roll forming method is more preferable.
• the present composition In the step of obtaining a sheet-like molded product, it is preferable to mold the present composition into a sheet-like shape with its surface protected by a release paper or a release film. In the step of obtaining a sheet-like molded product, it is preferable to obtain a sheet-like molded product in which a release paper or a release film is laminated on one or both sides.
• Examples of the above-mentioned curing step include a method of thermally polymerizing the sheet-like molded product by heating it, a method of polymerizing the present composition at room temperature, and the like.
• the heating temperature can be, for example, 70°C or more and 100°C or less, preferably 70°C or more and 90°C or less
• the heating time is, for example, 0.05 hour or more.
• the time can be 72 hours or more, and preferably 0.1 hour or more and 10 hours or less.
• the temperature of the room temperature can be 15° C. or more and 40° C.
• the curing time at room temperature is preferably 12 hours or more and 72 hours or less.
• the above-mentioned curing step may be performed in an air atmosphere, in a nitrogen atmosphere, in an argon atmosphere, or under vacuum conditions. Since the present composition can be cured at low temperatures, the environmental load when manufacturing a thermally conductive sheet using the present composition can be reduced.
• the curing temperature is, for example, 60° C. or more and 90° C. or less
• the curing time is, for example, 0.5 hours or more and 72 hours or less.
• the curing step may be performed in an air atmosphere, in a nitrogen atmosphere, in an argon atmosphere, or under vacuum conditions.
• the step of cutting out the thermally conductive sheet is, for example, a method of punching out a cured or cured sheet-like molded product using a press using a punching die; cutting with a cutter, an ultrasonic cutter, or laser processing, etc. Examples include a method to do so.
• the process of cutting out the thermally conductive sheet may be performed before or after the curing process.
• ⁇ Polyol compound> ⁇ Polyol compound (A-1) Pandex GCB-71 (manufactured by DIC Corporation). It is a polycarbonate polyol compound having a hydroxyl group, and the hydroxyl equivalent is 388.
• ⁇ Polyol compound (A-2) Pandex GCB-51 (manufactured by DIC Corporation). It is a polycarbonate polyol compound having a hydroxyl group, and the hydroxyl equivalent is 644.
• THF tetrahydrofuran
• NPG neopentyl glycol
• ⁇ Metal hydroxide filler> ⁇ Metal hydroxide filler (C1) BX053T (manufactured by Nippon Light Metal Co., Ltd.). This is an aluminum hydroxide filler that has been surface-treated with a titanate coupling agent. The average particle diameter of the aluminum hydroxide filler is 6 ⁇ m.
• ⁇ Plasticizer (cD) TOTM manufactured by J-Plus Co., Ltd.
• thermoly conductive sheet (Preparation of thermally conductive sheet) The resin composition obtained above was applied onto the fluororesin sheet using a bar coater so that the thickness after curing would be 1.0 mm, and then heated and cured at a temperature of 90°C to form a thermally conductive sheet. Created.
• the particle size distribution of the inorganic fillers (C2-1) and (C2-2) was measured by particle size distribution measurement using a laser diffraction scattering method, and the particle size at 50% cumulative volume was taken as the average particle size of the filler.
• solubility parameter of plasticizer (SP value)
• the solubility parameters (SP values) of the plasticizers (D-1), (D-2), and (cD) were calculated using the calculation method of Small.
• the cured products obtained using the resin compositions of Examples 1 to 7 have low hardness, excellent flexibility, and excellent thermal conductivity, while exhibiting poor heat resistance and flame retardancy. was also excellent.
• the solubility parameter (SP value) of the plasticizer (cD) contained in the resin composition is less than 9.0 (cal/cm 3 ) 1/2 , so the relationship between the plasticizer (cD) and the resin is It is considered that the compatibility decreased and the resin composition could not be cured.

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• 2022
  • 2022-09-09 JP JP2024545398A patent/JPWO2024053089A1/ja active Pending
  • 2022-09-09 WO PCT/JP2022/033894 patent/WO2024053089A1/ja not_active Ceased

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