Thermally conductive composition and cured product

Abstract

To provide a thermally conductive composition that can suppress the bleeding of a thermally conductive filler while ensuring thermal conductivity, and a cured product thereof.SOLUTION: A thermally conductive composition contains a polyisocyanate component and a polyol component, and a thermally conductive filler. The polyisocyanate component includes a polyisocyanate with an introduced hydrophilic group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermally conductive composition and a cured product thereof. [Background technology]

[0002] Electronic devices, including semiconductors and batteries, generate heat during operation, and the resulting temperature rise can lead to malfunctions and even destruction. Heat-dissipating materials are used to suppress this temperature rise. Heat-dissipating materials efficiently transfer heat from a heat source to a cooling medium or heat sink. Highly thermally conductive polyurethane resin compositions, for example, are known as heat-dissipating materials.

[0003] As such a polyurethane resin composition with high thermal conductivity, a composition containing a polyol (A), a polyisocyanate (B), an inorganic filler (C), and a surfactant (D) has been proposed (see, for example, Patent Document 1). In Patent Document 1, a polyoxyalkylene alkyl ether is used as the surfactant (Patent Document 1, Example 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2020 / 040177 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the highly thermally conductive polyurethane resin composition (thermally conductive composition) described in Patent Document 1 has the drawback of causing bleeding of the inorganic filler.

[0006] The present invention relates to a thermally conductive composition and a cured product thereof that can suppress bleeding of a thermally conductive filler while ensuring thermal conductivity. [Means for solving the problem]

[0007] The present invention [1] is a thermally conductive composition comprising a polyisocyanate component, a polyol component, and a thermally conductive filler, and the polyisocyanate component comprises a thermally conductive composition containing a polyisocyanate having a hydrophilic group introduced therein.

[0008] The present invention [2] includes the thermally conductive composition according to the above [1], in which the polyisocyanate is a derivative of an aliphatic polyisocyanate.

[0009] The present invention [3] includes the thermally conductive composition according to the above [2], in which the derivative is an isocyanurate derivative.

[0010] The present invention [4] includes the thermally conductive composition according to any one of the above [1] to [3], wherein the polyol component includes polycaprolactone polyol and / or castor oil polyol.

[0011] The present invention [5] includes the thermally conductive composition according to any one of the above [1] to [4], wherein the thermally conductive filler contains aluminum hydroxide and / or alumina.

[0012] The present invention [6] includes the thermally conductive composition according to any one of the above [1] to [5], in which the thermally conductive filler is contained in an amount of 200 parts by mass or more per 100 parts by mass of the total amount of the polyisocyanate component and the polyol component.

[0013] The present invention [7] includes a cured product of the thermally conductive composition according to any one of the above [1] to [6]. [Effects of the Invention]

[0014] The thermally conductive composition of the present invention is a thermally conductive composition containing a polyisocyanate component, a polyol component, and a thermally conductive filler, and the polyisocyanate component contains a polyisocyanate having a hydrophilic group introduced therein. Therefore, the thermally conductive composition of the present invention can suppress bleeding of the thermally conductive filler while ensuring thermal conductivity. Furthermore, the cured product of the present invention is a cured product of the thermally conductive composition, and can suppress bleeding of the thermally conductive filler while ensuring thermal conductivity. DETAILED DESCRIPTION OF THE INVENTION

[0015] The thermally conductive composition of the present invention contains a polyisocyanate component, a polyol component, and a thermally conductive filler.

[0016] (Polyisocyanate component) The polyisocyanate component contains a polyisocyanate into which a hydrophilic group has been introduced.

[0017] The polyisocyanate having a hydrophilic group introduced therein can be obtained by reacting a polyisocyanate with a hydrophilic group-containing active hydrogen compound (described later).

[0018] Examples of polyisocyanates include polyisocyanate monomers and polyisocyanate derivatives.

[0019] Examples of the polyisocyanate monomer include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates.

[0020] Examples of aliphatic polyisocyanates include aliphatic diisocyanates. Examples of aliphatic diisocyanates include 1,6-hexamethylene diisocyanate (1,6-HDI), 1,5-pentamethylene diisocyanate (1,5-PDI), tetramethylene diisocyanate, trimethylene diisocyanate, 1,2-, 2,3-, or 1,3-butylene diisocyanate, and 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate. Examples of aliphatic polyisocyanates include preferably aliphatic diisocyanates, more preferably 1,6-HDI and 1,5-PDI.

[0021] Examples of alicyclic polyisocyanates include alicyclic diisocyanates. Examples of alicyclic diisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4'-, 2,4'-, or 2,2'-methylenebis(cyclohexyl isocyanate), or mixtures thereof (H 12 MDI), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or a mixture thereof (H6XDI), bis(isocyanatomethyl)norbornane (NBDI), 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate.

[0022] Examples of aromatic polyisocyanates include aromatic diisocyanates, such as 4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate or a mixture thereof (MDI), 2,4- or 2,6-tolylene diisocyanate or a mixture thereof (TDI), o-tolidine diisocyanate, 1,5-naphthalene diisocyanate (NDI), m- or p-phenylene diisocyanate or a mixture thereof, 4,4'-diphenyl diisocyanate, and 4,4'-diphenyl ether diisocyanate.

[0023] Examples of araliphatic polyisocyanates include araliphatic diisocyanates, such as xylylene diisocyanate (1,2-, 1,3-, or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), and ω,ω′-diisocyanato-1,4-diethylbenzene.

[0024] The polyisocyanate monomers can be used alone or in combination of two or more kinds.

[0025] As the polyisocyanate monomer, from the viewpoint of suppressing bleeding of the thermally conductive filler while ensuring thermal conductivity, preferably, an aliphatic polyisocyanate, more preferably, an aliphatic diisocyanate, and even more preferably, 1,6-HDI and 1,5-PDI are used.

[0026] Examples of polyisocyanate derivatives include derivatives derived from the above polyisocyanate monomers by known methods. More specifically, examples of polyisocyanate derivatives include uretdione derivatives, isocyanurate derivatives, allophanate derivatives, polyol derivatives, biuret derivatives, urea derivatives, oxadiazinetrione derivatives, and carbodiimide derivatives. These can be used alone or in combination of two or more. Preferred examples of polyisocyanate derivatives include isocyanurate derivatives.

[0027] More specifically, from the viewpoint of suppressing bleeding of the thermally conductive filler while ensuring thermal conductivity, the polyisocyanate derivative is preferably a derivative of an aliphatic polyisocyanate, more preferably an isocyanurate derivative of an aliphatic polyisocyanate, even more preferably an isocyanurate derivative of an aliphatic diisocyanate, particularly preferably an isocyanurate derivative of 1,6-HDI and / or 1,5-PDI, and most preferably an isocyanurate derivative of 1,5-PDI.

[0028] The isocyanurate derivative is an isocyanurate reaction product of a polyisocyanate monomer. The isocyanurate derivative can be obtained by a known method. For example, a polyisocyanate monomer is subjected to an isocyanurate reaction in the presence of a known isocyanurate catalyst. The reaction conditions are appropriately set depending on the purpose and application.

[0029] Furthermore, if necessary, the polyisocyanate monomer may be modified with a known alcohol before the isocyanuration reaction. Furthermore, the isocyanurate derivative may contain an allophanate derivative. In this case, the isocyanurate derivative is an isocyanurate derivative composition containing an allophanate derivative and an isocyanurate derivative.

[0030] If necessary, unreacted polyisocyanate monomer may be separated from the reaction product liquid after the isocyanuration reaction. Examples of the separation method include distillation and extraction, and preferably distillation. Examples of the distillation method include thin film distillation. The distillation conditions are appropriately set depending on the purpose and application.

[0031] Specifically, the isocyanurate derivative is produced, for example, by the following method: In this method, the polyisocyanate monomer is reacted with an alcohol.

[0032] Examples of alcohols include low-molecular-weight alcohols. Low-molecular-weight alcohols are organic compounds that have one or more hydroxyl groups in one molecule and have a relatively low molecular weight. Note that a relatively low molecular weight refers to a molecular weight of less than 200 (the same applies hereinafter).

[0033] Examples of low molecular weight alcohols include aliphatic low molecular weight alcohols and aromatic low molecular weight alcohols, and preferably aliphatic low molecular weight alcohols. Examples of aliphatic low molecular weight alcohols include aliphatic low molecular weight alcohols having 1 to 12 carbon atoms. Examples of aliphatic low molecular weight alcohols include aliphatic low molecular weight monools (monohydric alcohols) and aliphatic low molecular weight polyols (dihydric or higher alcohols).

[0034] The aliphatic low-molecular-weight monool is an aliphatic organic compound having one hydroxyl group per molecule and a relatively low molecular weight. Examples of the aliphatic low-molecular-weight monool include aliphatic low-molecular-weight monohydric alcohols having 1 to 12 carbon atoms. Examples of the aliphatic low-molecular-weight monohydric alcohols having 1 to 12 carbon atoms include alkyl alcohols having 1 to 12 carbon atoms. Examples of the alkyl alcohols having 1 to 12 carbon atoms include methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, s-butanol, t-butanol, 2-ethylhexyl alcohol, and lauryl alcohol. These can be used alone or in combination of two or more.

[0035] The aliphatic low-molecular-weight polyol is an aliphatic organic compound having two or more hydroxyl groups in one molecule and a relatively low molecular weight. Examples of the aliphatic low-molecular-weight polyol include aliphatic low-molecular-weight polyols having 1 to 12 carbon atoms. Examples of the aliphatic low-molecular-weight polyol include aliphatic low-molecular-weight dihydric alcohols.

[0036] More specifically, examples of aliphatic low-molecular-weight polyols include aliphatic low-molecular-weight dihydric alcohols having 1 to 12 carbon atoms. Examples of aliphatic low-molecular-weight dihydric alcohols having 1 to 12 carbon atoms include alkylenediols having 1 to 12 carbon atoms. Examples of alkylenediols having 1 to 12 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and neopentyl glycol. These can be used alone or in combination of two or more types.

[0037] The alcohols can be used alone or in combination of two or more. The molecular weight of the low-molecular-weight alcohol (when used in combination, this may be the average molecular weight (the same applies hereinafter)) is, for example, less than 200, preferably less than 150. The molecular weight of the low-molecular-weight alcohol is, for example, 40 or more, preferably 50 or more.

[0038] The average number of hydroxyl groups in the alcohols is, for example, 1 or more. The average number of hydroxyl groups in the alcohols is, for example, 3 or less, preferably 2 or less.

[0039] More specifically, the alcohols are preferably aliphatic low-molecular-weight alcohols having 1 to 12 carbon atoms, more preferably aliphatic low-molecular-weight monohydric alcohols having 1 to 12 carbon atoms and aliphatic low-molecular-weight dihydric alcohols having 1 to 12 carbon atoms, even more preferably alkyl alcohols having 1 to 12 carbon atoms and alkylenediols having 1 to 12 carbon atoms, and particularly preferably isobutanol and 1,3-butanediol.

[0040] Alcohols can be used alone or in combination of two or more types.

[0041] The blending ratio of the polyisocyanate monomer and the alcohol is appropriately set within a range that does not impair the excellent effects of the present invention.

[0042] More specifically, the equivalent ratio (NCO / OH) of the isocyanate groups of the polyisocyanate monomer to the hydroxyl groups of the alcohols exceeds 5, for example, and is preferably 10 or more, and more preferably 15 or more. In addition, the equivalent ratio (NCO / OH) of the isocyanate groups of the polyisocyanate monomer to the hydroxyl groups of the alcohols is, for example, 2000 or less, preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less.

[0043] The amount of the alcohol is, for example, 0.01 part by mass or more, preferably 0.05 part by mass or more, more preferably 0.1 part by mass or more, relative to 100 parts by mass of the polyisocyanate monomer, and for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, relative to 100 parts by mass of the polyisocyanate monomer.

[0044] The reaction conditions for the polyisocyanate monomer and the alcohol are appropriately set within a range that does not impair the excellent effects of the present invention. More specifically, the environmental conditions are an inert atmosphere and normal pressure. The reaction temperature is, for example, 20°C or higher, preferably 40°C or higher. The reaction temperature is, for example, 100°C or lower, preferably 90°C or lower. The reaction time is, for example, 0.05 hours or higher, preferably 0.2 hours or higher. The reaction time is, for example, 10 hours or shorter, preferably 6 hours or shorter.

[0045] In this method, a urethanization catalyst can be added to the polyisocyanate monomer and alcohols as needed. Examples of the urethanization catalyst include known amines and known organometallic compounds. The amount of the urethanization catalyst added is not particularly limited and can be appropriately determined depending on the purpose and application.

[0046] This causes a urethane reaction between the polyisocyanate monomer and the alcohol, resulting in a urethane reaction product.

[0047] Next, in this method, the urethanized reaction product is subjected to an isocyanurate reaction.

[0048] More specifically, in this method, an isocyanuration catalyst (trimerization catalyst) is blended with the urethanization reaction product, and the mixture is heated.

[0049] The isocyanuration catalyst is not particularly limited as long as it is a catalyst that can promote the isocyanuration of isocyanate groups. Examples of isocyanuration catalysts include tertiary amines, Mannich bases, Friedel-Crafts catalysts, metal salts of alkylcarboxylic acids, organometallic compounds, halogen-substituted organophosphorus compounds, tetraalkylammonium hydroxides, weak organic acid salts of tetraalkylammonium, trialkylhydroxyalkylammonium hydroxides, and weak organic acid salts of trialkylhydroxyalkylammonium. These can be used alone or in combination of two or more types.

[0050] The isocyanuration catalyst preferably includes an organic weak acid salt of trialkylhydroxyalkylammonium.

[0051] Examples of trialkylhydroxyalkylammonium include N-(2-hydroxypropyl)-N,N,N-trimethylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium, and triethylhydroxyethylammonium. These can be used alone or in combination of two or more.

[0052] Examples of organic weak acid salts include acetate, propionate, 2-ethylhexanoate, octylate, caprate, myristate, and benzoate. These can be used alone or in combination of two or more.

[0053] The mixing ratio of the isocyanurate catalyst relative to 100 parts by mass of the polyisocyanate monomer is, for example, 0.01 part by mass or more, preferably 0.03 part by mass or more, and for example, 0.3 part by mass or less, preferably 0.1 part by mass or less, more preferably 0.08 part by mass or less.

[0054] The reaction conditions for the isocyanurate reaction are appropriately set within a range that does not impair the excellent effects of the present invention. More specifically, the environmental conditions are an inert atmosphere and atmospheric pressure. The reaction temperature is, for example, 25°C or higher, preferably 50°C or higher. The reaction temperature is, for example, 150°C or lower, preferably 100°C or lower. The reaction time is, for example, 30 minutes or longer, preferably 45 minutes or longer. The reaction time is, for example, 10 hours or shorter, preferably 5 hours or shorter.

[0055] Then, when the reaction rate (isocyanate group conversion rate) of the reaction solution reaches a predetermined value, a reaction terminator is added to the reaction solution. The conversion rate of the isocyanate group when the reaction is terminated is, for example, 5% by mass or more, preferably 10% by mass or more. The conversion rate of the isocyanate group when the reaction is terminated is, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 18% by mass or less. The conversion rate of the isocyanate group can be calculated by a known method.

[0056] Examples of reaction terminators include phosphoric acid, monochloroacetic acid, benzoyl chloride, dodecylbenzenesulfonic acid, o-toluenesulfonic acid, p-toluenesulfonic acid, methyl o-toluenesulfonate, methyl p-toluenesulfonate, o-toluenesulfonamide, and p-toluenesulfonamide. These can be used alone or in combination of two or more. The blending ratio of the reaction terminator is appropriately set depending on the purpose and application.

[0057] Alternatively, a catalyst adsorbent may be added instead of the reaction terminator. Examples of catalyst adsorbents include chelating resins and ion exchange resins. These may be used alone or in combination of two or more. The blending ratio of the catalyst adsorbent is appropriately determined depending on the purpose and application.

[0058] This stops the isocyanurate reaction.

[0059] In each of the above reactions, a known reaction solvent can be added. The mixing ratio of the reaction solvent is appropriately set depending on the purpose and application. In each of the above reactions, the reaction solution can be purified. Examples of purification methods include distillation and extraction. By purification, unreacted polyisocyanate monomer is removed from the reaction solution. In addition, the urethanization catalyst, isocyanuration catalyst, catalyst deactivator, and / or reaction solvent are removed together with the polyisocyanate monomer.

[0060] In the above reaction, the polyisocyanate monomer is modified with isocyanurate, resulting in an isocyanurate derivative of the polyisocyanate monomer as the reaction product.

[0061] The isocyanate group content (NCO%) of the isocyanurate derivative (sometimes referred to as isocyanate group content) is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, particularly preferably 21% by mass, and for example, 100% by mass or less, preferably 75% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, particularly preferably 30% by mass or less, and most preferably 25% by mass or less. The isocyanate group content is measured in accordance with JIS K-1603 (2007).

[0062] The hydrophilic group-containing active hydrogen compound is a compound having at least one hydrophilic group and at least one active hydrogen group in the molecule, preferably a compound having one hydrophilic group and one active hydrogen group in the molecule.

[0063] Examples of hydrophilic groups include anionic groups and nonionic groups. That is, the hydrophilic group includes anionic groups and / or nonionic groups. Examples of anionic groups include carboxylic acid groups (carboxy groups), sulfonic acid groups, and phosphoric acid groups. Preferably, sulfonic acid groups are used. Examples of nonionic groups include polyoxyethylene groups.

[0064] Examples of the active hydrogen group include a hydroxyl group, an amino group, and a mercapto group, and preferred examples of the active hydrogen group include a hydroxyl group and an amino group.

[0065] Specific examples of the hydrophilic group-containing active hydrogen compound include an anionic group-containing active hydrogen compound and a nonionic group-containing active hydrogen compound.

[0066] Examples of the anion group-containing active hydrogen compound include a carboxylic acid group-containing active hydrogen compound, a sulfonic acid group-containing active hydrogen compound, and a phosphoric acid group-containing active hydrogen compound.

[0067] The carboxylic acid group-containing active hydrogen compound is a compound containing one or more carboxylic acid groups and one or more active hydrogen groups.

[0068] Examples of carboxylic acid group-containing active hydrogen compounds include 2,2-dimethylolacetic acid, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, dimethylolheptanoic acid, dimethylolnonanoic acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylolvaleric acid. These can be used alone or in combination of two or more.

[0069] The sulfonic acid group-containing active hydrogen compound is a compound containing one or more sulfonic acid groups and one or more active hydrogen groups. Examples of the sulfonic acid group-containing active hydrogen compound include sulfonic acid group-containing monofunctional active hydrogen compounds. The sulfonic acid group-containing monofunctional active hydrogen compound has both one sulfonic acid group and one active hydrogen group.

[0070] Examples of sulfonic acid group-containing monofunctional active hydrogen compounds include hydroxyalkanesulfonic acids and aminosulfonic acids. Examples of hydroxyalkanesulfonic acids include hydroxymethanesulfonic acid, hydroxyethanesulfonic acid, and 3-hydroxypropanesulfonic acid. Examples of aminosulfonic acids include 2-(cyclohexylamino)-ethanesulfonic acid (CHES) and 3-(cyclohexylamino)-propanesulfonic acid (CAPS). These can be used alone or in combination of two or more. Preferred are aminosulfonic acids, and more preferred are 3-(cyclohexylamino)-propanesulfonic acid.

[0071] The phosphate group-containing active hydrogen compound is a compound containing one or more phosphate groups and one or more active hydrogen groups.

[0072] Examples of the phosphate group-containing active hydrogen compound include hydroxyalkylphosphonic acid and aminoalkylphosphonic acid.

[0073] The anionic group-containing active hydrogen compound can be used alone or in combination of two or more. As the anionic group-containing active hydrogen compound, preferably, a sulfonic acid group-containing active hydrogen compound, more preferably, a sulfonic acid group-containing monofunctional active hydrogen compound, even more preferably, an aminosulfonic acid, and particularly preferably, 3-(cyclohexylamino)-propanesulfonic acid (CAPS) can be used.

[0074] Examples of the nonionic group-containing active hydrogen compound include polyoxyethylene compounds. Examples of the polyoxyethylene compound include compounds having both an active hydrogen group and at least three consecutive ethylene oxide groups. Examples of such polyoxyethylene compounds include one-end-blocked polyoxyethylene glycol and polyoxyethylene side chain-containing diol.

[0075] Examples of the one-end-capped polyoxyethylene glycol include alkoxypolyethylene glycols in which one end is capped with an alkyl group having 1 to 20 carbon atoms. More specific examples include methoxypolyoxyethylene glycol and ethoxypolyoxyethylene glycol. The one-end-capped polyoxyethylene glycol can be produced by a known method.

[0076] Examples of the polyoxyethylene side chain-containing diol include a reaction product of a polyoxyethylene group-containing monoisocyanate and a dialkanolamine. The polyoxyethylene side chain-containing diol can be produced by a known method.

[0077] The number average molecular weight of the polyoxyethylene compound is, for example, 200 or more, preferably 300 or more. The number average molecular weight of the polyoxyethylene compound is, for example, 2000 or less, preferably 1000 or less, more preferably 500 or less.

[0078] The nonionic group-containing active hydrogen compound can be used alone or in combination of two or more kinds. As the nonionic group-containing active hydrogen compound, preferably a polyoxyethylene compound, more preferably a one-end-blocked polyoxyethylene glycol, even more preferably an alkoxypolyethylene glycol one-end-blocked with an alkyl group having 1 to 20 carbon atoms, and particularly preferably a methoxypolyoxyethylene glycol.

[0079] The hydrophilic group-containing active hydrogen compounds can be used alone or in combination of two or more.

[0080] When the hydrophilic group-containing active hydrogen compound is used alone, the hydrophilic group-containing active hydrogen compound is preferably an anionic group-containing active hydrogen compound or a nonionic group-containing active hydrogen compound.

[0081] When two or more hydrophilic group-containing active hydrogen compounds are used in combination, the hydrophilic active hydrogen component preferably includes a combination of an anionic group-containing active hydrogen compound and a nonionic group-containing active hydrogen compound.

[0082] When an anionic group-containing active hydrogen compound and a nonionic group-containing active hydrogen compound are used in combination, the ratio of these compounds used in combination is appropriately determined depending on the purpose and application.

[0083] For example, the amount of the anionic group-containing active hydrogen compound is, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more, based on the total amount of the anionic group-containing active hydrogen compound and the nonionic group-containing active hydrogen compound. Also, the amount of the anionic group-containing active hydrogen compound is, for example, 90% by mass or less, preferably 75% by mass or less, more preferably 50% by mass or less, and even more preferably 45% by mass or less.

[0084] The amount of the nonionic group-containing active hydrogen compound is, for example, 10% by mass or more, preferably 25% by mass or more, more preferably 50% by mass or more, and even more preferably 55% by mass or more, based on the total amount of the anionic group-containing active hydrogen compound and the nonionic group-containing active hydrogen compound. The amount of the nonionic group-containing active hydrogen compound is, for example, 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less.

[0085] The amount of the nonionic group-containing active hydrogen compound is, for example, 50 parts by mass or more, preferably 100 parts by mass or more, more preferably 120 parts by mass or more, and even more preferably 500 parts by mass or more, relative to 100 parts by mass of the anionic group-containing active hydrogen compound. The amount of the nonionic group-containing active hydrogen compound is, for example, 1000 parts by mass or less, preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and even more preferably 200 parts by mass or less.

[0086] The polyisocyanate having a hydrophilic group introduced therein can be produced, for example, by reacting the above-mentioned polyisocyanate with a hydrophilic group-containing active hydrogen compound.

[0087] More specifically, polyisocyanate and a hydrophilic group-containing active hydrogen compound are reacted in a ratio that leaves free isocyanate groups. The method for reacting polyisocyanate and a hydrophilic group-containing active hydrogen compound is not particularly limited. For example, polyisocyanate and a hydrophilic group-containing active hydrogen compound are mixed in a predetermined ratio and heated as necessary.

[0088] More specifically, the equivalent ratio of the active hydrogen groups of the hydrophilic group-containing active hydrogen compound to the isocyanate groups of the polyisocyanate (active hydrogen groups / NCO) is, for example, 0.30 or less, preferably 0.20 or less, and the equivalent ratio of the active hydrogen groups of the hydrophilic group-containing active hydrogen compound to the isocyanate groups of the polyisocyanate (active hydrogen groups / NCO) is, for example, 0.01 or more, preferably 0.10 or more.

[0089] The blending ratio of the hydrophilic group-containing active hydrogen compound is, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and particularly preferably 3.5 parts by mass or more, per 100 parts by mass of polyisocyanate. The blending ratio of the hydrophilic active hydrogen component is, for example, 100 parts by mass or less, preferably 75 parts by mass or less, more preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less, per 100 parts by mass of polyisocyanate.

[0090] The reaction conditions for the polyisocyanate and the hydrophilic group-containing active hydrogen compound are appropriately set within a range that does not impair the excellent effects of the present invention. More specifically, the environmental conditions are an inert atmosphere and normal pressure. The reaction temperature is, for example, 50°C or higher, preferably 70°C or higher. The reaction temperature is, for example, 150°C or lower, preferably 110°C or lower. The reaction time is, for example, 1 hour or longer, preferably 2.5 hours or longer, more preferably 5 hours or longer, and even more preferably 7 hours or longer. The reaction time is, for example, 48 hours or shorter, preferably 24 hours or shorter, more preferably 12 hours or shorter, and even more preferably 10 hours or shorter.

[0091] The completion of the reaction can be confirmed, for example, by the fact that the amount of isocyanate in the reaction mixture no longer changes. The amount of isocyanate is measured by titration or infrared absorption.

[0092] In addition, when an anionic group-containing active hydrogen compound is used as the hydrophilic active hydrogen component, it is preferable to add a neutralizing agent to the reaction solution to form a salt of the anionic group. That is, the anionic group may or may not be a salt. Preferably, the anionic group is a salt of the anionic group.

[0093] Neutralizing agents include conventional bases. Specific examples of bases include organic and inorganic bases. Organic bases include, for example, tertiary amines and secondary amines. Tertiary amines include, for example, trialkylamines and alkanolamines. Trialkylamines include, for example, trimethylamine, triethylamine, and N,N-dimethylcyclohexylamine. Alkanolamines include, for example, dimethylethanolamine, methyldiethanolamine, triethanolamine, and triisopropanolamine. Secondary amines include, for example, heterocyclic amines. Heterocyclic amines include, for example, morpholine. Inorganic bases include, for example, ammonia, alkali metal hydroxides, alkaline earth metal hydroxides, and alkali metal carbonates. Alkali metal hydroxides include, for example, lithium hydroxide, sodium hydroxide, and potassium hydroxide. Alkaline earth metal hydroxides include, for example, magnesium hydroxide and calcium hydroxide. Alkali metal carbonates include, for example, sodium carbonate and potassium carbonate. These can be used alone or in combination.

[0094] As the neutralizing agent, preferably, an organic base is used, more preferably, a tertiary amine is used, further preferably, a trialkylamine is used, and particularly preferably, N,N-dimethylcyclohexylamine (DMCHA) is used.

[0095] The amount of the neutralizing agent added is, for example, 0.4 equivalents or more, preferably 0.6 equivalents or more, relative to 1 equivalent of the anionic group, and is, for example, 1.2 equivalents or less, preferably 1.0 equivalent or less, relative to 1 equivalent of the anionic group.

[0096] This gives a polyisocyanate having a hydrophilic group introduced therein.

[0097] The polyisocyanate having a hydrophilic group introduced therein has an isocyanate group content of, for example, 5% by mass or more, or preferably 10% by mass or more, and for example, 40% by mass or less, or preferably 30% by mass or less.

[0098] The polyisocyanate component may further include a polyisocyanate into which no hydrophilic group has been introduced.

[0099] Examples of polyisocyanates into which no hydrophilic group has been introduced include the above-mentioned polyisocyanate monomers and polyisocyanate derivatives.

[0100] The proportion of polyisocyanate into which no hydrophilic group has been introduced is, for example, 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 0 part by mass, per 100 parts by mass of polyisocyanate into which a hydrophilic group has been introduced. That is, the polyisocyanate component particularly preferably consists of polyisocyanate into which a hydrophilic group has been introduced.

[0101] The proportion of the polyisocyanate component is, relative to 100 parts by mass of the thermally conductive composition, 0.1 parts by mass or more, preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, particularly preferably 4 parts by mass or more, and most preferably 5 parts by mass or more, and is, for example, 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, particularly preferably 7 parts by mass or less, and most preferably 6.5 parts by mass or less.

[0102] (Polyol component) The polyol component may, for example, be a macropolyol.

[0103] A macropolyol is a polyol having a number average molecular weight of 200 or more.

[0104] Examples of macropolyols include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, and vinyl monomer-modified polyols. These can be used alone or in combination of two or more.

[0105] The macropolyols preferably include polyester polyols and vegetable oil polyols.

[0106] Examples of polyester polyols include condensation polyester polyols and ring-opening polyester polyols. Examples of condensation polyester polyols include condensates of low-molecular-weight polyols (described below) and known polybasic acids. Examples of ring-opening polyester polyols include polycaprolactone polyols. Examples of polycaprolactone polyols include polycaprolactone diols. These can be used alone or in combination of two or more.

[0107] As the polyester polyol, preferably, a ring-opening polyester polyol is used, more preferably, a polycaprolactone polyol, and even more preferably, a polycaprolactone diol is used.

[0108] Polycaprolactone polyols can be obtained by ring-opening polymerization of lactones, such as β-lactone, γ-lactone, σ-lactone, and ε-lactone, using a low-molecular-weight polyol (described later) as an initiator.

[0109] Such polyester polyols are also available as commercially available products, for example, Capa 2043 (trade name, polycaprolactone diol, average molecular weight of about 400, manufactured by Ingevity).

[0110] Examples of vegetable oil polyols include coconut oil polyol and castor oil polyol, and preferably castor oil polyol.

[0111] Examples of castor oil polyols include unmodified castor oil polyols and ester-modified castor oil polyols.

[0112] Examples of unmodified castor oil polyols include castor oil (a vegetable oil containing a hydroxyl group).

[0113] Examples of ester-modified castor oil polyols include ester reaction products of castor oil fatty acids (such as ricinoleic acid) and known polyether polyols.

[0114] As the macropolyol, polycaprolactone polyol and / or castor oil polyol are preferably used from the viewpoint of carbon neutrality.

[0115] The number average molecular weight of the macropolyol is, for example, 200 or more, preferably 300 or more, and for example, 5000 or less, preferably 2000 or less, more preferably 1000 or less, and still more preferably 900 or less.

[0116] The hydroxyl equivalent of the macropolyol is, for example, 50 or more, preferably 100 or more, more preferably It is preferably 150 or more, and for example, 3000 or less, preferably 2000 or less, more preferably 1000 or less, and even more preferably 500 or less.

[0117] The average number of hydroxyl groups in the macropolyol is, for example, 1.8 or more, preferably 2 or more. The average number of hydroxyl groups in the macropolyol is, for example, 5 or less, preferably 4 or less, more preferably 3.5 or less, and even more preferably 3.0 or less.

[0118] The polyol component may include a low molecular weight polyol.

[0119] The low molecular weight polyol is a polyol having a number average molecular weight of less than 200.

[0120] Examples of low-molecular-weight polyols include dihydric alcohols, trihydric alcohols, and tetrahydric or higher alcohols. Examples of dihydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and dipropylene glycol. Examples of trihydric alcohols include glycerin and trimethylolpropane. Examples of tetrahydric or higher alcohols include pentaerythritol and diglycerin. These may be used alone or in combination.

[0121] The proportion of the low-molecular-weight polyol relative to 100 parts by mass of the macropolyol is, for example, 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 0 part by mass. That is, the polyol component particularly preferably consists of the macropolyol.

[0122] The proportion of the polyol component, relative to the total amount of the thermally conductive composition, is, for example, 2 mass% or more, preferably 5 mass% or more, more preferably 7 mass% or more, even more preferably 7.5 mass% or more, and particularly preferably 8 mass% or more, and for example, 40 mass% or less, preferably 20 mass% or less, more preferably 15 mass% or less, and even more preferably 12 mass% or less.

[0123] The proportion of the polyol component is set so that the equivalent ratio of the isocyanate groups of the isocyanate component to the hydroxyl groups of the polyol component is a predetermined ratio, i.e., the equivalent ratio (NCO / OH) of the isocyanate groups of the polyisocyanate component to the hydroxyl groups of the polyol component is, for example, 0.5 or more, preferably more than 0.7, more preferably 0.8 or more, and for example, 2.0 or less, preferably 1.5 or less, more preferably 1.2 or less.

[0124] (thermal conductive filler) Examples of the thermally conductive filler include inorganic particles, such as carbides, nitrides, oxides, hydroxides, metals, and carbon-based materials. The inorganic particles are not limited to the examples given and can be selected arbitrarily.

[0125] Examples of oxides include iron oxide, silicon oxide (silica), aluminum oxide (alumina), magnesium oxide (magnesia), titanium oxide, cerium oxide, and zirconium oxide. Examples of oxides also include transition metal oxides such as barium titanate, and oxides doped with metal ions, such as indium tin oxide and antimony tin oxide.

[0126] Hydroxides include, for example, aluminum hydroxide, calcium hydroxide, and magnesium hydroxide.

[0127] Nitrides include, for example, silicon nitride, boron nitride, aluminum nitride, gallium nitride, chromium nitride, tungsten nitride, magnesium nitride, molybdenum nitride, and lithium nitride.

[0128] These thermally conductive fillers can be used alone or in combination of two or more.

[0129] The thermally conductive filler is preferably a hydroxide and / or an oxide, more preferably aluminum hydroxide and / or alumina, even more preferably aluminum hydroxide or alumina, and particularly preferably alumina.

[0130] The shape of the thermally conductive filler is not particularly limited, and examples thereof include spherical, blocky, needle-like, amorphous, and plate-like (scale-like) shapes.

[0131] The size of the thermally conductive filler is not particularly limited, and for example, its maximum length (average particle diameter in the case of a spherical shape) is, for example, 1 μm or more, preferably 2 μm or more, more preferably 4 μm or more, even more preferably 6 μm or more, particularly preferably 8 μm or more, and most preferably 10 μm or more, and for example, 50 μm or less, preferably 40 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less, and particularly preferably 15 μm or less.

[0132] The proportion of the thermally conductive filler in the thermally conductive composition is, for example, 40% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, particularly preferably 85% by mass or more, and most preferably 90% by mass or more, and for example, 99% by mass or less, preferably 97% by mass or less, more preferably 95% by mass or less, even more preferably 94% by mass or less, particularly preferably 93% by mass or less, and most preferably 92% by mass or less.

[0133] The proportion of the thermally conductive filler in the thermally conductive composition is, for example, 40% by volume or more, preferably 50% by volume or more, more preferably 60% by volume or more, even more preferably 65% ​​by mass or more, and for example, 80% by volume or less, preferably 79% by volume or less, more preferably 78% by volume or less.

[0134] The proportion of the thermally conductive filler, relative to 100 parts by mass of the total of the polyisocyanate component and the polyol component, is, for example, 200 parts by mass or more, preferably 400 parts by mass or more, more preferably 500 parts by mass or more, even more preferably 550 parts by mass or more, particularly preferably 1000 parts by mass or more, and most preferably 2000 parts by mass or more, and is, for example, 6000 parts by mass or less, preferably 4000 parts by mass or less, more preferably 3500 parts by mass or less, even more preferably 3000 parts by mass or less, and particularly preferably 2800 parts by mass or less.

[0135] The thermally conductive composition can be produced by the following method. Specifically, a polyisocyanate component, a polyol component, and a thermally conductive filler are prepared in the above-mentioned proportions. Then, the thermally conductive filler is blended in the above-mentioned proportions with either or both of the polyisocyanate component and the polyol component. Preferably, the thermally conductive filler is blended in a mass ratio equal to the mass of the polyisocyanate component (curing agent) and the polyol compound (main component).

[0136] The thermally conductive composition may also contain additives, such as urethane catalysts and silane coupling agents.

[0137] Examples of the urethanization catalyst include known urethanization catalysts, such as amines and organometallic compounds.

[0138] Examples of amines include tertiary amines, quaternary ammonium salts, and imidazoles. Examples of tertiary amines include triethylamine, triethylenediamine, bis-(2-dimethylaminoethyl)ether, and N-methylmorpholine. Examples of quaternary ammonium salts include tetraethylhydroxylammonium. Examples of imidazoles include imidazole and 2-ethyl-4-methylimidazole. These amines can be used alone or in combination of two or more.

[0139] Organometallic compounds include, for example, organotin compounds, organolead compounds, organonickel compounds, organocobalt compounds, organocopper compounds, and organobismuth compounds. Organotin compounds include, for example, tin acetate, tin octoate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate (DBTDL), dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, and dibutyltin dichloride. Organolead compounds include, for example, lead octoate and lead naphthenate. Organonickel compounds include, for example, nickel naphthenate. Organocobalt compounds include, for example, cobalt naphthenate. Organocopper compounds include, for example, copper octenate. Organobismuth compounds include, for example, bismuth octoate and bismuth neodecanoate. These organometallic compounds can be used alone or in combination of two or more.

[0140] These organometallic compounds are also commercially available, and examples thereof include Neostan U-100 (organotin compound, manufactured by Nitto Kasei Co., Ltd.), Formate TK-1 (organotin compound, manufactured by Mitsui Chemicals, Inc.), Fomrez UL-28 (organotin compound, manufactured by Momentive Chemicals), and Stanoct (organotin compound, manufactured by Mitsubishi Chemical Corporation).

[0141] These catalysts (amines and organometallic compounds) can be used alone or in combination of two or more kinds, and are preferably organometallic compounds, more preferably organotin compounds, and even more preferably dibutyltin dilaurate.

[0142] The blending ratio of the catalyst (based on 100% active ingredient amount) is, for example, 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.015 part by mass or more, even more preferably 0.02 part by mass or more, per 100 parts by mass of the total amount of the polyisocyanate component and the polyol component, and is, for example, 0.2 part by mass or less, preferably 0.1 part by mass or less, more preferably 0.075 part by mass or less, even more preferably 0.05 part by mass or less, particularly preferably 0.04 part by mass or less, and most preferably 0.035 part by mass or less.

[0143] The urethane catalyst is added to the polyisocyanate component and / or the polyol component.

[0144] Examples of the silane coupling agent include known silane coupling agents. Examples of the known silane coupling agent include aminosilanes and epoxysilanes. Examples of the epoxysilane include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane.

[0145] Silane coupling agents are commercially available, and examples thereof include KBM-403 (product name, 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicones Co., Ltd.).

[0146] These silane coupling agents can be used alone or in combination of two or more. As the silane coupling agent, preferred is epoxy silane, and more preferred is 3-glycidoxypropyltrimethoxysilane.

[0147] The blending ratio of the silane coupling agent is, relative to 100 parts by mass of the total amount of the polyisocyanate component and the polyol component, for example, 10 parts by mass or more, preferably 20 parts by mass or more, more preferably 30 parts by mass or more, even more preferably 35 parts by mass or more, particularly preferably 100 parts by mass or more, and most preferably 150 parts by mass or more, and for example, 500 parts by mass or less, preferably 400 parts by mass or less, more preferably 300 parts by mass or less, and even more preferably 200 parts by mass or less.

[0148] The silane coupling agent is added to the polyisocyanate component and / or the polyol component.

[0149] The thermally conductive composition may further contain other additives. Examples of such additives include reaction solvents, catalysts, epoxy resins, coating property improvers, leveling agents, antifoaming agents, stabilizers (such as antioxidants and UV absorbers), thickeners, anti-settling agents, plasticizers, surfactants, pigments, fillers, organic or inorganic fine particles, and anti-fungal agents. The amount of additives to be added is determined appropriately depending on the purpose and application.

[0150] The present invention includes a cured product of the thermally conductive composition described above. The cured product can be obtained by curing the thermally conductive composition described above.

[0151] Specifically, the cured product can be obtained by molding the thermally conductive composition using a known molding method, followed by curing. Examples of molding methods include cast molding. The drying and curing conditions are known and are not particularly limited, and examples include drying and curing at room temperature (25°C) for one week.

[0152] By the above method, a cured product of the thermally conductive composition can be obtained.

[0153] The thermally conductive composition thus obtained contains a polyisocyanate component having a hydrophilic group introduced therein, and therefore the thermally conductive composition can suppress bleeding of the thermally conductive filler while ensuring thermal conductivity.

[0154] Furthermore, the cured product of the thermally conductive composition obtained in this manner contains a polyisocyanate having a hydrophilic group introduced therein as the polyisocyanate component of the thermally conductive composition, and therefore the cured product of the thermally conductive composition can suppress bleeding of the thermally conductive filler while ensuring thermal conductivity. [Example]

[0155] The present invention will be described in more detail below with reference to examples, but is not limited thereto. Specific numerical values ​​of the blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the upper limit values ​​(numeric values ​​defined as "not more than" or "less than") or lower limit values ​​(numeric values ​​defined as "not less than" or "exceeding") of the corresponding blending ratios (content ratios), physical property values, parameters, etc. described in the above "Form for Carrying Out the Invention." Note that "parts" and "%" are based on mass unless otherwise specified.

[0156] Synthesis Example 1 (Preparation of Polyisocyanate A) (HDI Isocyanurate A) A four-neck flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was charged with 1000.0 g of hexamethylene diisocyanate (manufactured by Tosoh Corporation) and 26.8 g of 1,3-butanediol (equivalent ratio (NCO / OH) of the isocyanate groups of hexamethylene diisocyanate to the hydroxyl groups of 1,3-butanediol: 20), and a urethane reaction was carried out at 80°C for 2 hours.

[0157] Next, 0.52 g of DABCO-TMR (N-(2-hydroxypropyl)-N,N,N-trimethylammonium-2-ethylhexanoate, manufactured by Air Products) was added as a trimerization catalyst to the resulting reaction solution, and the mixture was reacted at 70 to 80°C for 1 hour.

[0158] After it was confirmed by measuring the isocyanate group content that 16% of the remaining NCO groups after urethanization had been converted, 0.60 g of orthotoluenesulfonic acid was added to terminate the reaction.

[0159] The resulting reaction liquid was distilled using a thin-film distillation apparatus (vacuum degree 0.05 kPa, temperature 140°C) to remove unreacted hexamethylene diisocyanate, thereby obtaining Polyisocyanate A.

[0160] The isocyanate group content (NCO%) of this Polyisocyanate A was 21.0%.

[0161] Synthesis Example 2 (Preparation of Polyisocyanate B) (HDI Isocyanurate B) Polyisocyanate B was obtained in the same manner as in Synthesis Example 1, except that 1000.0 g of hexamethylene diisocyanate and 1.5 g of isobutanol were used (equivalent ratio (NCO / OH) of the isocyanate groups of hexamethylene diisocyanate to the hydroxyl groups of isobutanol: 600).

[0162] The isocyanate group content (NCO%) of this Polyisocyanate B was 23.3%.

[0163] Synthesis Example 3 (Preparation of Polyisocyanate C) (PDI Isocyanurate) Polyisocyanate C was obtained in the same manner as in Synthesis Example 1, except that 1,000.0 g of 1,5-pentamethylene diisocyanate (STABIO (registered trademark) PDI, manufactured by Mitsui Chemicals, Inc.) and 1.6 g of isobutanol were used (equivalent ratio (NCO / OH) of 1,5-pentamethylene diisocyanate groups to hydroxyl groups of isobutanol: 600).

[0164] The isocyanate group content (NCO%) of this Polyisocyanate C was 25.0%.

[0165] Synthesis Example 4 (Synthesis of Hydrophilic Group-Modified Polyisocyanate Composition D) (HDI Isocyanurate A / Anionic / Nonionic) 93.8 g of polyisocyanate A, 2.0 g of 3-(cyclohexylamino)-propanesulfonic acid, 1.2 g of dimethylcyclohexylamine, and 3 g of methoxy PEG-400 were mixed in a mass ratio and reacted under dry nitrogen at 80 to 90°C for 8 hours to obtain hydrophilic group-modified polyisocyanate composition D.

[0166] Synthesis Example 5 (Synthesis of Hydrophilic Group-Modified Polyisocyanate Composition E) (HDI Isocyanurate B / Anion) 96.2 g of Polyisocyanate B, 2.4 g of 3-(cyclohexylamino)-propanesulfonic acid, and 1.4 g of dimethylcyclohexylamine were mixed in a mass ratio and reacted under dry nitrogen at 80 to 90°C for 8 hours to obtain Hydrophilic Group-Modified Polyisocyanate Composition E.

[0167] Synthesis Example 6 (Synthesis of Hydrophilic Group-Modified Polyisocyanate Composition F) (HDI Isocyanurate B / Nonionic) 80.0 g of Polyisocyanate B and 20 g of Methoxy PEG-400 were mixed in a mass ratio and reacted under dry nitrogen at 80 to 90° C. for 8 hours to obtain Hydrophilic Group-Modified Polyisocyanate Composition F.

[0168] Synthesis Example 7 (Synthesis of Hydrophilic Group-Modified Polyisocyanate Composition G) (PDI Isocyanurate / Nonionic) 80.0 g of Polyisocyanate C and 20 g of Methoxy PEG-400 were mixed in a mass ratio and reacted under dry nitrogen at 80 to 90° C. for 8 hours to obtain Hydrophilic Group-Modified Polyisocyanate Composition G.

[0169] Examples 1 to 8, Comparative Example 1 The thermally conductive filler and the silane coupling agent were divided into polyisocyanate components and polyol components in the ratios shown in Tables 1 and 2. The polyisocyanate component was mixed with the previously divided thermally conductive filler and silane coupling agent to obtain polyisocyanate component (1). The polyol component was mixed with the previously divided thermally conductive filler and silane coupling agent to obtain polyol component (1). The polyisocyanate component (1), the polyol component (1), and the urethane catalyst (curing catalyst) were mixed in the ratios shown in Tables 1 and 2 to obtain the thermally conductive compositions of Examples 1 to 8 and Comparative Example 1.

[0170] Comparative Example 2 The thermally conductive filler and silane coupling agent were divided into polyisocyanate components and polyol components in the ratios shown in Comparative Example 2 in Table 2. The polyisocyanate component was mixed with the previously divided thermally conductive filler and silane coupling agent, and a dispersant was further added to obtain polyisocyanate component (2). The polyol component was mixed with the previously divided thermally conductive filler and silane coupling agent to obtain polyol component (2). The polyisocyanate component (2), polyol component (2), and urethane catalyst (curing catalyst) were mixed in the ratios shown in Comparative Example 2 in Table 2 to obtain the thermally conductive composition of Comparative Example 2.

[0171] <Preparation of test specimen> The thermally conductive compositions of each Example and Comparative Example prepared in the proportions shown in Tables 1 and 2 were poured into a mold with an inner diameter of 45 mm and left to cure at room temperature (25°C) for 7 days. The stability (bleed-out over time) of the resulting cured products was measured.

[0172] <Measurement of stability (bleed-out over time)> The test pieces were prepared, and after one month, they were placed on paper for one day, and the next day, the presence or absence of marks at the contact points was visually evaluated. The evaluation was rated as ◯ for those without marks, and x for those with marks. Note that in Comparative Example 1, a test piece with a smooth surface could not be prepared, so stability (bleed-out over time) could not be measured.

[0173] <Measurement of thermal conductivity (thermal conductivity)> (Experimental method: Preparation of test specimen) The thermally conductive compositions of each Example and Comparative Example prepared in the proportions shown in Tables 1 and 2 were poured into a mold having an inner diameter of 45 mm to a thickness of 10 mm, and left to harden at room temperature (25°C) for 7 days to obtain test specimens.

[0174] (Evaluation method: Thermal conductivity measurement) The obtained test pieces, each measuring 45 mm in diameter and 10 mm in thickness, were left to stand at 23°C for 2 hours, after which a sensor was sandwiched between two test pieces, and the thermal conductivity was measured in accordance with the test standard ISO / CD22007-2 using a hot disc method thermal property measuring device TPA-501 (manufactured by Kyoto Electronics Manufacturing Co., Ltd.) Note that in Comparative Example 1, it was not possible to measure the thermal conductivity (thermal conductivity) because it was not possible to prepare a test piece with a smooth surface.

[0175] [Table 1]

[0176] [Table 2]

[0177] Details of the abbreviations in the table are given below. HDI: 1,6-hexamethylene diisocyanate PDI: 1,5-pentamethylene diisocyanate Capa 2043: Trade name, polycaprolactone diol, average molecular weight approximately 400, manufactured by Ingevity Castor oil: Model number Diamond, manufactured by Ito Oil Mills V-325F: Product name, alumina, manufactured by Nippon Light Metal Co., Ltd. BX053: Product name, aluminum hydroxide, average particle size 6 μm, manufactured by Nippon Light Metal Co., Ltd. KBM-403: Product name, epoxy silane, manufactured by Shin-Etsu Chemical Co., Ltd. Neostan U-100: Trade name, urethane catalyst, dibutyltin dilaurate (organometallic catalyst, DBTDL), manufactured by Nitto Kasei Co., Ltd.

Claims

1. a polyisocyanate component and a polyol component; Thermally conductive filler and A thermally conductive composition comprising: The polyisocyanate component contains a polyisocyanate having a hydrophilic group introduced therein, the thermally conductive filler is contained in an amount of 200 parts by mass or more relative to 100 parts by mass of the total amount of the polyisocyanate component and the polyol component; Thermally conductive compositions.

2. A polyisocyanate component and a polyol component, Thermally conductive filler and A thermally conductive composition comprising: The polyisocyanate component contains a polyisocyanate having a hydrophilic group introduced therein, the polyol component comprises polycaprolactone polyol and / or castor oil polyol; Thermally conductive compositions.

3. A polyisocyanate component and a polyol component, Thermally conductive filler and A thermally conductive composition comprising: The polyisocyanate component contains a polyisocyanate having a hydrophilic group introduced therein, the polyisocyanate is a derivative of an aliphatic polyisocyanate, The derivative is an isocyanurate derivative. Thermally conductive compositions.

4. The thermally conductive filler comprises aluminum hydroxide and / or alumina. The thermally conductive composition according to any one of claims 1 to 3.

5. A cured product of the thermally conductive composition according to any one of claims 1 to 4.

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