TW202246371A - Isocyanate-containing composition and two-part reaction type polyurethane resin composition - Google Patents

Abstract

The present invention improves, in a polyurethane resin composition containing an inorganic filler, the miscibility of an isocyanate-containing composition with respect to a polyol-containing composition while suppressing the reduction in storage stability of the isocyanate-containing composition. An isocyanate-containing composition according to an embodiment of the present invention is to be used as a polyisocyanate component for a two-part reaction type polyurethane resin composition, and contains: an isocyanate group-containing urethane prepolymer obtained by causing a reaction between a polyisocyanate and a polyol having an average functional group number of 2.5 or less and a weight average molecular weight of 700 or more; an inorganic filler; a plasticizing agent; and at least one selected from the group consisting of compounds represented by general formula (1) and/or compounds represented by general formula (3).

Description

Isocyanate-containing composition and two-component reactive polyurethane resin composition

The present invention relates to a two-liquid reactive polyurethane resin composition and an isocyanate-containing composition usable as its polyisocyanate component.

It is known to impart heat dissipation by compounding an inorganic filler in a polyurethane resin composition. For example, Patent Document 1 discloses that an inorganic filler, a plasticizer, and a phosphoric acid ester are blended in a polyurethane resin obtained by reacting polyisocyanate and polybutadiene polyol. The compounding ratio contains an inorganic filler to improve heat dissipation. [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-150473

[Problem to be Solved by the Invention] When blending an inorganic filler into a polyurethane resin composition, generally, the inorganic filler is blended into a polyol component, and a polyisocyanate component that does not contain an inorganic filler is added thereto and mixed, React the two components. However, polyol components containing inorganic fillers have a problem of being difficult to mix with polyisocyanate components not containing inorganic fillers. In order to improve the miscibility of both, when an inorganic filler is blended in a polyisocyanate component, the storage stability of a polyisocyanate component will fall.

Embodiments of the present invention In view of the above points, an object of the present invention is to provide an isocyanate-containing composition that can suppress the isocyanate-containing composition that can be used as a polyisocyanate component in a polyurethane resin composition containing an inorganic filler. While reducing the storage stability of the product, it improves the miscibility with polyol-containing compositions that can be used as polyol components. [Means to solve the problem]

The present invention includes the embodiments shown below. [1] An isocyanate-containing composition that can be used as a polyisocyanate component of a two-component reactive polyurethane resin composition, the isocyanate-containing composition comprising: An isocyanate group-containing urethane prepolymer obtained by reacting a polyol with an average molecular weight of 700 or more with polyisocyanate, an inorganic filler, a plasticizer, and a compound represented by the following general formula (1) and the following At least one of the group of compounds represented by the above-mentioned general formula (3). In the general formula (1), R ¹ represents OH or a group shown in the following general formula (2), and it can also be R ¹ is a mixture of a compound represented by OH and a compound represented by R ¹ represented by general formula (2), in general formula (3), k represents the number of 1 or 0, and X represents -CH ₂ -, -CO(CH ₂ ) _p - or the linking group of -COCH=CH-, where p represents an integer of 2 to 6, Z represents carboxyl, sulfo or their salts, general formula (1), general formula (2) and general formula ( In 3), R ² and R ³ each independently represent a hydrocarbon group with 6 to 30 carbons, A ¹ O and A ³ O each independently represent an oxyalkylene group with 2 to 4 carbons, m and n are alkylene oxides The average added moles of each independently represents a number from 1 to 100, and (A ¹ O) _m and (A ³ O) _n each independently represent an oxyethylene group content of 20 mole % or more. [chemical 1]

[2] The isocyanate-containing composition according to [1], wherein the polyisocyanate is an aliphatic diisocyanate and/or an alicyclic diisocyanate. [3] The isocyanate-containing composition according to [1] or [2], which contains 50% by mass to 95% by mass of the inorganic filler in 100% by mass of the isocyanate-containing composition. [4] The isocyanate-containing composition according to any one of [1] to [3], wherein the plasticizer is a diester of phthalic acid and/or a diester of adipate. [5] A two-liquid reactive polyurethane resin composition, comprising: the isocyanate-containing composition as described in any one of [1] to [4], and a polyol and an inorganic filler Compositions containing polyols. [6] The two-component reactive polyurethane resin composition as described in [5], which can be used as a heat dissipation material. [Effect of the invention]

According to the embodiment of the present invention, it is possible to improve the miscibility with the polyol-containing composition while suppressing a decrease in the storage stability of the isocyanate-containing composition.

The two-component reactive polyurethane resin composition of the present embodiment includes a polyol-containing composition as a polyol component and an isocyanate-containing composition as a polyisocyanate component.

＜Isocyanate-containing composition＞ [Urethane prepolymer (a)] The isocyanate-containing composition contains a urethane prepolymer (a). In the present embodiment, as the urethane prepolymer (a), an isocyanate group-containing amine group having an average number of functional groups of 2.5 or less and a weight average molecular weight of 700 or more polyol and polyisocyanate as constituents can be used. formate prepolymer.

When the average number of functional groups (average number of hydroxyl groups) of the polyol is 2.5 or less, the hardness of the hardened polyurethane resin can be kept low. When the resin composition is used as a gap filler that fills the gap around the battery, it can reduce the reaction force against the external force. The average number of functional groups of the polyol is preferably less than 2.4, more preferably less than 2.3. The lower limit of the average number of functional groups of the polyol is not particularly limited, for example, the average number of functional groups may be 1.7 or more. The polyol preferably has hydroxyl groups at both ends, so the average number of functional groups is preferably 2.0 or more.

When the weight average molecular weight (Mw) of the polyol is 700 or more, the storage stability of the isocyanate-containing composition can be improved. The weight average molecular weight of the polyol is preferably 800 or more. The upper limit of the weight average molecular weight of a polyol is not specifically limited, For example, a weight average molecular weight may be 10000 or less, and may be 5000 or less. In the present specification, the weight average molecular weight is measured by gel permeation chromatography (GPC (Gel Permeation Chromatography) method) and calculated using a calibration curve based on standard polystyrene.

The polyol is not particularly limited, and examples include: polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene polyol, etc., which can be Use any one or a combination of two or more. Examples of polyether polyols include polyoxyalkylene polyols obtained by adding ethylene oxide or propylene oxide to polyols or polyamines. Examples of polyester polyols include those obtained by dehydrating condensation of carboxylic acids such as adipic acid and phthalic acid with polyhydric alcohols such as ethylene glycol and 1,4-butanediol. As a polybutadiene polyol, what has a hydroxyl group at both terminals of a polybutadiene structure is more preferable, and what hydrogenated may be sufficient as it. Among these, it is preferable to use polypropylene glycol and/or polybutadiene polyol.

The polyisocyanate is not particularly limited, and examples include: aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, etc., preferably aliphatic diisocyanate, alicyclic diisocyanate, and Use both.

Examples of the aliphatic diisocyanate include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate (Hexamethylene Diisocyanate, HDI), 2,2,4-trimethylhexa Methylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1 , 5-diisocyanate, etc. Moreover, these can also be used in combination of 2 or more types.

Examples of the alicyclic diisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methyl Cyclohexyl diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, etc. Moreover, these can also be used in combination of 2 or more types.

The urethane prepolymer (a) can be obtained by reacting the above polyol and polyisocyanate under the condition of excess isocyanate groups. The ratio (molar ratio) of the isocyanate group to the hydroxyl group used to obtain the urethane prepolymer (a) is not particularly limited, preferably isocyanate group:hydroxyl = 1.5~2.5:1, more preferably 1.7~ 2.3:1. The urethane prepolymer (a) is preferably a terminal isocyanate prepolymer having isocyanate groups at both terminals.

The blending amount of the urethane prepolymer (a) is not particularly limited, but is preferably 1.0% by mass to 15% by mass, more preferably 1.5% by mass to 10% by mass, based on 100% by mass of the isocyanate-containing composition .

[Inorganic filler (b)] The isocyanate-containing composition contains an inorganic filler (b). By compounding the inorganic filler (b), heat dissipation properties can be imparted to the cured polyurethane resin.

The inorganic filler (b) is not particularly limited, and examples thereof include metal oxides such as aluminum oxide and magnesium oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and metal nitrides such as aluminum nitride and boron nitride. Wait. These may be used either alone or in combination of two or more.

The amount of the inorganic filler (b) to be blended is preferably 50% by mass to 95% by mass based on 100% by mass of the isocyanate-containing composition. When this compounding quantity is 50 mass % or more, the heat dissipation of a polyurethane resin can be improved. When the compounding amount is 95% by mass or less, the storage stability of the isocyanate-containing composition can be improved. The blending amount is more preferably at least 60% by mass, more preferably at least 70% by mass, still more preferably at least 80% by mass, and more preferably at most 90% by mass.

[Plasticizer (c)] The isocyanate-containing composition contains a plasticizer (c). By blending the plasticizer (c) together with the component (d) described later, the storage stability of the isocyanate-containing composition improves, and the miscibility with the polyol-containing composition can be improved.

The plasticizer (c) is not particularly limited, and conventionally known ones formulated in polyurethane resins can be used, for example, dioctyl phthalate, diisononyl phthalate, Phthalic acid diesters such as di-undecyl phthalate; adipate diesters such as dioctyl adipate and diisononyl adipate; trioctyl trimellitate, trimellitic acid Trimellitic acid esters such as triisononyl triacid; pyromellitic acid esters such as tetraoctyl pyromellitic acid and tetraisononyl pyromellitic acid; tricresyl phosphate, tris(xylene) phosphate, Phosphate triesters such as cresyl diphenyl phosphate and the like can be used either alone or in combination of two or more. Among these, the plasticizer (c) is preferably a diester of phthalic acid and/or a diester of adipate.

The blending amount of the plasticizer (c) is not particularly limited. For example, it may be 1% by mass to 40% by mass, 3% to 35% by mass, or 5% by mass based on 100% by mass of the isocyanate-containing composition. % by mass to 30% by mass, or 10% by mass to 20% by mass.

[compound (d)] The isocyanate-containing composition contains at least one compound selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (3) (hereinafter, may be referred to as compound (d)). By compounding the compound (d) together with the plasticizer (c), the storage stability of the isocyanate-containing composition is improved, and the miscibility with the polyol-containing composition can be improved.

Among the compounds (d), the compound represented by the following general formula (1) is a phosphoric acid ester. [Chem 2]

In formula (1), R ¹ represents OH or a group represented by the following general formula (2). The phosphoric acid ester represented by formula ( ¹ ) may be a compound (monoester) represented by R1 being OH, or a compound (diester) represented by R1 as general formula ( ² ), or a combination of both. mixture. [Chem 3]

In formula (1) and formula (2), R ² represents a hydrocarbon group with 6 to 30 carbons, more preferably a hydrocarbon group with 8 to 20 carbons. Examples of the hydrocarbon group include linear or branched alkyl groups, alkenyl groups, aryl groups, or aralkyl groups, and these groups may have a substituent.

Specific examples of the alkyl group include hexyl, isohexyl, heptyl, isoheptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, deca Monoalkyl, Isoundecyl, Dodecyl, Isododecyl, Tridecyl, Isotridecyl, Tetradecyl, Isotetradecyl, Pentadecyl, Isodecyl Pentadecyl, Hexadecyl, Isohexadecyl, 2-Hexyldecyl, Heptadecyl, Isohexadecyl, Octadecyl, Isooctadecyl, 2-Octyldecyl, 2-Hexyldodecyl, nonadecyl, isononadecyl, eicosyl, isoeicosyl, eicosyl, isoeicosyl, docosyl, iso Docosyl, tricosyl, isotricosyl, tetracosyl, isotetracosyl, pentadecyl, isopentacyl, hexacyl , Isohexacyl, Hectadecyl, Isohexacyl, etc.

Specific examples of alkenyl include: hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleene Base etc.

Specific examples of the aryl group include: phenyl, tolyl, xylyl, cumyl, mesityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, Hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, styrenated phenyl, p-cumylphenyl, Phenylphenyl, benzylphenyl, α-naphthyl, β-naphthyl, etc.

Specific examples of the aralkyl group include benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl and the like.

In formula (1) and formula (2), A ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms. m represents the average addition mole number of alkylene oxide, and is a number of 1 to 100, preferably a number of 3 to 50, more preferably a number of 5 to 30, and more preferably a number of 7 to 20. In the oxyalkylene chain represented by (A ¹ O) _m , the content of the oxyethylene group is 20 mol % or more. That is, when the oxyethylene group is EO and the oxyethylene group other than the oxyethylene group is AO, EO/AO (molar ratio)=100/0 to 20/80. The content of the oxyethylene group is preferably at least 50 mol%, more preferably at least 70 mol%, even more preferably at least 80 mol%, and may be 100 mol%. When the oxyalkylene chain contains multiple oxyalkylene groups, the oxyalkylene groups may be added randomly or in blocks.

The phosphoric acid ester represented by formula (1) can be produced, for example, by adding an alkylene oxide to monoalcohols or phenols having 6 to 30 carbon atoms by a known method, and then making phosphoric anhydride, orthophosphoric acid, polyphosphoric acid Phosphating agents such as phosphoric acid oxychloride react with the hydroxyl groups at the alkylene oxide terminals of the obtained polyether monoalcohol. Depending on the production method, a monoester compound and a diester compound may be obtained as a mixture, but these may be separated or used as a mixture as it is. Moreover, it can also be used by reacting in presence of water, and increasing the content rate of a monoester type compound.

Among the compounds (d), the compound represented by the following general formula (3) is a sulfuric acid ester, a sulfonic acid, or a carboxylic acid, and any of these may be used, or two or more of them may be used in combination. [chemical 4]

In the formula (3), k represents a number of 1 or 0. X represents a linking group that is -CH ₂ -, -CO(CH ₂ ) _p - or -COCH=CH-, where p represents an integer of 2-6.

Z in the formula (3) represents a carboxyl group (-COOH), a sulfo group (-SO ₃ H) or a salt thereof, and the acid form and the salt form may also exist in mixture. Examples of salts include alkali metal salts, alkaline earth metal salts, ammonium salts, and alkanolamine salts. Examples of alkali metal salts include sodium salts, potassium salts, and lithium salts. As an example of an alkaline earth metal salt, a calcium salt, a magnesium salt, etc. are mentioned. Examples of alkanolamine salts include monoethanolamine salts, diethanolamine salts, triethanolamine salts, and triisopropanolamine salts.

R ³ in formula (3) represents a hydrocarbon group having 6 to 30 carbons, more preferably a hydrocarbon group having 8 to 20 carbons. Examples of the hydrocarbon group include linear or branched alkyl groups, alkenyl groups, aryl groups, or aralkyl groups, and these groups may have a substituent. Specific examples of alkyl, alkenyl, aryl, and aralkyl are the same as R ² .

In formula (3), A ³ O represents an oxyalkylene group having 2 to 4 carbon atoms. n represents the average addition mole number of alkylene oxide, and is a number of 1 to 100, preferably a number of 3 to 50, more preferably a number of 5 to 30, and more preferably a number of 7 to 20. In the oxyalkylene chain represented by (A ³ O) _m , the content of the oxyethylene group is 20 mol % or more. That is, when the oxyethylene group is EO and the oxyethylene group other than the oxyethylene group is AO, EO/AO (molar ratio)=100/0 to 20/80. The content of the oxyethylene group is preferably at least 50 mol%, more preferably at least 70 mol%, even more preferably at least 80 mol%, and may be 100 mol%. When the oxyalkylene chain contains multiple oxyalkylene groups, the oxyalkylene groups may be added randomly or in blocks.

When the said Z is a carboxyl group, the compound represented by formula (3) is a carboxylic acid. In this case, the carboxylic acid of formula (3) can be produced, for example, by adding an alkylene oxide to a monoalcohol or phenol having 6 to 30 carbon atoms by a known method, and then using monohalogenated acetic acid or The salt reacts with the hydroxyl group at the terminal of the alkylene oxide in the presence of a base. Alternatively, an acid anhydride can be used for production by a method based on a ring-opening reaction with a hydroxyl group at the terminal of an alkylene oxide. In the case of using monohalogenated acetic acid or a salt thereof, a carboxylic acid in which k=1, X is -CH ₂ -, and Z is COOH or a salt thereof in formula (3) can be obtained. In addition, when an acid anhydride is used, a carboxylic acid in which k=1, X is -CO(CH ₂ ) _p - or -COCH=CH-, and Z is COOH can be obtained.

When Z is a sulfo group, the compound represented by the formula (3) is a sulfuric acid ester if k=0, and a sulfonic acid if k=1. For example, sulfuric acid esters can be produced by adding alkylene oxides to monoalcohols or phenols having 6 to 30 carbon atoms by a known method, and reacting sulfamic acid with hydroxyl groups at the end of the alkylene oxides. . Also, for example, sulfonic acid can be produced by reacting with a hydroxyl group at the terminal of an alkylene oxide using a monohalogenated sulfonic acid or a salt thereof after adding the above-mentioned alkylene oxide.

The compounding amount of the compound (d) is not particularly limited, for example, it may be 0.01% by mass to 5% by mass, 0.03% by mass to 2% by mass, or 0.05% by mass in 100% by mass of the isocyanate-containing composition ~1% by mass.

[other ingredients] In the isocyanate-containing composition, as the polyisocyanate compound, the above-mentioned urethane prepolymer (a) may be used alone, or other polyisocyanate compounds may be used together with the urethane prepolymer (a).

The other polyisocyanate compounds are not particularly limited, and various polyisocyanate compounds having two or more isocyanate groups in one molecule can be used, for example, aliphatic polyisocyanate, alicyclic polyisocyanate and aromatic polyisocyanate, and Any one or more of these modifiers and polynuclear bodies may be used, or two or more of them may be used in combination. Specific examples of the aliphatic polyisocyanate and the alicyclic polyisocyanate include the aforementioned aliphatic diisocyanate and alicyclic diisocyanate. Examples of the aromatic polyisocyanate include Tolylene Diisocyanate (TDI), Diphenylmethane Diisocyanate (MDI), 4,4'-dibenzyl diisocyanate, 1,5 - Naphthylene diisocyanate, xylylene diisocyanate (Xylylene Diisocyanate, XDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, etc. Modifiers of these polyisocyanate compounds include, for example, isocyanurate modified products, allophanate modified products, biuret modified products, adduct modified products, carbodiamide modified products, and polyisocyanate modified products. Imine modifiers, etc.

Among these, as the other polyisocyanate compound, it is preferable to use a modified isocyanurate of the above-mentioned polyisocyanate compound, more preferably a modified isocyanurate of an aliphatic polyisocyanate. In this case, the blending amount of the isocyanurate modifier is not particularly limited, for example, it is preferably 0.05% by mass to 5% by mass, more preferably 0.1% by mass in 100% by mass of the isocyanate-containing composition %~2 mass%. Furthermore, the polyisocyanate compound is preferably composed mainly of the above-mentioned urethane prepolymer (a), and even when other polyisocyanate compounds are used in combination, it is preferable that the polyisocyanate compound exceeds 50% by mass of the entire polyisocyanate compound. , more preferably 60% by mass or more is the urethane prepolymer (a).

In the isocyanate-containing composition, in addition to the above-mentioned components, for example, moisture absorbents, antioxidants, foam stabilizers, diluents, flame retardants, ultraviolet absorbers, Various additives such as colorants.

The isocyanate value (NCOV) of the isocyanate-containing composition is not particularly limited, and may be 1.0 mgKOH/g to 10 mgKOH/g, 1.5 mgKOH/g to 8.0 mgKOH/g, or 2.0 mgKOH/g to 7.5 mgKOH/g.

＜Compositions containing polyols＞ [Polyol (e)] The polyol-containing composition contains polyol (e). The polyol (e) is not particularly limited, and examples thereof include polyether polyols, polyester polyols, polycarbonate polyols, polybutadiene polyols, polyisoprene polyols, and the like. Any one type or a combination of two or more types may be used. Among these, polybutadiene polyol is preferably used. As a polybutadiene polyol, what has a hydroxyl group at both terminals of a polybutadiene structure is more preferable, and what hydrogenated may be sufficient as it. The average functional group number of polybutadiene polyol is preferably 2.0～2.5, more preferably 2.1～2.4.

The blending amount of the polyol (e) is not particularly limited, but it is preferably 2% by mass to 30% by mass, more preferably 3% by mass to 25% by mass, and still more preferably 5% by mass, based on 100% by mass of the polyol-containing composition. Mass% to 20 mass%.

[Inorganic filler (f)] The polyol-containing composition contains an inorganic filler (f). By compounding the inorganic filler (f), heat dissipation properties can be imparted to the cured polyurethane resin. The inorganic filler (f) is not particularly limited, and examples thereof include: metal oxides such as aluminum oxide and magnesium oxide; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; metal nitrogen such as aluminum nitride and boron nitride. compounds etc. These may be used either alone or in combination of two or more.

The blending amount of the inorganic filler (f) is preferably 50 mass % to 95 mass % in 100 mass % of the polyol-containing composition, more preferably 60 mass % or more, more preferably 70 mass % or more, still more preferably 80 mass % or more, and preferably 90 mass % or less. [Plasticizer (g)] The polyol-containing composition may also contain a plasticizer (g). By including the plasticizer (g), the hardness of the polyurethane resin after hardening can be reduced. The plasticizer (g) is not particularly limited, and examples thereof include the above-mentioned phthalic acid diester, adipate diester, trimellitate, pyromellitic acid ester, and phosphoric acid triester. These can be used either alone or in combination of two or more. Among these, the plasticizer (g) is preferably a phthalic acid diester and/or an adipate diester.

The blending amount of the plasticizer (g) is not particularly limited. For example, it may be 1% by mass to 30% by mass, 3% to 25% by mass, or 3% by mass to 100% by mass of the composition containing polyol. 5% by mass to 20% by mass, or 5% by mass to 15% by mass. [Phosphate (h)] The polyol-containing composition may also contain phosphoric acid ester (h). By including the phosphoric acid ester (h), the viscosity of the polyol-containing composition (h) can be reduced. As the phosphoric acid ester (h), a compound represented by the formula (1) is used.

The blending amount of phosphoric acid ester (h) is not particularly limited, for example, it may be 0.01% by mass to 5% by mass, 0.03% by mass to 2% by mass, or 0.05% by mass in 100% by mass of the polyol-containing composition. Mass % ~ 1 mass %.

[other ingredients] In the polyol-containing composition, in addition to the above-mentioned components, for example, a hygroscopic agent, a catalyst, an antioxidant, a foam stabilizer, a diluent, a flame retardant, Various additives such as UV absorbers and colorants.

As the catalyst, for example, metal catalysts such as organic tin catalysts, organic lead catalysts, and organic bismuth catalysts, and various urethane polymerization catalysts such as amine catalysts can be used.

The hydroxyl value (OHV) of the polyol-containing composition is not particularly limited, and may be 1.0 mgKOH/g to 15 mgKOH/g, or 2.0 mgKOH/g to 10 mgKOH/g.

＜Two-component reactive polyurethane resin composition＞ The two-liquid reactive polyurethane resin composition of this embodiment generally includes a first liquid as a polyol-containing composition and a second liquid as an isocyanate-containing composition, except for the polyol-containing composition and the isocyanate-containing composition. In addition to the isocyanate-containing composition, one containing the above-mentioned other components as optional components may be included as the third liquid.

The two-component reactive polyurethane resin composition can be produced by separately preparing a polyol-containing composition and an isocyanate-containing composition, that is, the polyol-containing composition and the isocyanate-containing composition can be filled separately in different containers. The polyol-containing composition and the isocyanate-containing composition filled in each container may be mixed at the time of use, whereby the polyol and polyisocyanate react to form a polyurethane resin and harden it. At this time, it can also be cured by heating. The two-liquid reactive polyurethane resin composition of the embodiment may be obtained by mixing a polyol-containing composition and an isocyanate-containing composition, may be liquid before hardening, and may be hardened.

In the two-component reactive polyurethane resin composition, the mixing ratio of the polyol-containing composition and the isocyanate-containing composition is not particularly limited. For example, the isocyanate group contained in the isocyanate-containing composition is relatively The molar ratio NCO/OH (index) of the hydroxyl group contained in the polyol composition may be 0.5-1.2, or may be 0.6-0.9. Here, NCO/OH is calculated as NCOV/OHV from the above-mentioned isocyanate value (NCOV) and hydroxyl value (OHV).

In the two-component reactive polyurethane resin composition, the volume ratio of the polyol-containing composition to the isocyanate-containing composition is not particularly limited, but is preferably a polyol-containing composition/isocyanate-containing composition Matter=30/70～70/30, more preferably 40/60～60/40, and then preferably 45/55～55/45.

The hardness of the two-component reactive polyurethane resin composition after hardening is not particularly limited, but the shore C hardness is preferably 60 or less, and may be 30 to 60.

The thermal conductivity (Japanese Industrial Standards (JIS) R2618) of the two-component reactive polyurethane resin composition after curing is not particularly limited, for example, it may be 1.0 W/m·K or more, It may be 2.0 W/m·K or more, or 2.0 W/m·K to 3.0 W/m·K.

＜Applications of two-component reactive polyurethane resin composition＞ The application of the two-component reaction type polyurethane resin composition of the present embodiment is not particularly limited, and it can be used in various applications such as electric and electronic parts or for vehicles. It has heat dissipation properties by compounding inorganic fillers, so it can be preferably used as a heat dissipation material. As one embodiment, it can be suitably used as a heat-dissipating gap filler for heat sources such as batteries. [Example]

Hereinafter, the two-liquid reaction type polyurethane resin composition will be described in detail based on Examples and Comparative Examples, but the present invention is not limited thereto.

Raw materials used in Examples and Comparative Examples are shown below. [Inorganic filler] Aluminum hydroxide: Sumitomo Chemical Co., Ltd. "CW-350" (density 2.4 g/cm ³ ) Alumina 1: Denka Chemicals (DENKA) Co., Ltd. "DAW-45" (density 4.0 g/cm ³ ) Alumina 2: "DAW-03" manufactured by Denka Corporation (DENKA) (density 4.0 g/cm ³ )

[Polyol] ·Polybutadiene polyol: "POLYVEST HT" manufactured by EVONIK, with an average functional base of 2.3 [Plasticizer] DUP: di-undecyl phthalate DOA: di-2-ethylhexyl adipate

[Polyisocyanate compound] ·Isocyanurate: HDI modified by isocyanurate, manufactured by Wanhua Chemical "HT600" [Hygroscopic agent] ・Hygroscopic agent: "Molecular sieve (molecular sieve) 3AB" manufactured by Union Showa Co., Ltd.

Synthesis examples of prepolymer 1 to prepolymer 7 which are isocyanate group-containing urethane prepolymers used in Examples and Comparative Examples are shown below.

[Prepolymer 1] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen blowing tube, 33 parts by mass of hexamethylene diisocyanate (HDI) ("Duranate 50M" manufactured by Asahi Kasei Co., Ltd.) and poly Propylene glycol (average functional group number 2.0, weight average molecular weight 700, hydroxyl value 160) ("Excenol 720" manufactured by AGC Co., Ltd.) was reacted at 90°C for 2 hours with 67 parts by mass to obtain an isocyanate group-terminated amine urethane prepolymer (prepolymer 1).

[Prepolymer 2] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen blowing tube, 26 parts by mass of hexamethylene diisocyanate (HDI) (manufactured by Asahi Kasei Co., Ltd. "Duranate 50M") was mixed with poly Propylene glycol (average functional group number 2.0, weight average molecular weight 1000, hydroxyl value 112) ("Excenol 1020" manufactured by AGC Co., Ltd.) 74 parts by mass was reacted at 90°C for 2 hours to obtain an isocyanate group-terminated amine urethane prepolymer (prepolymer 2).

[Prepolymer 3] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen blowing tube, 10 parts by mass of hexamethylene diisocyanate (HDI) (manufactured by Asahi Kasei Co., Ltd. "Duranate 50M") was mixed with poly Propylene glycol (average number of functional groups 2.0, weight average molecular weight 3000, hydroxyl value 35) ("Excenol 3020" manufactured by AGC Co., Ltd.) was reacted at 120°C for 6 hours with 90 parts by mass to obtain an isocyanate group-terminated amine urethane prepolymer (prepolymer 3).

[Prepolymer 4] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen blowing tube, 31 parts by mass of isophorone diisocyanate (IPDI) (manufactured by EVONIK "IPDI") was mixed with polypropylene glycol (Average functional group number 2.0, weight average molecular weight 1000, hydroxyl value 112) ("Excenol 1020" manufactured by AGC Co., Ltd.) 69 parts by mass were reacted at 90°C for 2 hours to obtain an isocyanate group-terminated amino group Formate Prepolymer (Prepolymer 4).

[Prepolymer 5] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen blowing tube, 46 parts by mass of hexamethylene diisocyanate (HDI) (manufactured by Asahi Kasei Co., Ltd. "Duranate 50M") was mixed with poly Propylene glycol (average functional group number 2.0, weight average molecular weight 400, hydroxyl value 281) ("Excenol 420" manufactured by AGC Co., Ltd.) was reacted at 90°C for 2 hours with 54 parts by mass to obtain an isocyanate group-terminated amine urethane prepolymer (prepolymer 5).

[Prepolymer 6] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen blowing tube, 12 parts by mass of hexamethylene diisocyanate (HDI) ("Duranate 50M" manufactured by Asahi Kasei Co., Ltd.) and poly Butadiene polyol (average number of functional groups: 2.3, weight average molecular weight: 3,000, hydroxyl value: 46) ("POLYVEST HT" manufactured by EVONIK) 88 parts by mass were reacted at 90°C for 2 hours , whereby an isocyanate-terminated urethane prepolymer (prepolymer 6) was obtained.

[Prepolymer 7] In a four-necked flask including a stirrer, a reflux cooling tube, a thermometer, and a nitrogen blowing tube, 33 parts by mass of hexamethylene diisocyanate (HDI) ("Duranate 50M" manufactured by Asahi Kasei Co., Ltd.) and castor 68 parts by mass of sesame oil (average number of functional groups 2.7, weight average molecular weight 941, hydroxyl value 161) ("URIC H30" manufactured by Ito Oil Co., Ltd.) was reacted at 90°C for 2 hours to obtain isocyanate group-terminated carbamate Prepolymer (prepolymer 7).

Synthesis examples of phosphoric acid ester 1 to phosphoric acid ester 3, ammonium sulfate salt, and carboxylic acid 1 to carboxylic acid 3, which are compounds (d) used in Examples and Comparative Examples, are shown below.

[Phosphate ester 1] Into an autoclave with a temperature regulator including a stirrer, a thermometer, a nitrogen introduction pipe, an introduction pipe for charging raw materials, and an exhaust pipe for decompression, 200 g of tridecyl alcohol (1.0 mol), 5 g of potassium hydroxide as a catalyst, the environment in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was gradually introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130 °C and After making it react, it neutralized with acetic acid. Then, 47 g (0.33 mol) of phosphoric anhydride was reacted with the obtained 10 mol adduct of ethylene oxide at 80°C for 5 hours, thereby obtaining phosphoric acid ester 1 of general formula (1) (wherein, R ² : Tridecyl, A ¹ O: EO, m: 10, a mixture of monoester and diester in a molar ratio of 1:1).

[Phosphate ester 2] Into an autoclave equipped with a temperature regulator including a stirrer, a thermometer, a nitrogen introduction tube, an introduction tube for raw material charging, and an exhaust tube for decompression, 186 g (1.0 mol) of lauryl was charged , Potassium hydroxide 5 g as a catalyst, use nitrogen to replace the environment in the autoclave, and gradually introduce 815 g (18.5 moles) of ethylene oxide under the conditions of a pressure of 0.15 MPa and a temperature of 130 ° C and make it react Afterwards, neutralize with acetic acid. Then, 47 g (0.33 mol) of phosphoric anhydride was reacted with the obtained 18.5 mol adduct of ethylene oxide at 80°C for 5 hours, thereby obtaining phosphoric acid ester 2 of general formula (1) (wherein, R ² : lauryl, A ¹ O: EO, m: 18.5, a mixture of monoester and diester with a molar ratio of 1:1).

[Phosphate ester 3] Into an autoclave with a temperature regulator including a stirrer, a thermometer, a nitrogen introduction pipe, an introduction pipe for charging raw materials, and an exhaust pipe for decompression, 200 g of tridecyl alcohol (1.0 Mole), 5 g of potassium hydroxide as a catalyst, use nitrogen to replace the environment in the autoclave, and make 264 g (6 mole) of ethylene oxide and ring under the conditions of pressure 0.15 MPa and temperature 130 After reacting 290 g (5 moles) of oxypropane at the same time, neutralize with acetic acid. Then, 47 g (0.33 moles) of phosphoric anhydride was reacted with the obtained adducts of ethylene oxide and propylene oxide at 80° C. for 5 hours, thereby obtaining phosphoric acid ester 3 of general formula (1) (wherein, R ² : Tridecyl, (A ¹ O) _m : Random adduct of EO/PO (oxypropylene) = 6/5 (molar ratio), m: 11, of monoester and diester mol ratio 1:1 mixture).

[Ammonium sulfate salt] In a reaction vessel including a stirrer, a thermometer, and a reflux pipe, styrenated phenol (monostyrenated phenol: distyrenated phenol: tristyrenated phenol=80:19:1 (mass ratio ) mixture) 220 g (1.0 mol) was transferred to an autoclave, using potassium hydroxide as a catalyst, under the conditions of a pressure of 0.15 MPa and a temperature of 130°C, 792 g (18 mol) of ethylene oxide into a reaction to obtain polyoxyethylene styrenated phenyl ether. Next, the obtained polyoxyethylene styrenated phenyl ether was transferred to a reaction vessel including a stirrer, a thermometer and a nitrogen introduction tube, and 97 g of sulfamic acid ( l mole) reaction. Then, monoethanolamine was added to adjust the pH of the 1% by mass aqueous solution to 7.5 to obtain the ammonium sulfate salt of the general formula (3) (wherein, R ³ : styrenated phenyl, A ³ O: EO, n: 18 , k: 0, Z: -SO ₃ NH ₄ ).

[Carboxylic acid 1] In an autoclave with a temperature regulator including a stirrer, a thermometer, a nitrogen introduction pipe, an introduction pipe for charging raw materials, and an exhaust pipe for decompression, 200 g of tridecyl alcohol (1.0 mol), 5 g of potassium hydroxide as a catalyst, the environment in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was gradually introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130 °C and After making it react, it neutralized with acetic acid. Then, 151 g (1.3 moles) of the ethylene oxide adduct and sodium monochloroacetate were taken into the reactor in toluene solvent, and stirred until uniform. Then, under the condition that the temperature of the reaction system was 60° C., after adding 52 g (1.3 mol) of sodium hydroxide, the temperature of the reaction system was raised to 80° C. and reacted for 3 hours. After the reaction, 120 g (1.2 mol) of 98% by mass sulfuric acid was added dropwise to obtain a white suspension solution. Then, the white suspension solution was washed with distilled water, and the solvent was distilled off under reduced pressure to obtain carboxylic acid 1 of general formula (3) (wherein, R ³ : tridecyl, A ³ O: EO, n: 10, k: 1, X: -CH ₂ -, Z: -COOH).

[Carboxylic acid 2] Into an autoclave with a temperature regulator including a stirrer, a thermometer, a nitrogen introduction pipe, an introduction pipe for charging raw materials, and an exhaust pipe for decompression, 200 g of tridecyl alcohol (1.0 mol), 5 g of potassium hydroxide as a catalyst, the environment in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was gradually introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130 °C and After making it react, it neutralized with acetic acid. Then, 156 g (1 mol) of suberic anhydride was reacted at 120°C for 2 hours, thereby obtaining carboxylic acid 2 of general formula (3) (wherein, R ³ : tridecyl, A ³ O: EO , n: 10, k: 1, X: -CO-(CH ₂ ) ₆ -, Z: -COOH).

[Carboxylic acid 3] Into an autoclave with a temperature regulator including a stirrer, a thermometer, a nitrogen introduction pipe, an introduction pipe for charging raw materials, and an exhaust pipe for decompression, 200 g of tridecyl alcohol (1.0 mol), 5 g of potassium hydroxide as a catalyst, the environment in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was gradually introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130 °C and After making it react, it neutralized with acetic acid. Then, 198 g (1 mol) of maleic anhydride was reacted at 120°C for 2 hours to obtain carboxylic acid 3 of general formula (3) (wherein, R ³ : tridecyl, A ³ O: EO , n: 10, k: 1, X: -CO-CH ₂ =CH ₂ -, Z: -COOH).

The methods for measuring the average number of functional groups, weight average molecular weight, hydroxyl value, and isocyanate value are as follows. [average functional base] The number average molecular weight (Mn) was measured by GPC (gel permeation chromatography), and the hydroxyl value (mgKOH/g) was measured according to the A method of JISK1557-1:2007, and the average functional group number was calculated by the following formula. Average number of functional groups={(hydroxyl value)×(Mn)}/(56.11×1000)

[Weight average molecular weight and number average molecular weight] It is a value calculated from the dissolution time of the measurement sample by using a calibration curve prepared from the molecular weight of standard polystyrene and the dissolution time by GPC (gel permeation chromatography). Regarding the measurement conditions, TSKge1 Hxl (Tosoh Co., Ltd.) was used as a column, tetrahydrofuran (THF) was used as the mobile phase, the flow rate of the mobile phase was 1.0 mL/min, the column temperature was 40°C, and the sample injection volume was 50°C. μL and a sample concentration of 0.2% by mass.

[hydroxyl value] Measurement was performed in accordance with A method of JIS K1557-1:2007.

56.11：氫氧化鉀的分子量 1000：自g向mg的轉換係數 42.02：NCO的分子量 100：自百分率向/g的轉換係數 [Isocyanate value] is a value obtained by measuring the isocyanate content in accordance with the method A of JIS K1603-1:2007, and calculating the isocyanate value by the following formula from the obtained isocyanate content. [number 1]

56.11: Molecular weight of potassium hydroxide 1000: Conversion factor from g to mg 42.02: Molecular weight of NCO 100: Conversion factor from percentage to /g

[Example 1～Example 16 and Comparative Example 1～Comparative Example 5] Polyol-containing composition A1 to polyol-containing composition A7 were prepared according to the formulation (mass %) shown in Table 1 below, and an isocyanate-containing composition was prepared according to the formulation (mass %) shown in Table 2 below B1～isocyanate-containing composition B21. Regarding the isocyanate-containing composition B1 to the isocyanate-containing composition B21, the storage stability was evaluated. In addition, polyol-containing compositions A1 to polyol-containing compositions A7 and isocyanate-containing compositions B1 to isocyanate-containing compositions B21 were mixed in the combinations and volumetric ratios shown in Table 3 below. sex is evaluated. In addition, the hardness of the hardened product was measured after mixing and hardening. The measurement/evaluation methods of storage stability, miscibility and hardness are as follows.

[Storage Stability] The properties of the prepared isocyanate-containing composition were evaluated after being stored at 60°C for one month. Table 3 shows the case of maintaining the liquid as "liquid" and the case of curing from the liquid in Table 3. For "cure".

[mixed] Stir the polyol-containing composition and the isocyanate-containing composition at room temperature at 2000 rpm for 30 minutes using a self-rotation-revolving mixer. Those that can be mixed are shown as "○" in Table 3, and those that cannot be mixed are shown in Table 3. The case of is shown as "×" in Table 3.

[hardness] The polyol-containing composition and the isocyanate-containing composition were mixed and cured at room temperature, and the hardness (Shore C) after 7 days at room temperature was measured according to JIS K7312:1996 (spring hardness test type C).

[Table 1] Compositions containing polyols A1 A2 A3 A4 A5 A6 A7 Blending (mass%) Aluminum hydroxide 82.1 60.1 40.8 82.1 87.3 81.9 Aluminum oxide 1 52.9 Aluminum oxide 2 35.3 44.4 polybutadiene polyol 10.0 22.0 5.6 7.1 10.0 3.5 5.0 DUP 7.8 17.8 6.1 7.6 9.1 13.0 DOA 7.8 Phosphate 1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 total 100 100 100 100 100 100 100 OHV (mgKOH/g) 4.7 10.3 2.6 3.3 4.7 2.3 2.3 Inorganic filler dosage (volume%) 64 37 64 64 64 73 64 Inorganic filler dosage (mass%) 82 60 88 85 82 87 82

[Table 2] Isocyanate-containing composition B1 B2 B3 B4 B5 B6 B7 B8 B9 B10 B11 B12 B13 B14 B15 B16 B17 B18 B19 B20 B21 Blending (mass%) Aluminum hydroxide 82.3 82.2 82.2 82.2 82.2 82.2 82.2 82.2 82.2 82.2 82.2 82.2 59.3 40.9 82.3 82.3 82.3 82.3 81.7 Aluminum oxide 1 52.7 Aluminum oxide 2 35.1 44.5 Prepolymer 1 2.9 Prepolymer 2 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 7.0 1.7 1.8 2.5 2.5 20.0 17.2 Prepolymer 3 2.1 Prepolymer 4 2.5 Prepolymer 5 2.3 Prepolymer 6 2.2 Prepolymer 7 2.8 Isocyanurate 0.5 1.0 0.5 0.9 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.3 0.4 0.5 0.2 0.5 0.5 DUP 14.2 14.2 14.2 14.2 14.2 14.0 14.2 14.2 14.2 14.2 14.2 14.2 32.6 9.5 11.9 14.2 14.8 14.2 80.0 DOA 14.2 Phosphate 1 0.1 0.1 0.1 0.1 0.1 0.3 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Phosphate 2 0.1 Phosphate 3 0.1 ammonium sulfate 0.1 Carboxylic acid 1 0.1 Carboxylic acid 2 0.1 Carboxylic acid 3 0.1 Hygroscopic agent 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 NCOV (mgKOH/g) 3.2 3.6 3.6 3.5 3.6 3.6 3.6 3.6 3.6 3.6 3.6 3.6 7.2 2.3 2.6 3.6 3.5 3.5 3.6 23.8 15.4 Inorganic filler dosage (volume%) 65 65 65 65 65 65 65 65 65 65 65 65 37 64 65 65 65 65 65 0 65 Inorganic filler dosage (mass%) 82 82 82 82 82 82 82 82 82 82 82 82 59 88 85 82 82 82 82 0 82

[table 3] Composition of two-component reactive polyurethane resin composition Evaluation Compositions containing polyols Isocyanate-containing composition Capacity deployment ratio NCO/OH index Inorganic filler dosage (mass%) Plasticizer dosage (mass%) storage stability Mixed hardness Example 1 A1 B1 A1/B1=100/100 0.7 82 11 liquid ○ 60 Example 2 A1 B2 A1/B2=100/100 0.8 82 11 liquid ○ 58 Example 3 A1 B3 A1/B3=100/100 0.8 82 11 liquid ○ 59 Example 4 A1 B4 A1/B4=100/100 0.8 82 11 liquid ○ 58 Example 5 A1 B5 A1/B5=100/100 0.8 82 11 liquid ○ 54 Example 6 A1 B6 A1/B6=100/100 0.8 82 11 liquid ○ 54 Example 7 A1 B7 A1/B7=100/100 0.8 82 11 liquid ○ 59 Example 8 A1 B8 A1/B8=100/100 0.8 82 11 liquid ○ 57 Example 9 A1 B9 A1/B9=100/100 0.8 82 11 liquid ○ 59 Example 10 A1 B10 A1/B10=100/100 0.8 82 11 liquid ○ 57 Example 11 A1 B11 A1/B11=100/100 0.8 82 11 liquid ○ 58 Example 12 A1 B12 A1/B12=100/100 0.8 82 11 liquid ○ 58 Example 13 A2 B13 A2/B13=100/100 0.7 60 25 liquid ○ 40 Example 14 A3 B14 A3/B11=100/100 0.9 88 8 liquid ○ 54 Example 15 A4 B15 A4/B12=100/100 0.8 85 10 liquid ○ 60 Example 16 A5 B16 A5/B13=100/100 0.8 82 11 liquid ○ 56 Comparative example 1 A1 B17 A1/B17=100/100 0.8 82 11 liquid ○ 72 Comparative example 2 A1 B18 A1/B18=100/100 0.8 82 11 to solidify ○ 60 Comparative example 3 A1 B19 A1/B19=100/100 0.8 82 11 to solidify ○ 58 Comparative example 4 A6 B20 A6/B20=100/15 0.7 82 13 liquid x 58 Comparative Example 5 A7 B21 A7/B21=100/10 0.7 82 11 to solidify x 58

The results are shown in Table 3. In Comparative Example 1, since the average number of functional groups of the polyol constituting the isocyanate group-containing urethane prepolymer was large, the hardness of the cured product was high. In Comparative Example 2, the weight average molecular weight of the polyol constituting the isocyanate group-containing urethane prepolymer was small, so the isocyanate-containing composition solidified during storage at 60° C. for 1 month, and the storage stability was low. In Comparative Example 3, since the compound (d) such as phosphoric acid ester or ammonium sulfate salt was not formulated in the isocyanate-containing composition, the storage stability decreased. In Comparative Example 4, since no inorganic filler was blended in the isocyanate-containing composition, the miscibility of the isocyanate-containing composition and the polyol-containing composition was poor. In Comparative Example 5, no plasticizer was blended in the isocyanate-containing composition, so the storage stability was poor, and the miscibility with the polyol-containing composition was also poor.

On the other hand, in Examples 1 to 16, the storage stability of the isocyanate-containing composition is excellent, and the miscibility with the polyol-containing composition is also good, and the hardness after curing is also 60 or less. Good results can be obtained.

Some embodiments of the present invention have been described above, but these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in other various forms, and various omissions, substitutions, and changes can be made without departing from the scope of the invention. These embodiments, omissions, substitutions, changes, and the like are included in the scope or spirit of the invention, and are also included in the inventions described in the claims and their equivalent scopes.

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Claims (6)

An isocyanate-containing composition that can be used as a polyisocyanate component of a two-liquid reactive polyurethane resin composition. An isocyanate group-containing urethane prepolymer obtained by reacting a polyol with a concentration of more than 700 and a polyisocyanate, an inorganic filler, a plasticizer, and a compound represented by the following general formula (1) and the following general formula (3) At least one of the group consisting of compounds represented by the general formula (1), R ¹ represents OH or the group shown in the following general formula (2), and R ¹ can also be represented by OH The compound represented by R ¹ is a mixture of the compound represented by the general formula (2). In the general formula (3), k represents the number of 1 or 0, and X represents -CH ₂ -, -CO(CH ₂ ) _p - Or the linking group of -COCH=CH-, where p represents an integer of 2 to 6, Z represents carboxyl, sulfo or their salts, in general formula (1), general formula (2) and general formula (3) , R ² and R ³ each independently represent a hydrocarbon group with 6 to 30 carbons, A ¹ O and A ³ O each independently represent an oxyalkylene group with 2 to 4 carbons, m and n are the average addition of alkylene oxide Mole number and each independently represent a number from 1 to 100, (A ¹ O) _m and (A ³ O) _n each independently represent an oxyethylene content of 20 mole % or more;

. The isocyanate-containing composition according to claim 1, wherein the polyisocyanate is aliphatic diisocyanate and/or alicyclic diisocyanate. The isocyanate-containing composition according to claim 1 or claim 2, wherein the inorganic filler is contained in 50% by mass to 95% by mass in 100% by mass of the isocyanate-containing composition. The isocyanate-containing composition according to any one of claim 1 to claim 3, wherein the plasticizer is phthalate diester and/or adipate diester. A two-liquid reactive polyurethane resin composition, comprising: The isocyanate-containing composition as described in any one of claim 1 to claim 4; and A polyol-containing composition comprising a polyol and an inorganic filler. The two-liquid reactive polyurethane resin composition as described in claim 5 can be used as a heat dissipation material.