JP7053936B1 - Isocyanate-containing composition and two-component reaction type polyurethane resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an isocyanate-containing composition which improves the mixing property with a polyol-containing composition while suppressing a decrease in storage stability of the isocyanate-containing composition in a polyurethane resin composition containing an inorganic filler. SOLUTION: This is used as a polyisocyanate component of a two-component reaction type polyurethane resin composition, and is obtained by reacting a polyol having an average number of functional groups of 2.5 or less and a weight average molecular weight of 700 or more with a polyisocyanate. An isocyanate-containing composition comprising an isocyanate group-containing urethane prepolymer, an inorganic filler, a plasticizer, and a specific polyoxyethylene compound. [Selection diagram] None

Description

The present invention relates to a two-component reaction type polyurethane resin composition and an isocyanate-containing composition used as a polyisocyanate component thereof.

It is known that heat dissipation is imparted by blending an inorganic filler with 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 a reaction between a polyisocyanate and a polybutadiene polyol. The heat dissipation can be improved by containing it in a high compounding ratio.

Japanese Unexamined Patent Publication No. 2010-150473

When an inorganic filler is blended in a polyurethane resin composition, generally, an inorganic filler is blended with a polyol component, a polyisocyanate component containing no inorganic filler is added thereto, and the mixture is mixed, and both components are reacted. There is. However, the polyol component containing an inorganic filler has a problem that it is difficult to mix with the polyisocyanate component containing no inorganic filler. When an inorganic filler is added to the polyisocyanate component in order to improve the mixing property of the two, the storage stability of the polyisocyanate component is lowered.

In view of the above points, the embodiment of the present invention is a polyol used as a polyol component in a polyurethane resin composition containing an inorganic filler while suppressing a decrease in storage stability of the isocyanate-containing composition used as a polyisocyanate component. It is an object of the present invention to provide an isocyanate-containing composition capable of improving the mixability with the contained composition.

The present invention includes embodiments shown below.
[1] An isocyanate-containing composition used as a polyisocyanate component of a two-component reaction type polyurethane resin composition, in which a polyol having an average number of functional groups of 2.5 or less and a weight average molecular weight of 700 or more is reacted with polyisocyanate. At least selected from the group consisting of the isocyanate group-containing urethane prepolymer, the inorganic filler, the plasticizer, and the compound represented by the following general formula (1) and the compound represented by the following general formula (3). In the general formula (1), R ¹ represents OH or a group represented by the following general formula (2), and R ^{1 is represented by a compound represented by OH and R 1 is} represented by the general formula (2). It may be a mixture with a compound, and in the general formula (3), k represents a number of 1 or 0, and X is a linking group having −CH _2- , −CO (CH ₂ ) _p − or −COCH = CH −. Representing here, p represents an integer of 2 to 6, Z represents a carboxy group, a sulfo group or a salt thereof, and in the general formula (1), the general formula (2) and the general formula (3), R ² and R ³ independently represents a hydrocarbon group having 6 to 30 carbon atoms, A ¹ O and A ³ O independently represent an oxyalkylene group having 2 to 4 carbon atoms, and m and n represent the average addition of an alkylene oxide. The number of moles represents 1 to 100 independently, and (A ¹ O) _m and (A ³ O) _n each independently have an oxyethylene group content of 20 mol% or more, and an isocyanate-containing composition. thing.

[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], wherein the inorganic filler is contained in an amount of 50 to 95% by mass 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 phthalic acid diester and / or an adipic acid diester.
[5] A two-component reaction type polyurethane resin composition comprising the isocyanate-containing composition according to any one of [1] to [4] and a polyol-containing composition containing a polyol and an inorganic filler.
[6] The two-component reaction type polyurethane resin composition according to [5] used as a heat radiating material.

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

The two-component reaction type polyurethane resin composition according to 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 the urethane prepolymer (a). As the urethane prepolymer (a), in the present embodiment, an isocyanate group-containing urethane prepolymer containing a polyol having an average number of functional groups of 2.5 or less and a weight average molecular weight of 700 or more and polyisocyanate as constituents is used. ..

When the average number of functional groups (average number of hydroxyl groups) of the polyol is 2.5 or less, the hardness of the cured polyurethane resin can be suppressed to a low level. When used as a gap filler to fill in, the reaction force generated with respect to an external force can be reduced. The average number of functional groups of the polyol is preferably 2.4 or less, more preferably 2.3 or less. The lower limit of the average number of functional groups of the polyol is not particularly limited, and for example, the average number of functional groups may be 1.7 or more. The polyol preferably has hydroxyl groups at both ends, and therefore 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 the polyol is not particularly limited, and for example, the weight average molecular weight may be 10,000 or less, or may be 5000 or less. In the present specification, the weight average molecular weight is a value calculated by measuring by the GPC method (gel permeation chromatography method) using a calibration curve using standard polystyrene.

The polyol is not particularly limited, and examples thereof include a polyether polyol, a polyester polyol, a polycarbonate polyol, a polybutadiene polyol, a polyisoprene polyol, and the like, and any one of them or a combination of two or more thereof can be used. Examples of the polyether polyol include a polyoxyalkylene polyol obtained by adding ethylene oxide or propylene oxide to a polyhydric alcohol or polyamine. Examples of the polyester polyol include those obtained by dehydration condensation of a carboxylic acid such as adipic acid or phthalic acid and a polyhydric alcohol such as ethylene glycol or 1,4-butanediol. The polybutadiene polyol preferably has hydroxyl groups at both ends of the polybutadiene structure, and may be hydrogenated. Among these, polypropylene glycol and / or polybutadiene polyol is preferably used.

The polyisocyanate is not particularly limited, and examples thereof include an aliphatic diisocyanate, an alicyclic diisocyanate, and an aromatic diisocyanate. However, an aliphatic diisocyanate and an alicyclic diisocyanate are preferably used. It may be used together.

Examples of the aliphatic diisocyanate include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate, 2 -Methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate and the like can be mentioned. Moreover, you may use these in combination of 2 or more types.

Examples of the alicyclic diisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexanediisocyanate, methylcyclohexylene diisocyanate, and 1,3-bis (isocyanitemethyl) cyclohexane. Can be mentioned. Moreover, you may use these in combination of 2 or more types.

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

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

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

The inorganic filler (b) is not particularly limited, and for example, metal oxides such as alumina and magnesium oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and metal nitrides such as aluminum nitride and boron nitride. And so on. These can be used alone or in combination of two or more.

The blending amount of the inorganic filler (b) is preferably 50 to 95% by mass in 100% by mass of the isocyanate-containing composition. When the blending amount is 50% by mass or more, the heat dissipation of the polyurethane resin can be improved. When the blending amount is 95% by mass or less, the storage stability of the isocyanate-containing composition can be improved. The blending amount is more preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and further preferably 90% by mass or less.

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

The plasticizer (c) is not particularly limited, and conventionally known ones blended in a polyurethane resin can be used. For example, phthalates such as dioctylphthalate, diisononylphthalate, and diundecylphthalate, dioctyl adipate, and the like. Adiponic acid diesters such as diisononyl adipate, trimellitic acid esters such as trioctyl limerite, triisononyl trimellitate, pyromellitic acid esters such as tetraoctylpyromerite and tetraisononylpyromerite, tricresyl phosphate. , Trixylenyl phosphate, phosphoric acid triesters such as cresyldiphenyl phosphate and the like, and these can be used alone or in combination of two or more. Among these, the plasticizer (c) is preferably a phthalic acid diester and / or an adipic acid diester.

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

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

In formula (1), R ¹ represents OH or a group represented by the following general formula (2). The phosphoric acid ester represented by the formula (1) may be a compound (monoester) in which R ¹ is represented by OH, a compound (diester) in which R ¹ is represented by the general formula (2), or a mixture of both. good.

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

Specific examples of the alkyl group include a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, a 2-ethylhexyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecylic group, an isoundecyl group and a dodecyl group. Group, isododecyl group, tridecylic group, isotridecylic group, tetradecyl group, isotetradecyl group, pentadecyl group, isopentadecyl group, hexadecyl group, isohexadecyl group, 2-hexyldecyl group, heptadecyl group, isoheptadecyl group, octadecyl group, Isooctadecyl group, 2-octyldecyl group, 2-hexyldodecyl group, nonadecyl group, isononadecyl group, eicosyl group, isoeicosyl group, heneikosyl group, isoheneicosyl group, docosyl group, isodocosyl group, tridecylic group, isotricosyl group, tetracosyl Examples thereof include a group, an isotetracosyl group, a pentacosyl group, an isopentacosyl group, a hexacosyl group, an isohexacosyl group, a heptacosyl group, and an isoheptacosyl group.

Specific examples of the alkenyl group include a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tetradecenyl group, an oleyl group and the like.

Specific examples of the aryl group include a phenyl group, a trill group, a xylyl group, a cumenyl group, a mesityl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group and an octylphenyl group. , Nonylphenyl group, decylphenyl group, undecylphenyl group, dodecylphenyl group, styrenated phenyl group, p-cumylphenyl group, phenylphenyl group, benzylphenyl group, α-naphthyl group, β-naphthyl group and the like.

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

In the formula (1) and the formula (2), A ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms. m represents the average number of moles of alkylene oxide added, which is 1 to 100, preferably 3 to 50, more preferably 5 to 30, and even more preferably 7 to 20. Is. The oxyalkylene chain represented by (A ¹ O) _m has an oxyethylene group content of 20 mol% or more. That is, when the oxyethylene group is EO and the oxyalkylene 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 50 mol% or more, more preferably 70 mol% or more, further preferably 80 mol% or more, and even 100 mol%. When the oxyalkylene chain consists of a plurality of types of oxyalkylene groups, the oxyalkylene group may be randomly added or may be block-added.

The phosphoric acid ester represented by the formula (1) is obtained by adding an alkylene oxide to a monoalcohol or a phenol having 6 to 30 carbon atoms by a known method, and then using the alkylene oxide terminal of the obtained polyether monool. It can be produced by reacting a hydroxyl group with a phosphoric acid such as anhydrous phosphoric acid, orthophosphoric acid, polyphosphoric acid, and oxychloride phosphoric acid. Depending on the production method, a monoester-type compound and a diester-type compound can be obtained as a mixture, but these may be separated or used as they are as a mixture. It can also be used by reacting in the presence of water to increase the content ratio of the monoester type compound.

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

In equation (3), k represents a number of 1 or 0. X represents a linking group of -CH _2- , -CO (CH ₂ ) _p- or -COCH = CH-, where p represents an integer of 2-6.

Z in the formula (3) represents a carboxy group (-COOH), a sulfo group (-SO _3H ), or a salt thereof, and an acid type and a salt type may be mixed. Examples of the salt include an alkali metal salt, an alkaline earth metal salt, an ammonium salt, and an alkanolamine salt. Examples of alkali metal salts include sodium salts, potassium salts, lithium salts and the like. Examples of alkaline earth metal salts include calcium salts and magnesium salts. Examples of alkanolamine salts include monoethanolamine salts, diethanolamine salts, triethanolamine salts, triisopropanolamine salts and the like.

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

In formula ( ³ ), A3O represents an oxyalkylene group having 2 to 4 carbon atoms. n represents the average number of moles of alkylene oxide added, which is 1 to 100, preferably 3 to 50, more preferably 5 to 30, and even more preferably 7 to 20. Is. The oxyalkylene chain represented by (A ³ O) _m has an oxyethylene group content of 20 mol% or more. That is, when the oxyethylene group is EO and the oxyalkylene 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 50 mol% or more, more preferably 70 mol% or more, further preferably 80 mol% or more, and even 100 mol%. When the oxyalkylene chain consists of a plurality of types of oxyalkylene groups, the oxyalkylene group may be randomly added or may be block-added.

When the above Z is a carboxy group, the compound represented by the formula (3) is a carboxylic acid. In that case, the carboxylic acid of the formula (3) is prepared 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 a salt thereof in the presence of a base. It can be produced by reacting with the hydroxyl group at the terminal of the alkylene oxide. Alternatively, it can be produced by a method of ring-opening reaction with a hydroxyl group at the terminal of an alkylene oxide using an acid anhydride. When monohalogenated acetic acid or a salt thereof is used, in the formula (3), a carboxylic acid in which k = 1, X is _−CH2- , and Z is COOH or a salt thereof is obtained. 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 when k = 0 and a sulfonic acid when k = 1. For example, a sulfuric acid ester can be produced by adding an alkylene oxide to a monoalcohol or phenol having 6 to 30 carbon atoms by a known method, and then reacting sulfamic acid with a hydroxyl group at the terminal of the alkylene oxide. Further, for example, sulfonic acid can be produced by adding the above-mentioned alkylene oxide and then reacting with the hydroxyl group at the terminal of the alkylene oxide using monohalogenated sulfonic acid or a salt thereof.

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

[Other ingredients]
In the isocyanate-containing composition, the polyisocyanate compound may be the urethane prepolymer (a) alone, or may be used in combination with another polyisocyanate compound 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 polyisocyanates, alicyclic polyisocyanates, and alicyclic polyisocyanates. Examples thereof include aromatic polyisocyanates, and modified and polynuclear compounds thereof, and any one of them may be used or two or more thereof may be used in combination. Specific examples of the aliphatic polyisocyanate and the alicyclic polyisocyanate include the above-mentioned aliphatic diisocyanate and the alicyclic diisocyanate. Examples of the aromatic polyisocyanate include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate (XDI), 1,3-. Examples thereof include phenylenedi isocyanate and 1,4-phenylenedi isocyanate. Examples of the modified product of these polyisocyanate compounds include an isocyanurate modified product, an allophanate modified product, a bullet modified product, an adduct modified product, and a carbodiimide modified product.

Among these, as the other polyisocyanate compound, it is preferable to use the isocyanurate-modified product of the above-mentioned polyisocyanate compound, and more preferably, the isocyanurate-modified product of the aliphatic polyisocyanate. In that case, the blending amount of the isocyanurate modified product is not particularly limited, but is preferably 0.05 to 5% by mass, more preferably 0.1 to 2% by mass in 100% by mass of the isocyanate-containing composition. It is mass%. The polyisocyanate compound preferably contains the urethane prepolymer (a) as a main component, and even when other polyisocyanate compounds are used in combination, the polyisocyanate compound is more than 50% by mass, more preferably 60% by mass. The above is preferably the urethane prepolymer (a).

In addition to the above components, the isocyanate-containing composition contains various additives such as a hygroscopic agent, an antioxidant, a defoaming agent, a diluent, a flame retardant, an ultraviolet absorber, and a colorant, for the purpose of the present embodiment. It can be added as long as it does not impair.

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

<Polycarbonate-containing composition>
[Polyformer (e)]
The polyol-containing composition comprises the polyol (e). The polyol (e) is not particularly limited, and examples thereof include a polyether polyol, a polyester polyol, a polycarbonate polyol, a polybutadiene polyol, a polyisoprene polyol, and the like, which may be used alone or in combination of two or more. .. Among these, it is preferable to use a polybutadiene polyol. The polybutadiene polyol preferably has hydroxyl groups at both ends of the polybutadiene structure, and may be hydrogenated. The average number of functional groups of the polybutadiene polyol is preferably 2.0 to 2.5, more preferably 2.1 to 2.4.

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

[Inorganic filler (f)]
The polyol-containing composition contains an inorganic filler (f). By blending the inorganic filler (f), heat dissipation can be imparted to the cured polyurethane resin. The inorganic filler (f) is not particularly limited, and for example, metal oxides such as alumina and magnesium oxide, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and metal nitrides such as aluminum nitride and boron nitride. And so on. These can be used alone or in combination of two or more.

The blending amount of the inorganic filler (f) is preferably 50 to 95% by mass, more preferably 60% by mass or more, and more preferably 70% by mass or more in 100% by mass of the polyol-containing composition. More preferably, it is 80% by mass or more, and more preferably 90% by mass or less.
[Plasticizer (g)]
The polyol-containing composition may contain a plasticizer (g). By containing the plasticizer (g), the hardness of the polyurethane resin after curing can be lowered. The plasticizer (g) is not particularly limited, and examples thereof include the above-mentioned phthalic acid diester, adipic acid diester, trimellitic acid ester, pyromellitic acid ester, and phosphoric acid triester, and any one or two of these can be mentioned. The above can be used in combination. Among these, as the plasticizer (g), a phthalic acid diester and / or an adipic acid diester is preferable.

The blending amount of the plasticizer (g) is not particularly limited, and may be, for example, 1 to 30% by mass, 3 to 25% by mass, or 5 to 20% by mass in 100% by mass of the polyol-containing composition. It may be 5 to 15% by mass.
[Phosphate ester (h)]
The polyol-containing composition may contain a phosphoric acid ester (h). By containing 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 above formula (1) is used.

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

[Other ingredients]
In addition to the above components, the polyol-containing composition contains various additives such as a hygroscopic agent, a catalyst, an antioxidant, a defoaming agent, a diluent, a flame retardant, an ultraviolet absorber, and a colorant in the present embodiment. It can be added as long as it does not impair the purpose.

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

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

<Two-component reaction type polyurethane resin composition>
The two-component reaction type polyurethane resin composition according to the present embodiment is usually composed of a first solution which is a polyol-containing composition and a second solution which is an isocyanate-containing composition, but the polyol-containing composition and isocyanate are contained. In addition to the contained composition, a liquid containing the above-mentioned other components as optional components may be provided as the third liquid.

The two-component reaction type polyurethane resin composition can be produced by preparing a polyol-containing composition and an isocyanate-containing composition, respectively, that is, the polyol-containing composition and the isocyanate-containing composition are filled in separate containers. It may be a polyol. The polyol-containing composition and the isocyanate-containing composition packed in separate containers may be mixed at the time of use to react the polyol and the polyisocyanate to form a polyurethane resin, which may be cured. At that time, it may be cured by heating. The two-component reaction type polyurethane resin composition according to the embodiment may be obtained by mixing a polyol-containing composition and an isocyanate-containing composition, may be a liquid before curing, or may be cured. ..

In the two-component reaction type polyurethane resin composition, the mixing ratio of the polyol-containing composition and the isocyanate-containing composition is not particularly limited, and for example, the isocyanate group contained in the isocyanate-containing composition with respect to the hydroxyl group contained in the polyol-containing composition. The molar ratio NCO / OH (index) of may be 0.5 to 1.2 or 0.6 to 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 reaction type polyurethane resin composition, the volume mixing ratio of the polyol-containing composition and the isocyanate-containing composition is not particularly limited, but the polyol-containing composition / isocyanate-containing composition = 30/70 to 70/30. It is preferably 40/60 to 60/40, and even more preferably 45/55 to 55/45.

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

The thermal conductivity (JIS R2618) of the two-component reaction type polyurethane resin composition after curing is not particularly limited, and may be, for example, 1.0 W / m · K or more, 2.0 W / m · K or more, and 2 It may be 0.0 to 3.0 W / m · K.

<Use of two-component reaction type polyurethane resin composition>
The application of the two-component reaction type polyurethane resin composition according to the present embodiment is not particularly limited, and can be used for various applications such as electric and electronic parts and automobiles. It is suitably used as a heat-dissipating material because it has heat-dissipating properties by blending an inorganic filler. As one embodiment, it is suitably used as a heat-dissipating gap filler for a heat source such as a battery.

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

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

[Polyol]
-Polybutadiene polyol: "POLYVEST HT" manufactured by Evonik, with an average number of functional groups of 2.3
[Plasticizer]
-DUP: Diundecyl phthalate-DOA: Di2-ethylhexyl adipate

[Polyisocyanate compound]
-Isocyanurate: Isocyanurate-modified HDI, "HT600" manufactured by Mange Kagaku
[Heat absorbent]
・ Moisture absorbent: "Molecular Sheave 3AB" manufactured by Union Showa Co., Ltd.

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

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

[Prepolymer 2]
In a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer and a nitrogen blowing tube, 26 parts by mass of hexamethylene diisocyanate (HDI) (“Duranate 50M” manufactured by Asahi Kasei Co., Ltd.) and polypropylene glycol (average number of functional groups). 2.0, weight average molecular weight 1000, hydroxyl value 112) (“Exenol 1020” manufactured by AGC Co., Ltd.) by reacting with 74 parts by mass at 90 ° C. for 2 hours to obtain an isocyanate group-terminated urethane prepolymer (prepolymer 2). Obtained.

[Prepolymer 3]
Hexamethylene diisocyanate (HDI) (“Duranate 50M” manufactured by Asahi Kasei Co., Ltd.) by 10 parts by mass and polypropylene glycol (average number of functional groups) in a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer and a nitrogen blowing tube. 2.0, weight average molecular weight 3000, hydroxyl value 35) (“Exenol 3020” manufactured by AGC Co., Ltd.) 90 parts by mass is reacted at 120 ° C. for 6 hours to obtain an isocyanate group-terminated urethane prepolymer (prepolymer 3). Obtained.

[Prepolymer 4]
In a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer and a nitrogen blowing tube, 31 parts by mass of isophorone diisocyanate (IPDI) (“IPDI” manufactured by EVONIC) and polypropylene glycol (average number of functional groups 2.0). , Weight average molecular weight 1000, hydroxyl value 112) (“Excelol 1020” manufactured by AGC Co., Ltd.) was reacted at 90 ° C. for 2 hours to obtain an isocyanate group-terminated urethane prepolymer (prepolymer 4).

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

[Prepolymer 6]
Hexamethylene diisocyanate (HDI) (“Duranate 50M” manufactured by Asahi Kasei Co., Ltd.) by 12 parts by mass and a polybutadiene polyol (average number of functional groups) in a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer and a nitrogen blowing tube. 2.3, weight average molecular weight 3000, hydroxyl value 46) ("POLYVEST HT" manufactured by EVONIC) 88 parts by mass was reacted at 90 ° C. for 2 hours to obtain an isocyanate group-terminated urethane prepolymer (prepolymer 6). rice field.

[Prepolymer 7]
In a four-necked flask equipped with 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 oil (average number of functional groups 2). .7, Weight average molecular weight 941, hydroxyl value 161) ("URIC H30" manufactured by Itoh Oil Chemicals, Inc.) 68 parts by mass was reacted at 90 ° C. for 2 hours to obtain an isocyanate group-terminated urethane prepolymer (prepolymer 7). Obtained.

Examples of synthesis of phosphoric acid esters 1 to 3, ammonium sulfate salts, and carboxylic acids 1 to 3, which are the compounds (d) used in Examples and Comparative Examples, are shown below.

[Phosphate ester 1]
200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen introduction pipe, an introduction pipe for charging raw materials, and an exhaust pipe for depressurization. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was sequentially introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130 ° C. for reaction, and then neutralized with acetic acid. Next, 47 g (0.33 mol) of anhydrous phosphoric acid was reacted with the obtained 10 mol adduct of ethylene oxide at 80 ° C. for 5 hours to carry out the phosphoric acid ester 1 of the general formula (1) (in the formula, ^R2 : tridecyl, A ¹ O: EO, m: 10, a mixture of monoester and diester in a molar ratio of 1: 1) was obtained.

[Phosphate ester 2]
186 g (1.0 mol) of lauryl and 5 g of potassium hydroxide as a catalyst were charged into an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen introduction pipe, a raw material charging introduction pipe, and a depressurizing exhaust pipe. The atmosphere in the autoclave was replaced with nitrogen, and 815 g (18.5 mol) of ethylene oxide was sequentially introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130 ° C. for reaction, and then neutralized with acetic acid. Next, 47 g (0.33 mol) of anhydrous phosphoric acid was reacted with the obtained 18.5 mol adduct of ethylene oxide at 80 ° C. for 5 hours to cause the phosphoric acid ester 2 of the general formula (1) (in the formula, ^R2 :. ^A mixture of lauryl, A1 O: EO, m: 18.5, and a molar ratio of monoester and diester of 1: 1) was obtained.

[Phosphate ester 3]
200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen introduction pipe, an introduction pipe for charging raw materials, and an exhaust pipe for depressurization. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 264 g (6 mol) of ethylene oxide and 290 g (5 mol) of propylene oxide were reacted simultaneously under the conditions of a pressure of 0.15 MPa and a temperature of 130 ° C., and then neutralized with acetic acid. bottom. Then, 47 g (0.33 mol) of anhydrous phosphoric acid was reacted with the obtained ethylene oxide and propylene oxide adduct at 80 ° C. for 5 hours to carry out the phosphoric acid ester 3 of the general formula (1) (in the formula, ^R2 : tridecyl). , (A ¹ O) _m : EO / PO (oxypropylene group) = 6/5 (molar ratio) random adduct, m: 11, a mixture of monoester and diester in molar ratio 1: 1) was obtained.

[Ammonium sulfate salt]
220 g (1.0) of styrene phenol (mixture of monostyrene phenol: distyrene phenol: tristyrene phenol = 80: 19: 1 (mass ratio)) in a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube. Mol) is transferred to an autoclave, and 792 g (18 mol) of ethylene oxide is subjected to an addition reaction under the conditions of a pressure of 0.15 MPa and a temperature of 130 ° C. using potassium hydroxide as a catalyst to cause a polyoxyethylene styrenated phenyl ether. Got Subsequently, the obtained polyoxyethylene styrenated phenyl ether was transferred to a reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube, and 97 g (1 mol) of sulfamic acid was transferred under a nitrogen atmosphere at a temperature of 120 ° C. Was reacted. Then, monoethanolamine was added to adjust the pH in a 1% by mass aqueous solution to 7.5, and the ammonium sulfate salt of the general formula ( ³ ) (in the formula, R ³ : styrenated phenyl, A3 O: EO). , N: 18, k: 0, Z: −SO ₃ NH ₄ ) was obtained.

[Carboxylic acid 1]
200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen introduction pipe, an introduction pipe for charging raw materials, and an exhaust pipe for depressurization. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was sequentially introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130 ° C. for reaction, and then neutralized with acetic acid. Then, 151 g (1.3 mol) of the above ethylene oxide adduct and sodium monochloroacetate were placed in a toluene solvent and stirred so as to be uniform. Then, under the condition that the temperature of the reaction system was 60 ° C., 52 g (1.3 mol) of sodium hydroxide was added, and then the temperature of the reaction system was raised to 80 ° C. and the reaction was carried out for 3 hours. After the reaction, 120 g (1.2 mol) of 98 mass% sulfuric acid was added dropwise to obtain a white suspension solution. Next, this white suspension solution was washed with distilled water and the solvent was distilled off under reduced pressure to obtain the carboxylic acid 1 of the general formula ( ³ ) (in the formula, R ³ : tridecyl, A3 O: EO, n: 10, k: 1, X: -CH _2- , Z: -COOH).

[Carboxylic acid 2]
200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen introduction pipe, an introduction pipe for charging raw materials, and an exhaust pipe for depressurization. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was sequentially introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130 ° C. for reaction, and then neutralized with acetic acid. Then, by reacting 156 g (1 mol) of suberic acid anhydride at 120 ° C. for 2 hours, the carboxylic acid 2 of the general formula ( ³ ) (in the formula, R ³ : tridecylic acid, A3 O: EO, n: 10, k) 1, X: -CO- (CH ₂ ) _6- , Z: -COOH).

[Carboxylic acid 3]
200 g (1.0 mol) of tridecyl alcohol and 5 g of potassium hydroxide as a catalyst in an autoclave equipped with a temperature controller equipped with a stirrer, a thermometer, a nitrogen introduction pipe, an introduction pipe for charging raw materials, and an exhaust pipe for depressurization. After charging, the atmosphere in the autoclave was replaced with nitrogen, and 440 g (10 mol) of ethylene oxide was sequentially introduced under the conditions of a pressure of 0.15 MPa and a temperature of 130 ° C. for reaction, and then neutralized with acetic acid. Then, 198 g (1 mol) of maleic anhydride was reacted at 120 ° C. for 2 hours to obtain the carboxylic acid 3 of the general formula ( ³ ) (in the formula, R ³ : tridecylic acid, A3 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 cardinal number]
For the average number of functional groups, the number average molecular weight (Mn) is measured by GPC (gel permeation chromatography), and the hydroxyl value (mgKOH / g) is measured according to the method A of JIS K1557-1: 2007 from the following formula. It is a calculated value.
Average number of functional groups = {(hydroxyl value) x (Mn)} / (56.11 x 1000)

[Weight average molecular weight and number average molecular weight]
It is a value calculated from the elution time of the measurement sample by measuring by the GPC method (gel permeation chromatography method) and using a calibration curve prepared from the molecular weight and elution time of standard polystyrene. Regarding the measurement conditions, using TSKgel Hxl (Tosoh Corporation) for the column, the mobile phase is THF (tetrahydrofuran), the mobile phase flow rate is 1.0 mL / min, the column temperature is 40 ° C., the sample injection amount is 50 μL, and the sample concentration is The measurement was performed under the condition of 0.2% by mass.

[Hydroxy group value]
Measured according to JIS K1557-1: 2007 method A.

５６．１１：水酸化カリウムの分子量
１０００：ｇからｍｇへの変換係数
４２．０２：ＮＣＯの分子量
１００：百分率から／ｇへの変換係数 [Isocyanate value]
The isocyanate content is measured according to the method A of JIS K1603-1: 2007, and the isocyanate value is calculated from the obtained isocyanate content by the following formula.

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

[Examples 1 to 16 and Comparative Examples 1 to 5]
Polyol-containing compositions A1 to 7 were prepared according to the formulations (% by mass) shown in Table 1 below, and isocyanate-containing compositions B1 to 21 were prepared according to the formulations (% by mass) shown in Table 2 below. The isocyanate-containing compositions B1 to 21 were evaluated for storage stability. Further, the polyol-containing compositions A1 to 7 and the isocyanate-containing compositions B1 to 21 were mixed according to the combinations and volume compounding ratios shown in Table 3 below, and the mixing property of both was evaluated. In addition, the hardness of the cured product was measured after mixing and curing. The methods for measuring and evaluating storage stability, mixing properties, and hardness are as follows.

[Storage stability]
The properties of the prepared isocyanate-containing composition after being stored at 60 ° C. for one month were evaluated, and Table 3 shows the case where the composition remained as a liquid as "liquid" and the case where it was solidified from the liquid as "solidification".

[Mixability]
Using a rotation / revolution mixer, the polyol-containing composition and the isocyanate-containing composition are stirred at room temperature at 2000 rpm for 30 minutes, and if they can be mixed by this, they are "○", and if they cannot be mixed, they are "×". Is shown 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 by JIS K7312: 1996 (spring hardness test type C).

The results are shown in Table 3. In Comparative Example 1, the hardness of the cured product was high because the average number of functional groups of the polyol constituting the isocyanate group-containing urethane prepolymer was large. In Comparative Example 2, since the weight average molecular weight of the polyol constituting the isocyanate group-containing urethane prepolymer was small, the isocyanate-containing composition solidified after storage at 60 ° C. for 1 month, and the storage stability was low. In Comparative Example 3, since the compound (d) such as a phosphoric acid ester or ammonium sulfate was not blended in the isocyanate-containing composition, the storage stability was lowered. In Comparative Example 4, since the inorganic filler was not blended in the isocyanate-containing composition, the mixability between the isocyanate-containing composition and the polyol-containing composition was poor. In Comparative Example 5, since the isocyanate-containing composition did not contain a plasticizer, the storage stability was inferior, and the mixability with the polyol-containing composition was also inferior.

On the other hand, in Examples 1 to 16, the isocyanate-containing composition is excellent in storage stability, the mixability with the polyol-containing composition is good, and the hardness after curing is 60 or less, which is good. The result was obtained.

Although some embodiments of the present invention have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other embodiments, and various omissions, replacements, and changes can be made without departing from the gist of the invention. These embodiments, omissions, replacements, changes, etc. thereof are included in the scope and gist of the invention, as well as in the scope of the invention described in the claims and the equivalent scope thereof.

Claims (5)

An isocyanate-containing composition used as a polyisocyanate component of a two-component reaction-type polyurethane resin composition used as a heat-dissipating gap filler that fills a gap around a battery .
An isocyanate group-containing urethane prepolymer obtained by reacting a polyol having an average number of functional groups of 2.5 or less and a weight average molecular weight of 700 or more with polyisocyanate.
Inorganic filler,
Plasticizer and
It comprises at least one selected from the group consisting of the compound represented by the following general formula (1) and the compound represented by the following general formula (3).
In the general formula (1), R ¹ represents OH or a group represented by the following general formula (2), and a mixture of a compound in which R ¹ is represented by OH and a compound in which R ¹ is represented by the general formula (2). But well,
In the general formula (3), k represents a number of 1 or 0, X represents a linking group of -CH _2- , -CO (CH ₂ ) _p- or -COCH = CH-, where p is 2. Represents an integer of ~ 6, where Z represents a carboxy group, a sulfo group or a salt thereof.
In the general formula (1), the general formula (2) and the general formula (3), R ² and R ³ each independently represent a hydrocarbon group having 6 to 30 carbon atoms, and A ¹ O and A ³ O are independent of each other. Represents an oxyalkylene group having 2 to 4 carbon atoms, and m and n are the average number of moles of alkylene oxide added and independently represent numbers of 1 to 100, respectively, (A ¹ O) _m and (A ³ O). Each of _n has an oxyethylene group content of 20 mol% or more independently.
Isocyanate-containing composition.

The isocyanate-containing composition according to claim 1, wherein the polyisocyanate is an aliphatic diisocyanate and / or an alicyclic diisocyanate. The isocyanate-containing composition according to claim 1 or 2, wherein the inorganic filler is contained in an amount of 50 to 95% by mass in 100% by mass of the isocyanate-containing composition. The isocyanate-containing composition according to any one of claims 1 to 3, wherein the plasticizer is a phthalic acid diester and / or an adipic acid diester. A two-component reactive polyurethane resin composition used as a heat-dissipating gap filler that fills the gap around the battery.
The isocyanate-containing composition according to any one of claims 1 to 4 and the isocyanate-containing composition.
A two-component reaction type polyurethane resin composition comprising a polyol-containing composition containing a polyol and an inorganic filler.