WO2004078819A1

WO2004078819A1 - Polyisocyanate composition and aqueous curing composition using same

Info

Publication number: WO2004078819A1
Application number: PCT/JP2004/002831
Authority: WO
Inventors: Kenji Yamasaki; Shigeru Murata
Original assignee: Kyowa Hakko Chemical Co., Ltd.
Priority date: 2003-03-06
Filing date: 2004-03-05
Publication date: 2004-09-16
Also published as: JPWO2004078819A1

Abstract

A polyisocyanate composition and the like containing lysine ester triisocyanate represented by the general formula (I): (wherein R represents a lower alkylene) and an emulsifying agent is disclosed.

Description

Specification

Polyisocyanate composition and aqueous curable composition using the same

Technical field

The present invention relates to a water-dispersible polyisocyanate composition useful for applications such as paints, coatings, inks, adhesives, resist materials, sealing agents, and the like, and an aqueous curing composition containing the polyisocyanate composition. The present invention relates to an acidic composition.

Background art

In recent years, while the use of volatile organic solvents has been required to be reduced due to environmental problems, attempts have been made in many fields to make organic solvent-based compositions containing polyisocyanates aqueous. For example, polyisocyanate and polyoxyalkylene glycol, polyisocyanate

A water-dispersible isocyanate composition comprising a combination of No. 1 and a vinyl polymer containing a nonionic group has been reported (Japanese Patent No. 29614755, Japanese Patent Application Publication No.

(See No. 1 9 4 2 3 7) o

Japanese Patent Application Laid-Open Publication No. 2002-19442437 discloses 2-isocyanatoethyl (2,6-diisocyanato) hexanoate as a polyisocyanate. In the embodiment, only the hexamethylene diisocyanate is shown.

However, polyisocyanate compositions using polyisocyanates derived from hexamethylene diisocyanate do not have sufficient miscibility with polyol components such as aqueous acrylpolyol. There is a problem that a stirrer is required and mixing takes time.

Disclosure of the invention

An object of the present invention is to provide a polyisocyanate composition excellent in water dispersibility, storage stability, mechanical strength of a cured product, water resistance and the like, and an aqueous curable composition containing the polyisocyanate composition. It is in.

The present invention provides the following (1) to (7).

(1) General formula (I)

OCN—— (CH ₂ ) ₄ — CH—— NCO

(I)

OC— OR— NCO

(Wherein, R represents a lower alkylene) and a polyisocyanate composition comprising a lysine ester triisocyanate represented by the formula: (2) The polyisocyanate composition according to (1), wherein the weight ratio of the lysine ester triisocyanate and the emulsifier is 5:95 to 99.5: 0.5.

(3) The polyisocyanate composition according to (1) or (2), wherein the polyisocyanate composition has an isocyanate group concentration of 25 to 47% by weight.

(4) The polyisocyanate composition according to any one of (1) to (3), which has a viscosity at 20 ° C of 25 to 500 cps.

(5) The emulsifier is a compound obtained by reacting an anionic hydrophilic compound or a nonionic hydrophilic compound having an active hydrogen-containing group that reacts with an isocyanate group with a hydrophobic polyisocyanate. (4) The polyisocyanate composition according to any one of (1) to (4).

(6) The polyisocyanate composition according to any one of (1) to (5), wherein R is ethylene.

(7) An aqueous curable composition comprising the polyisocyanate composition according to any one of (1) to (6) and an aqueous resin having an active hydrogen-containing group that reacts with an isocyanate group.

In the definition of the group in the general formula (I), the lower alkylene includes, for example, a linear or branched alkylene having 2 to 8 carbon atoms, and specific examples thereof include ethylene, propylene, and butylene. , Isobutylene, pentylene, hexylene, heptylene, octylene and the like. Among them, ethylene is preferable. Hereinafter, the lysine ester triisocyanate represented by the general formula (I) may be simply referred to as lysine ester triisocyanate.

The lysine ester triisocyanate used in the present invention is not particularly limited, but can be produced by a known method (for example, a method described in Japanese Patent Publication No. 2002-3462). For example, 2-isocyanatoethyl-1,2,6-diisocyanatocaproate in which R in the general formula (I) is ethylene can be obtained as a commercial product.

The emulsifier used in the present invention is not particularly limited as long as it is a substance having a surfactant activity having both a hydrophilic group and a hydrophobic group. Examples thereof include anionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers, nonionic emulsifiers, and other widely used industrial emulsifiers, anionic hydrophilic compounds or nonionic hydrophilic compounds having an active hydrogen-containing group that reacts with an isocyanate group. And the like, which are obtained by the reaction of a polyisocyanate and a hydrophobic polyisocyanate. Among them, an anionic hydrophilic compound having an active hydrogen-containing group which reacts with an isocyanate group or A compound obtained by reacting a nonionic hydrophilic compound with a hydrophobic polyisocyanate is preferable, and a compound obtained by reacting a nonionic hydrophilic compound having an active hydrogen-containing group that reacts with an isocyanate group with a hydrophobic polyisocyanate is preferred. The resulting compounds are more preferred.

Examples of the anionic emulsifier include fatty acids such as stearic acid and oleic acid, alkyl benzene sulfonate, alkyl phosphoric acid and the like or salts thereof, alkyl sulfate, alkyl ether sulfate and the like.

Examples of the cationic emulsifier include quaternary ammonium salts such as alkyldimethyl benzylammonium chloride, benzyltriptylammonium chloride, ethyl trifluorophenyl phosphonium bromide, and ethyl triphenyl phosphonium. And quaternary phosphonium salts such as muaiodide.

Examples of amphoteric emulsifiers include acetic acid acetate, amide acid, sulfoacetic acid, imidazolium acetic acid, and amide oxide.

Examples of nonionic emulsifiers include polyethylene oxide, sorbin ester, ethylene oxide adduct of sorbin ester, ethylene oxide adduct of long-chain alcohol having 5 or more carbon atoms, and ethylene oxide of alkylphenol such as nonylphenol. Oxide adducts, alkyl darcosides and the like can be mentioned.

Examples of the active hydrogen-containing group that reacts with the isocyanate group include a group containing an active methylene group such as a hydroxyl group, a hydroxyl group, an amino group, an amide group, and an acetoacetyl group. Groups are preferred.

Examples of the anionic hydrophilic compound having an active hydrogen-containing group that reacts with an isocyanate group include 3-hydroxy-1,2,2-dimethylpropionic acid, 2,2-bis (hydroxymethyl) acetic acid, and 2,2-bis ( (Hydroxymethyl) propionic acid, 3-amino-2,2-dimethylpropionic acid, 2,2-bis (aminomethyl) acetic acid, 2,2-bis (aminomethyl) propionic acid, 3-mercapto-1,2,2-dimethylpropion Acid, 2,2-bis (mercaptomethyl) acetic acid, 2,2-bis (mercaptomethyl) propionic acid, etc., or those in which the carboxyl group in them is partially or completely neutralized with tertiary amine Can be Examples of the tertiary amine used in this case include triethylamine, N-methylpyrrolidine, N-methylbiperidine, N-methylmorpholine and the like. Examples of the nonionic hydrophilic compound having an active hydrogen-containing group that reacts with an isocyanate group include, for example, polyalkylene oxide or an amino group or a terminal hydroxyl group thereof. Is a compound converted to a mercapto group. Examples of the polyalkylene oxide include polyethylene oxide, polypropylene oxide and the like, and polyethylene oxide is preferable. The polyalkylene oxide is obtained, for example, by adding an alkylene oxide to a monoalcohol such as methanol, ethanol, or butanol, and the number average molecular weight is preferably from 200 to 50,000, It is more preferable to set it to 300 to 1,500. In the case of a polyalkylene oxide such as a copolymer of polyethylene oxide and polypropylene oxide, the content of ethylene oxide is preferably 50% by weight or more. The conversion of a terminal hydroxyl group to an amino group or a mercapto group can be performed by a known method. The conversion of a terminal hydroxyl group to an amino group can be performed, for example, by the method described in “Morrison Boyd Organic Chemistry (Medium), Third Edition, The conversion of a terminal hydroxyl group to a mercapto group in accordance with pp. 197, pp. 653 and 911 is described in, for example, Pfizer Latest Organic Chemistry I, Showa 39, 377 It can be performed according to.

As the hydrophobic polyisocyanate, various known and commonly used polyisocyanates having no hydrophilic groups such as anionic groups, cationic groups and nonionic groups can be used. Representative examples of hydrophobic polyisocyanates include [1] tetramethylene diisocyanate, ethyl (2,6 diisocyanate) hexanoate, hexamethylene diisocyanate, dodecamethylene diisocyanate. Aliphatic diisocyanates such as isocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate, [2] 3-isocyanate hexamethylene diisocyanate, 1 , 8-diisocyanate-14-isocyanate methyloctane, aliphatic triisocyanate such as lysine ester triisosocyanate, [3] 1,3- or 1,4-bis (isocyanatemethyl) cyclohexane, 1 , 3- or 1,4-dicyclohexane, isophorone dioxonate, dicyclohexylmethane_4,4, diisocene Alicyclic diisocyanates such as 2,5- or 2,6-bis (isocyanatomethyl) norbornane, [4] 2,5- or 2,6-bis (isosianetomethyl) —2-iso Alicyclic triisocyanates such as cyanate propyl norbornane, [5] m-xylylene diisocyanate, hi,, aralkylene dicysocyanate such as'α'-tetramethyl-1 m-xylylene diisocyanate, [6] m- or p-phenylenediisocyanate, tolylene-1,2,4- or 2,6-diisocyanate, diphenylmethane-1,4,4,1-diisocyanate, naphthylene-1,5-diisocyanate, diphenylene 4, 4 'diisocyanate, Aromatic diisocyanates such as 4,4,1-diisocyanate-1,3,3-dimethyldiphenyl, 3-methyldiphenylmethane-1,4,4,1-diisocyanate, diphenylether-1,4,4, diisocyanate, etc., [7] triphenyl Aromatic triisocyanates such as methane triisocyanate and tris (isocyanate phenyl) thiophosphate; [8] cyclization by bonding the above-mentioned various diisocyanates or isocyanate groups of triisocyanate. A polyisocyanate having a dimerized uretdione structure, [9] a polyisocyanate having an isocyanurate structure in which the isocyanate groups of the various diisocyanates or triisocyanates described above are bonded to each other to form a cyclotrimerized structure; [10] The above-mentioned various disocyanates or tris A polyisocyanate having a burette structure obtained by reacting a succinate with water, [11] an oxadiazine obtained by reacting the above-mentioned various diisocyanates or triisocyanates with carbon dioxide Polyisocyanates having a trion structure, polyisocyanates having a [12] arophanate structure, and the like are preferred. Of these, hydrophobic aliphatic or alicyclic di- or tri-isocyanates are preferred, and lysine ester tris is preferred. More preferred is isocyanate, hexamethylene disocyanate or isophorone disocyanate. In the reaction between an anionic hydrophilic compound or a nonionic hydrophilic compound having an active hydrogen-containing group that reacts with an isocyanate group and a hydrophobic polyisocyanate, the reaction temperature is not particularly limited, but is preferably 20 to The temperature is preferably 120 ° C., more preferably 40 to 110 ° C. The ratio of the raw materials of the anionic hydrophilic compound or nonionic hydrophilic compound having an active hydrogen-containing group that reacts with the isocyanate group and the hydrophobic polyisocyanate is as follows:

The molar ratio of (mol number of isocyanate group) / (mol number of active hydrogen-containing group) is preferably from 1 to 20 and more preferably from 1 to 10. The reaction is preferably continued until the active hydrogen-containing group has been reacted with the isocyanate group. At this time, a reaction catalyst may be used if necessary. Examples of the reaction catalyst include Lewis acids such as organic tin and organic titanium, and tertiary amines.

In the polyisocyanate composition of the present invention, the ratio (weight ratio) of the lysine ester triisocyanate to the emulsifier is not particularly limited, but is preferably 5:95 to 99.5: 0.5. More preferably, it is 40:60 to 90:10.

The isocyanate group concentration (hereinafter, abbreviated as NCO concentration) of the polyisocyanate composition of the present invention is preferably 25 to 47% by weight, more preferably 30 to 45% by weight. The polyisocyanate composition of the present invention is colorless or pale yellow, and has a viscosity at 2 CTC of preferably 25 to 500 cps, more preferably 30 to 400 cps, and still more preferably 50 to 300 cps.

The polyisocyanate composition of the present invention may be used by using a solvent. Solvents that can be used at that time are those that are inert to the isocyanate group. For example, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, 1- Methoxypropyl mono 2-acetate, 2-butane nonone, 4-methylpentanone, cyclohexanone, propylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl acetate, diethylene glycol butyl ether acetate, N-methylpyrroli Don, N-methylcaprolactam and the like.

The polyisocyanate composition of the present invention does not crystallize during long-term storage or storage at low temperature, does not apply a high shearing force, and can be easily stirred with water by simply stirring by hand. Emulsified in water.

The polyisocyanate composition of the present invention is useful for applications such as paints, coatings, inks, adhesives, resist materials, and sealing agents.

Next, an aqueous curable composition containing an aqueous resin having an active hydrogen-containing group that reacts with the isocyanate group will be described.

Examples of the active hydrogen-containing group that reacts with the isocyanate group include those described above.

Examples of the aqueous resin having an active hydrogen-containing group that reacts with an isocyanate group include those in a known and commonly used form such as an aqueous solution type, an aqueous dispersion type such as colloidal dispense and emulsion. Resin, styrene-butadiene resin, styrene-acrylonitrile resin, acrylic resin, fluoroolefin resin, silicon-modified vinyl polymer, vinyl polymer such as polyvinyl alcohol, ②polyester resin, polyurethane Resins, phenolic resins, melamine resins, epoxy resins, alkyd resins, polyamide resins, polyether resins, silicone resins, and other synthetic resins other than vinyl polymers, ③ animal proteins, starch , Cellulose derivatives, dextrin, gum arabic, etc. Natural polymers and the like can be mentioned, and among them, acrylic resins are preferred. The amount of the active hydrogen-containing group that reacts with the isocyanate group contained in the aqueous resin having an active hydrogen-containing group that reacts with the salt group depends on the curability of the aqueous curable composition of the present invention and the water resistance of the obtained cured product. From the viewpoint of properties, the amount is preferably 0.01 to 6 mol, more preferably 0.05 to 4 mol, and still more preferably 0.1 to 2 mol, per 100 g of the solid content of the aqueous resin. . These aqueous resins may be used alone or as a mixture of two or more.

In the aqueous curable composition of the present invention, the ratio of the number of moles of isocyanate groups in the polyisocyanate composition to the number of moles of active hydrogen-containing groups reacting with the isocyanate groups contained in the aqueous resin is preferably 0. 1: 1 to 10: 1, more preferably 0.3:;! 5: 1, more preferably 0.5: 1 to 3: 1.

In preparing the aqueous curable composition of the present invention, a high-speed stirrer may be used, but the composition can also be homogenized by stirring manually.

The aqueous curable composition of the present invention can be used as a clear composition containing no pigment, and can also be used as a colored composition by blending various known and commonly used organic or inorganic pigments. .

The aqueous curable composition thus prepared includes paints, adhesives, inks, waterproofing materials, sealing agents, natural fibers, synthetic fibers, various fibers such as glass fibers, paper impregnating agents, natural fibers, synthetic fibers, It can be used for various applications such as various fibers such as glass fibers and surface treatment agents for paper. In particular, when used as a water-based paint, a coating film having excellent appearance such as transparency and gloss, water resistance, and solvent resistance can be obtained.

The aqueous curable composition of the present invention may further contain, if necessary, additives suitable for various uses, such as a surfactant, a filler, a leveling agent, a thickener, a defoaming agent, Various well-known and commonly used additives such as a film assistant, an organic solvent, an ultraviolet absorber, an antioxidant, and a pigment dispersant can also be blended.

The aqueous curable composition of the present invention can be cured by evaporating water, and can be cured under room temperature to heating conditions.

BEST MODE FOR CARRYING OUT THE INVENTION

Example 1

Hexamethylene diisocyanate (hereinafter abbreviated as HDI) isocyanurate-type polyisocyanate in a four-necked flask equipped with a stirrer, thermometer, cooling tube and nitrogen inlet tube. ト [Sumidur N 3300, manufactured by Sumitomo Bayer Urethane Co., Ltd., NCO concentration 21.6% by weight, nonvolatile content 100% by weight] 50 g and methoxypolyethylene glycol [Uniox M-400, NOF Corporation And an average molecular weight of 400], and reacted at 100 ° C for 2 hours under a nitrogen stream. After the reaction, 168 g of lysine ester triisocyanate [LTI, manufactured by Kyowa Hakko Kogyo Co., Ltd., NCO concentration: 47.2% by weight] was added, and the mixture was stirred to obtain a homogeneous solution. The polyisocyanate composition obtained was a colorless and transparent liquid, the NCO concentration was 35.5% by weight, and the viscosity was 200 cps (20 ° C).

Example 2

In a four-necked flask equipped with a stirrer, thermometer, cooling pipe and nitrogen inlet pipe, an HD I-type polyisocyanate type polyisocyanate [Sumidur N 3300, manufactured by Sumitomo Bayer Urethane Co., Ltd., NCO concentration 21 6 wt%, nonvolatile content 100 wt%] 50 g and methoxypolyethylene glycol [UNIOX M-1000, Nippon Oil & Fats Co., Ltd., average molecular weight 1000] 85 g and added at 100 ° C for 2 hours under a nitrogen stream Reacted. After the reaction, 675 g of lysine ester triisocyanate [LT I, manufactured by Kyowa Hakko Kogyo Co., Ltd., NCO concentration: 47.2% by weight] was added, and the mixture was stirred to obtain a homogeneous solution. The obtained polyisocyanate composition was a colorless and transparent liquid having an NCO concentration of 40.1% by weight and a viscosity of 100 cps.

(20 ° C).

Example 3

Lysine ester triisocyanate [LT I, manufactured by Kyowa Hakko Kogyo Co., Ltd., NCO concentration: 47.2% by weight] in a four-necked flask equipped with a stirrer, thermometer, cooling tube and nitrogen inlet tube g and 90 g of methoxypolyethylene glycol [UNIOX M-1000, manufactured by Nippon Yushi Co., Ltd., average molecular weight: 1000], and reacted at 100 ° C for 2 hours under a nitrogen stream. The obtained polyisocyanate composition was a colorless and transparent liquid, the NCO concentration was 39.4% by weight, and the viscosity was 250 cps (20 ° C).

Comparative Example 1

In a four-necked flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube, HDI-type isocyanurate type polyisocyanate [Sumidur N 3300, manufactured by Sumitomo Bayer Urethane Co., Ltd., NCO concentration 21. 6% by weight, non-volatile content 100% by weight] 500 g and methoxypolyethylene glycol [UNIOX M-400, manufactured by NOF CORPORATION, average molecular weight 400] 75 g, and added at 100 ° C under a nitrogen stream. Allowed to react for hours. Poly obtained The coating composition was a colorless and transparent liquid having an NCO concentration of 17.0% by weight and a viscosity of 3250 cps (20 ° C). -Comparative Example 2

In a four-necked flask equipped with a stirrer, thermometer, cooling tube and nitrogen inlet tube, HDI-type isocyanurate type polyisocyanate [Sumidur N 3300, manufactured by Sumitomo Bayer Urethane Co., Ltd., NCO concentration 21. 6% by weight, nonvolatile content 100% by weight], 500 g, and 75 g of methoxypolyethylene glycol [UNIOX M-1000, manufactured by NOF CORPORATION, average molecular weight 1000], and added at 100 ° C under a nitrogen stream. Allowed to react for hours. The obtained polyisocyanate composition was a colorless and transparent liquid, and had an NCO concentration of 17.7% by weight and a viscosity of 3500 cps (20 ° C).

Test Example 1 Evaluation of water dispersibility of polyisocyanate composition

In a 20 OmL beaker, add 70 g of water and 30 g of each of the polyisocyanate compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2, and maintain the mixture at 23 ° C. with a magnetic stirrer and a rotor (total length 30 mm). And a diameter of 8 mm) with a stirring speed of 200 rpm, and the dispersion behavior (◎: uniform dispersion within 10 seconds from the start of stirring, 〇: uniform dispersion within 1 minute from the start of stirring, Δ: uniformly dispersed within 10 minutes from the start of stirring, X: dispersed, but partially dissolved, XX: not dispersed) were visually evaluated. Table 1 shows the evaluation results.

Table 1

As shown in Table 1, the polyisocyanate compositions obtained in Examples 1 to 3 were excellent in water dispersibility.

Reference example Preparation of acryl-based resin emulsion

417.2 g of water was placed in a four-separable flask equipped with a stirrer, thermometer, cooling tube and nitrogen inlet tube, heated to 70 ° C under a nitrogen stream, and then Aqualon HS-10 [Daiichi Kogyo Pharmaceutical Co., Ltd.] 10.8 g, 2-hydroxyethyl methyl acrylate 11.3 g, methyl methyl acrylate 11.9.4 g, butyl acrylate 176.5 g, polystyrene 36.0 Of the mixture of g and 6.lg of methacrylic acid, an amount corresponding to 1/5 was added all at once. Then, a solution prepared by dissolving 8 g of ammonium persulfate in 80 g of distilled water was added. When the temperature was stabilized at 70 ° C after the initial polymerization, the remaining mixture was added dropwise over 2 hours. After completion of the dropwise addition, the temperature was raised to 80 ° C, and the mixture was aged for 2 hours. After completion of the aging, the mixture was neutralized with 4.5 g of a 28% aqueous ammonia solution to obtain a hydroxyl group-containing acrylyl resin emulsion having a nonvolatile content of 42.0% by weight and a solid content hydroxyl value of 13.5 mgKOH / g.

Examples 4 to 6 and Comparative Examples 3 and 4

NCO / OH = 2 / l (molar ratio) using the polyisocyanate compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 and the acrylic resin emulsion obtained in Reference Example. Each aqueous curable composition was prepared as described above.

Test Example 2 Evaluation of aqueous curable composition

Each of the aqueous curable compositions obtained in Examples 4 to 6 and Comparative Examples 3 and 4 was applied on a glass plate by using an applicator so that the thickness of the dried film was 30 zm, and the temperature was 23. It was cured and dried for one week at 50 ° C and 50% humidity. The cured coating film was evaluated for its appearance, gel fraction, water resistance and mechanical strength as follows. .

Coating film appearance: Visually evaluated.

Gel fraction: A coating film formed on a glass plate was cut from the glass plate, immersed in tetrahydrofuran (THF) under reflux conditions for 8 hours, and then dried at 80 ° C using a vacuum dryer. 1. The gel was dried under the conditions of 33 kPa for 6 hours, and the gel fraction was calculated by the following equation. '' Gel fraction (%) = (weight of coating after immersion in THF) / (weight of coating before immersion in THF) X 100 Water resistance: The coating prepared on a glass plate was placed in deionized water at 23 ° C, immersed for 24 hours, and visually evaluated the appearance of the coating film (◎: no change, Δ: very slight whitening, Δ: fairly whitening, X: extremely whitening).

The obtained aqueous curable composition was applied on a glass plate using an applicator so that the dry film thickness became 200 zm, and cured at 80 ° C for 2 hours. After that, it was dried at a temperature of 23 ° C and a humidity of 50% for one day. The mechanical strength of the cured coating film was evaluated by a tensile test as described below.

Tensile test: The coating film was peeled off from the glass plate and dried at a temperature of 23 ° C and a humidity of 50% for 2 days. A dumbbell-shaped test piece was cut out from this coating film, and the following equipment was used in accordance with JISK 7113. The stress at break and strain at break were measured under the following conditions.

Equipment: A G-1 Autograph (Shimadzu Corporation)

Damper: No. 2 (distance between marked lines: 20 mm) Tensile speed: 300 mm / min

Table 2 shows the evaluation results.

Table-2

As shown in Table 1, the aqueous curable compositions obtained in Examples 4 to 6 were excellent in coating film appearance, water resistance, mechanical strength, and the like.

Industrial Available '

According to the present invention, there is provided a polysocyanate composition excellent in water dispersibility, storage stability, mechanical strength of a cured product, water resistance and the like, and an aqueous curable composition containing the polysuccinate composition.

Claims

The scope of the claims

1. General formula (I)

0CN—— (CH ₂ ) ₄ — CH— NC0

(I)

0C— OR— CO

(Wherein, R represents a lower alkylene) and a polyisocyanate composition comprising a lysine ester triisocyanate represented by the formula:

2. The polyisocyanate composition according to claim 1, wherein the ratio of the lysine ester triisocyanate to the emulsifier is 5:95 to 99.5: 0.5 by weight.

3. The polyisocyanate composition according to claim 1, wherein the polyisocyanate composition has an isocyanate group concentration of 25 to 47% by weight.

4. The polysocyanate composition according to any one of claims 1 to 3, wherein the viscosity at 20 ° C is 25 to 500 cps.

5. The emulsifier according to claim 1, wherein the emulsifier is a compound obtained by reacting an anionic hydrophilic compound or a nonionic hydrophilic compound having an active hydrogen-containing group that reacts with an isocyanate group with a hydrophobic polysocyanate 1. The polysocyanate composition according to any one of the above.

6. The polyisocyanate composition according to any one of claims 1 to 5, wherein R is ethylene. ■ '

7. An aqueous curable composition comprising an aqueous resin having an active hydrogen-containing group that reacts with a polyisocyanate composition according to any one of claims 1 to 6.