JPH09328654A - Polyisocyanate composition having high emulsifiability and stability, and aqueous coating composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyisocyanate composition excellent in water dispersibility, suppressing the reaction of water with the terminal isocyanate groups of the polyisocyanate in a water-dispersed state, and exhibiting high stability. SOLUTION: This polyisocyanate composition comprises (a) a hydrophilic polyisocyanate comprising a base polyisocyanate consisting of an aliphatic diisocyanate, an aliphatic diisocyanate or a polyisocyanate derived from the diisocyanate and having two or more terminal isocyanate groups and a hydrophilic group bound to the base polyisocyanate and containing on the average 5-50 ethylene oxide repeating units, and (b) a substantially water-free ionic surfactant in an amount of 0.5-20wt.% based on the total amount of the components (a) and (b). A two-pack type coating composition comprising the polyisocyanate composition and an aqueous polyol is excellent in pot life, water resistance, etc., and is extremely useful for various kinds of aqueous coating materials, adhesives, building materials, sealants, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a highly emulsifying polyisocyanate composition, and a room temperature crosslinkable two-liquid water-based urethane coating composition comprising an aqueous polyol and a highly emulsifying polyisocyanate composition. More specifically,
The present invention provides a hydrophilic poly (isocyanate) having a nonionic hydrophilic group bonded to at least one base polyisocyanate selected from the group consisting of (a) aliphatic and / or alicyclic diisocyanates and polyisocyanates derived therefrom. The present invention relates to a novel polyisocyanate composition having a high emulsifying property and stability, which is composed of an isocyanate and (b) an ionic surfactant substantially free of water. The present invention also relates to a room temperature crosslinkable two-component water-based urethane coating composition comprising a combination of an aqueous polyol as a main agent and the above novel polyisocyanate composition as a curing agent. This water-based coating composition has excellent pot life and is capable of forming a coating film excellent in water resistance, etc., and is mainly used for construction water-based paints, automobile water-based paints, household water-based paints, adhesives, building materials, etc. It is useful as a coating agent and a sealing agent, and in addition, it can be used as a cross-linking agent for ink vehicles, a curing agent in casting, a resin component such as elastomer, a cross-linking agent for urethane foam, and a treating agent for fibers and fabrics. Is.

[0002]

2. Description of the Related Art In recent years, guidelines concerning volatile organic compounds have become strict, and regulations in the United States and Germany have already been implemented. Therefore, it has been desired that the room temperature crosslinkable two-component urethane coating composition, which has conventionally used an organic solvent, be made water-based. However, the polyisocyanate used as a curing agent in the two-component urethane coating composition is difficult to disperse in water and easily reacts with water, and carbon dioxide is generated when it reacts.

Therefore, Japanese Examined Patent Publication No. 55-7472 (US Pat. No. 3,996,154) and Japanese Unexamined Patent Publication (Kokai) No.
-222150 (U.S. Pat. No. 5,252,696)
As a method for obtaining a polyisocyanate having a high emulsifying property, a polyisocyanate in which a nonionic hydrophilic group is introduced into the polyisocyanate is proposed in (Japanese Patent No. 4). Further, in JP-A-6-17004, in order to improve the dispersibility of polyisocyanate, an aqueous polyol in which a specific carboxylic acid group or sulfonic acid group which imparts emulsifying property to polyisocyanate is introduced is used as a main agent. Is proposed. Further, in JP-A-7-48429 (US Pat. No. 5,373,050) and JP-A-7-113005, a nonionic hydrophilic group and a lipophilic group are introduced in order to extend the pot life. Polyisocyanates have been proposed.

However, since the conventional polyisocyanate shown above uses only the nonionic hydrophilic group as the hydrophilic component, the reactivity between the isocyanate group and water cannot be sufficiently suppressed in the water-dispersed state. In addition, the pot life has not reached a level at which it can be used practically, and the coating composition of the coating composition using the polyisocyanate as a crosslinking component has a low water resistance.

[0005]

SUMMARY OF THE INVENTION However, one object of the present invention is to provide excellent emulsifiability, which is excellent in water dispersion stability and in which the reactivity between the terminal isocyanate group of polyisocyanate and water in the water dispersion state is suppressed. Moreover, it is to provide a novel polyisocyanate composition having high stability. Another object of the present invention is to provide a water-based coating composition capable of forming a coating film having excellent pot life and excellent water resistance.

[0006]

Means for Solving the Problems The present inventors have solved the above-mentioned problems of conventional highly emulsifying polyisocyanates, have high emulsifying properties, and are capable of reacting isocyanate groups with water in a water-dispersed state. We have conducted intensive research to develop a polyisocyanate that suppresses As a result, (a) aliphatic and / or
Or a hydrophilic polyisocyanate obtained by bonding a nonionic hydrophilic group to at least one base polyisocyanate selected from the group consisting of alicyclic diisocyanates and polyisocyanates derived therefrom, and (b) substantially water The novel polyisocyanate composition consisting of an ionic surfactant not containing is not only excellent in water dispersibility, but also shows high stability by suppressing the reaction between the terminal isocyanate group of polyisocyanate and water in a water dispersed state. I found this surprisingly. Furthermore, the present inventors have found that a two-component water-based coating composition in which the novel polyisocyanate composition as a curing agent is combined with an aqueous polyol as a main component is excellent in pot life and is excellent in water resistance. It was found that it can form a film and is extremely useful as various water-based paints, adhesives, building materials, and sealing agents. The present invention is based on these new findings.

That is, according to one aspect of the present invention,
(A) at least one diisocyanate selected from an aliphatic diisocyanate and an alicyclic diisocyanate, and at least one selected from the group consisting of polyisocyanates having two or more terminal isocyanate groups derived from the at least one diisocyanate A hydrophilic polyisocyanate comprising one kind of a base polyisocyanate and a nonionic hydrophilic group bonded to the base polyisocyanate and having an average number of 5 to 50 ethylene oxide repeating units, wherein the hydrophilic group is , 2 based on the total weight of the base polyisocyanate and the hydrophilic groups
˜50 wt% and (b) 0.5-20 wt% of substantially water-free ionic surfactant, based on the total weight of component (a) and component (b). A polyisocyanate composition is provided.

According to another aspect of the present invention, (A)
An aqueous solution or emulsion of a polyol having a hydroxyl value of 1 to 300 mgKOH / g, and (B) the polyisocyanate composition described above.
O / OH) is in the range of 0.5 to 5.0, and component (A)
And component (B) are provided separately from each other, and an aqueous coating composition is provided which is configured to be mixed at the time of use.

Hereinafter, the present invention will be described in detail. Examples of the aliphatic diisocyanate and alicyclic diisocyanate used in the present invention, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, 1,
4-diisocyanate cyclohexane etc. are mentioned.
Of these, hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated xylene diisocyanate are industrially readily available and preferred.

The above-mentioned aliphatic diisocyanates, alicyclic diisocyanates and polyisocyanates having two or more terminal isocyanate groups derived from these diisocyanates have a biuret structure, isocyanurate structure, urethane structure and uretdione in the molecule. It includes polyisocyanates having a structure and an allophanate structure, respectively.

In the present invention, the term "base polyisocyanate" means at least one diisocyanate selected from an aliphatic diisocyanate and an alicyclic diisocyanate, and two or more end groups derived from the at least one diisocyanate. It means a polyisocyanate itself selected from the group consisting of polyisocyanates having an isocyanate group, in which a nonionic hydrophilic group is not bonded.

Regarding the method for producing the polyisocyanates having the above-mentioned biuret structure, isocyanurate structure, urethane structure, uretdione structure and allophanate structure from diisocyanate, for example, Japanese Patent Publication No. Sho 64-10023, JP-A-58-38713.
Japanese Patent Publication No. 63-89574, Japanese Patent Laid-Open No. 6-9
5041, Japanese Patent Application Laid-Open No. 4-306218, Japanese Patent Application No. 6-133321, and US Pat. No. 3,124,605.
The specification can be referred to. Those having a biuret structure are excellent in adhesiveness, those having an isocyanurate structure are excellent in weather resistance, and those having a urethane structure using an alcohol having a long side chain are excellent in elasticity and extensibility. Those having a uretdione structure or an allophanate structure are characterized by low viscosity.

The hydrophilic polyisocyanate which is the component (a) of the polyisocyanate composition of the present invention is at least one diisocyanate selected from the above aliphatic diisocyanates and alicyclic diisocyanates, and the at least one diisocyanate. From at least one base polyisocyanate selected from the group consisting of polyisocyanates having two or more terminal isocyanate groups derived from 2 to 50% by weight based on the total weight of the base polyisocyanate and the hydrophilic group.

The nonionic hydrophilic group containing an average number of ethylene oxide repeating units of 5 to 50 includes ethylene having an average number of 5 to 50 in poly (C ₁ -C ₂₀ alkylene) oxide monoalkyl ether alcohol. A group derived from a compound containing an oxide repeating unit, such as polyethylene glycol mono (C ₁ -C ₂₀ alkyl) ether such as polyethylene glycol monoethyl ether, polypropylene oxide or a poly (ethylene oxide) repeating unit at one end or both ends. tetramethylene oxide are added, their compounds and which one is alkyl etherified hydroxyl groups, ethylene oxide and propylene oxide or tetrahydrofuran or the like is random polymerization, one of those hydroxyl groups (C ₁ -C ₂₀ alkyl There may be mentioned etherified compound, group with an average number of ease of industrial availability are derived from polyethylene glycol monomethyl ether containing 5 to 50 ethylene oxide repeating units is most appropriate. When the average number of ethylene oxide repeating units is less than 5, it is not preferable because high emulsifying ability cannot be exhibited. If the number exceeds 50, the crystallinity of the hydrophilic polyisocyanate becomes high and the solid polyisocyanate easily becomes solid, which is not preferable.

(A) of the polyisocyanate composition of the present invention
The amount of the hydrophilic group bonded to the component hydrophilic polyisocyanate is 2 to 50% by weight based on the total amount of the base polyisocyanate and the hydrophilic group. If it is less than 2% by weight, the effect of lowering the interfacial tension is not sufficient, and high emulsifying ability cannot be exhibited, which is not preferable. If it exceeds 50% by weight, the hydrophilicity of the highly emulsifying polyisocyanate composition of the present invention is too high, and the reaction between the isocyanate group and water during water dispersion cannot be suppressed, which is not preferable. The method of introducing a hydrophilic group into the base polyisocyanate is a method of reacting a terminal isocyanate group contained in the base polyisocyanate with a compound that gives a hydrophilic group such as the above-mentioned polyethylene glycol monomethyl ether. More specifically, for example, the above-mentioned base polyisocyanate and polyalkylene oxide monoalkyl ether alcohol may be mixed to carry out an ordinary urethanization reaction. Regarding the reaction conditions of the urethanization reaction, for example, Japanese Patent Publication No. 64-10023, Japanese Patent Laid-Open No. 58-38713 and Japanese Patent Publication No. 63-89574 can be referred to.

The novel highly emulsifying polyisocyanate composition of the present invention comprises the above-mentioned hydrophilic polyisocyanate as the component (a) and an ionic surfactant containing substantially no water as the component (b). It can be obtained by mixing 0.5 to 20% by weight with respect to the total weight of the components (a) and (b). The term "substantially free of water" as used herein means that water and hydrophilic polyisocyanate (a) contained in the mixed ionic surfactant (b) are included.
Foaming by reacting with the terminal isocyanate group contained in
It means a state in which water is removed to the extent that cloudiness and an increase in viscosity do not occur, and actually it is 1% by weight or less based on the weight of the ionic surfactant.

The substantially water-free ionic surfactant is a high boiling organic solvent capable of dissolving the ionic surfactant in the water-containing ionic surfactant, for example, polyethylene glycol monomethyl ether. It is obtained by mixing a polyalkylene oxide monoalkyl ether alcohol such as the above and a polyalkylene oxide dialkyl ether such as triethylene glycol dimethyl ether or diethylene glycol diethyl ether, and distilling off water by heating or the like. When an ionic surfactant containing water is mixed with the hydrophilic polyisocyanate (a), water reacts with the terminal isocyanate group contained in the hydrophilic polyisocyanate to cause foaming, cloudiness, and increase in viscosity. Not desirable to happen. Further, when water is distilled off without mixing a high boiling point organic solvent with an ionic surfactant containing water, the ionic surfactant becomes a solid and the (a) is dissolved in the above-mentioned hydrophilic polyisocyanate. It is difficult because it is difficult.

Whether the anionic or cationic ionic surfactant is used depends on whether the polyisocyanate composition [component (B)] of the present invention is an aqueous polyol solution used as a main agent. Or aqueous polyol emulsion [(A) component]
(Hereinafter, both are often referred to simply as "aqueous polyol"). That is, a polyol used as an aqueous polyol is one in which an acid component such as a carboxylic acid or a sulfonic acid is incorporated into a molecule in order to have solubility or dispersibility in water, and an alkali such as sodium hydroxide or ammonia is used. It can be neutralized with components, but when the aqueous polyol thus obtained is used as the component (A) of the aqueous coating composition, it is appropriate to use an anionic surfactant.

When a cationic surfactant is used when the above-mentioned aqueous polyol is used, the aqueous polyol and the highly emulsifying polyisocyanate composition may form an aggregate, which is not suitable. Conversely, when an alkaline component such as an amine is incorporated into the molecule of the aqueous polyol and the aqueous polyol neutralized with an acid component such as hydrochloric acid is used,
It is expedient to use cationic surfactants. Either may be used when the aqueous polyol is used without being neutralized.

Examples of the anionic surfactants, carboxylate type, sulfate type, sulfonate type, phosphate type is suitable, for example, (C ₁ -C ₂₀ alkyl) ammonium benzenesulfonate, (C ₁ -C ₂₀ alkyl ) Sodium disulfate, sodium alkyldiphenyl ether disulfonate, di (C ₁ -C ₂₀
Alkyl) sulfosuccinate, polyoxyethylene C ₆ -C ₃₀ sodium aryl ether sulfonate, ammonium polyoxyethylene C ₆ -C ₃₀ aryl ether sulfonate and the like. Suitable examples of cationic surfactants are quaternary ammonium salts, pyridinium salts and imidazolinium salts, such as C ₁
-C ₂₀ alkyl trimethyl ammonium bromide, C
₁ -C ₂₀ alkyl pyridinium bromide, it may be mentioned imidazolinium laurate.

If the amount of the ionic surfactant (b) added to the hydrophilic polyisocyanate (a) is less than 0.5% by weight, the effect of water dispersion stability by mixing the ionic surfactant is obtained. Not suitable because it is not expressed. If it exceeds 20% by weight, the dispersed particle size becomes too small.
The pot life of the water-based coating composition prepared from the highly emulsifying polyisocyanate composition of the present invention and an aqueous polyol is shortened, and since the components not involved in crosslinking in the highly emulsifying polyisocyanate composition are excessively increased, an aqueous system This may cause brittleness of the coating formed from the coating composition, which is not preferable.

The highly emulsifiable polyisocyanate composition of the present invention is excellent in water dispersion stability and has a high stability in a long pot by using a nonionic hydrophilic group and an ionic surfactant in combination. You can achieve life. Although the reason for this has not been clarified yet, when a water-based coating composition is prepared from the highly emulsifying polyisocyanate composition of the present invention and a water-based polyol, the polyisocyanate oil droplets formed in a water-dispersed state and the water interface An ionic surfactant is located to form a double protective film in which nonionic hydrophilic groups are arranged on the polyisocyanate oil droplet side with respect to the ionic surfactant, and the isocyanate group is a polyisocyanate oil droplet. It is considered that the reason is that it has a structure located inside. By the way, Japanese Examined Patent Publication No. 55-7472, Japanese Unexamined Patent Publication No. 5-222150, Japanese Unexamined Patent Publication No. 6-17004, and Japanese Unexamined Patent Publication No. 7-4842.
In JP 9 and JP-A 7-113005, since only the nonionic hydrophilic group is used, the unique double protective film structure as described above is not formed.

The introduction of the nonionic hydrophilic group into the polyisocyanate is effective in improving the dispersibility of the resulting hydrophilic polyisocyanate composition in water, but it is prepared from the composition. The water-based coating composition cannot achieve a practically usable pot life. This is because the nonionic hydrophilic group alone has only a single protective film of the nonionic hydrophilic group at the interface between the polyisocyanate oil droplet and the water, and the non-ionic hydrophilic group is sufficient for the protective film to form an interface. Since they cannot be arranged, water is allowed to enter the polyisocyanate oil droplets when the hydrophilic polyisocyanate is dispersed in water, and the reaction between water and the isocyanate group starts. It is considered that this is because the residual rate of the group decreases. Further, only by mixing an ionic surfactant with a polyisocyanate not introducing a nonionic hydrophilic group, since the dispersibility in water is poor, the water dispersion stability such as the highly emulsifying polyisocyanate composition of the present invention is stable. Can not achieve sex.

The most important feature of the highly emulsifying polyisocyanate composition of the present invention is the combined use of a nonionic hydrophilic group and an ionic surfactant. Regarding this mechanism, as described above, due to the interaction of the nonionic hydrophilic group and the ionic surfactant, when the highly emulsifying polyisocyanate of the present invention is dispersed in water, the ionic property at the interface between the polyisocyanate oil droplets and the water is ionic. It is considered that a double protective film consisting of a surfactant and a nonionic hydrophilic group is formed, and this strong protective film prevents water from entering the isocyanate oil droplets,
It is believed that the polyisocyanate groups in the polyisocyanate oil droplets can be protected from water.

The highly emulsifiable polyisocyanate composition of the present invention contains an ionic surfactant which does not substantially contain water. In contrast to this, a polyisocyanate containing only a nonionic hydrophilic group is introduced. In a system in which an ionic surfactant is added and dispersed in water, a water-based urethane coating composition prepared therefrom cannot achieve a long pot life. This is because in such a system, when the polyisocyanate oil droplets are generated, the water coordinated around the ionic surfactant is entangled inside the polyisocyanate oil droplets, so that the reaction between water and the isocyanate group occurs. It is considered that this is because the residual ratio of the terminal isocyanate groups of the polyisocyanate decreases in a short time after the start of

The highly emulsifying polyisocyanate composition of the present invention has an isocyanate group content of 3 to 25% by weight, measured by measuring the polyisocyanate composition in a state where the nonvolatile content is substantially 100%. Average molecular weight is 3
50-10,000, viscosity 50-20,000 mPa
It is preferably s (25 ° C). In the present invention, the polyisocyanate composition has a nonvolatile content of substantially 100.
% Means a state in which the highly emulsifying polyisocyanate composition does not substantially contain volatile components such as a solvent, and the volatile component is 1% in the highly emulsifying polyisocyanate.
Refers to the following conditions.

The isocyanate group content of the highly emulsifying polyisocyanate composition of the present invention is 3 to 3 when the non-volatile content of the polyisocyanate composition is substantially 100%.
It is preferably 25% by weight. Below 3% by weight,
When a water-based coating composition is prepared from a highly emulsifying polyisocyanate composition and a water-based polyol, the number of cross-linking points in the coating composition decreases, and the curing rate decreases,
It has the disadvantage of causing brittleness of the coating formed from the coating composition. If the isocyanate group content of the highly emulsifiable polyisocyanate composition exceeds 25% by weight, the amount of hydrophilic groups introduced into the polyisocyanate composition will be small, and the water dispersibility of the polyisocyanate composition may be low. .

Further, the viscosity of the highly emulsifying polyisocyanate composition of the present invention is preferably 50 to 20,000 mPa · s (25 ° C.) when the nonvolatile content is substantially 100%. If it exceeds 20,000 mPa · s, it is difficult to disperse it in water, which is not suitable. Considering dispersion in water, the lower the viscosity is, the better. However, if it is less than 50 mPa · s, it means that a large amount of diisocyanate having a low crosslinking ability is contained, which is not preferable.

The highly emulsifiable polyisocyanate composition of the present invention has a weight average molecular weight of 350 to 10,000. If the weight average molecular weight is less than 350, it may not be possible to introduce a sufficient amount of hydrophilic groups to obtain sufficient water dispersibility. When it exceeds 10,000, the viscosity of the highly emulsifying polyisocyanate composition becomes high and it becomes difficult to disperse it in water, which is not suitable.

The highly emulsifying polyisocyanate composition of the present invention is prepared by adding the polyisocyanate composition to 4 parts with respect to water.
600 rp of a mixture mixed with water in a weight ratio of 0:60
m at room temperature for 10 minutes to obtain an aqueous dispersion,
When left for an hour, the residual rate of unreacted isocyanate groups is 5
It is preferably 0% or more. If it is less than 50%, the pot life of the aqueous coating composition is shortened, and further the water resistance of the coating formed therefrom is lowered,
It is not preferable because the coating becomes brittle. In the present invention, a high residual ratio of unreacted isocyanate groups of 50% or more can be achieved by the mutual effect of the ionic surfactant component mixed with the introduced hydrophilic group component, as described above. This is because the reaction of can be suppressed. In the above-mentioned water dispersion, the highly emulsifiable polyisocyanate composition is O / W type dispersed in water.

The highly emulsifiable polyisocyanate composition of the present invention has high water dispersibility and high stability. The water dispersibility and stability referred to in the present invention are the dispersion retention of oil droplets of the highly emulsifiable polyisocyanate composition dispersed in water by the above method and the stability of the terminal isocyanate group in water. The highly emulsifiable polyisocyanate composition of the present invention shows no precipitate when left at 20 ° C. for 8 hours in a water-dispersed state, and has a residual ratio of unreacted isocyanate groups of 50% or more when left at 20 ° C. for 6 hours. Is. This is also achieved by the mutual effect of the introduced hydrophilic group component and the ionic surfactant used in combination. Next, a method for producing the highly emulsifying polyisocyanate composition of the present invention will be described.

The highly emulsifiable polyisocyanate composition of the present invention comprises a base polyisocyanate selected from the group consisting of the above-mentioned aliphatic and / or alicyclic diisocyanates and polyisocyanates obtained therefrom, and polyalkylene oxide monoalkyl ether alcohol. A compound giving a nonionic hydrophilic group such as
It can be obtained by carrying out a urethanization reaction at a temperature of several minutes to several days and then adding an ionic surfactant containing substantially no water. When obtaining a water-free ionic surfactant, when using a compound that also acts as a compound that gives a nonionic hydrophilic group as an organic solvent having a high boiling point, such as polyalkylene oxide monoalkyl ether alcohol, After heating the mixture of the alkylene oxide monoalkyl ether alcohol and the ionic surfactant to dehydrate the ionic surfactant, the resulting mixture is added to the above-mentioned base polyisocyanate compound to carry out a urethanization reaction. Can also be obtained by

Further, the highly emulsifying polyisocyanate composition of the present invention has the purpose of providing an aliphatic and / or alicyclic diisocyanate with a biuret structure, an isocyanurate structure, a urethane structure, a uretdione structure, an allophanate structure, etc. in the molecule. Before, during, or after the reaction to obtain the structure, a polyalkylene oxide monoalkyl ether alcohol is added to carry out a urethanization reaction to form a diisocyanate-bonded hydrophilic group, and then substantially contains water. Ionic surfactant, or a mixture of polyalkylene oxide monoalkyl ether alcohol and an ionic surfactant that does not substantially contain water, and if necessary, further urethanization reaction is carried out, and if necessary. Unreacted aliphatic and /
Alternatively, it can be obtained by distilling off the alicyclic diisocyanate.

The highly emulsifying polyisocyanate composition of the present invention can be used after adding an organic solvent. Highly emulsifying polyisocyanate composition mixed with an organic solvent,
Since the viscosity becomes low, the dispersibility in water is improved, and the residual ratio of isocyanate groups at the time of water dispersion becomes high, so that the pot life becomes long. In this case, it is necessary that the organic solvent does not have a functional group that reacts with the isocyanate group. In addition, the organic solvent must be compatible with the highly emulsifying polyisocyanate composition of the present invention. Examples of such organic solvents include ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate,
Pentyl acetate, methoxypropyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate,
2-ethylhexyl acetate, cyclohexyl acetate,
Ester compounds such as methyl propionate, butyl propionate, butyl butyrate, dioctyl adipate and diisopropyl glutarate; ether compounds such as diisopropyl ether, dibutyl ether, dioxane and diethoxyethane; 2-pentanone, 3-pentanone, 2-hexanone , Methyl isobutyl ketone, 2-heptanone, 4
-Ketone compounds such as heptanone, diisobutyl ketone, isophorone, cyclohexanone, methylcyclohexanone; benzene, toluene, xylene, ethylbenzene,
Examples thereof include aromatic compounds such as butylbenzene and p-cymene; polyethylene glycol dialkyl ether compounds such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and triethylene glycol dimethyl ether; and polyethylene glycol dicarboxylate compounds such as diethylene glycol diacetate.

The amount of the organic solvent added to the highly emulsifying polyisocyanate composition of the present invention is preferably 1 to 50% by weight based on the total amount of the polyisocyanate composition and the organic solvent. If it is less than 1% by weight, the merit of mixing an organic solvent, that is, the improvement of water dispersibility and the effect of extending the pot life are not observed, which is not preferable. 50% by weight
When it exceeds, the amount of the volatile organic compound in the water-based coating composition increases when the water-based coating composition is prepared from the highly emulsifying polyisocyanate composition, which is not preferable.

As described above, according to another aspect of the present invention, the hydroxyl value of the component (A) is 1 to 300.
A water-based coating prepared by blending mgKOH / g of an aqueous polyol and the above-mentioned highly emulsifying polyisocyanate composition as the component (B) in an isocyanate group / hydroxyl group equivalent ratio of 0.5 to 5.0. A composition is provided.
The polyol used in the present invention is a water-soluble polyol or a water-dispersible polyol, which is used as a polyol aqueous solution or a polyol aqueous emulsion, respectively. The water-soluble polyol is a water-soluble resin having a hydroxyl group, and the water-soluble polyol resin can be classified into a synthetic water-soluble polymer and a natural water-soluble polymer.

Examples of synthetic water-soluble polymers include, for example:
(Meth) acrylic acid C ₁ -C ₁₂ alkyl ester,
At least one hydroxyl group component selected from (meth) acrylic acid 2-hydroxyethyl ester and (meth) acrylic acid 2-hydroxypropyl ester is an essential component, and in some cases, (meth) acrylic acid, styrene, acrylic Regarding a copolymer having at least one unsaturated compound selected from unsaturated compounds such as nitrile and acrylamide as a comonomer, a part or all of the remaining carboxylic acid is neutralized with an alkali component such as sodium hydroxide or ammonia. (Meth) acrylic acid ester-based resin: at least one selected from polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, and their anhydrides Seed polybasic acid (poly) ethylene glycol,
One of the polybasic acids remaining in the polyester resin obtained by esterification with at least one polyhydric alcohol selected from polyhydric alcohols such as (poly) propylene glycol, trimethylolpropane, pentaerythritol, and sorbitol. Polyester resin obtained by neutralizing all or part of it with an alkali component such as sodium hydroxide or ammonia;
Aromatic, aliphatic or alicyclic diisocyanates or isocyanate oligomers derived therefrom, and polyhydric alcohols such as (poly) ethylene glycol, (poly) propylene glycol, trimethylolpropane, pentaerythritol and sorbitol, or bishydroxymethyl At least one alcohol compound selected from hydroxycarboxylic acids such as propionic acid and hydroxyacetic acid is subjected to a urethanization reaction, and part or all of the carboxylic acid remaining in the produced resin is sodium hydroxide or ammonia. Polyurethane resin neutralized with an alkali component such as vinyl acetate and at least one of (meth) acrylic acid 2-hydroxyethyl ester and (meth) acrylic acid 2-hydroxypropyl ester as a hydroxyl group component
Seed is an essential component, and in some cases, at least one unsaturated compound selected from unsaturated compounds such as (meth) acrylic acid, C ₁ -C ₁₂ alkyl ester of (meth) acrylic acid, and styrene is a comonomer. In the copolymer, a vinyl acetate resin obtained by neutralizing a part or all of the remaining carboxylic acid; an epoxy resin such as a condensate of epichlorohydrin and polyhydric phenol; a repeating unit of polyethylene glycol or ethylene oxide while,
Polyalkylene oxide polyol-based resin such as a compound in which polypropylene oxide, polytetramethylene oxide or the like is added to one end or both ends, or a compound in which ethylene oxide and propylene oxide or tetrahydrofuran are randomly polymerized; polyvinyl alcohol, or a hydroxyl group of polyvinyl alcohol Examples thereof include synthetic polymers obtained by esterifying a part of them with a carboxylic acid or sulfonic acid compound.

Examples of natural water-soluble polymers include natural water-soluble polymers such as methyl cellulose, hydroxyethyl cellulose and soluble starch. The water-dispersible polyol is a resin that is dispersible in water having a hydroxyl group, and is, for example, vinylidene chloride and (meth) acrylic acid 2-hydroxyethyl ester or (meth) acrylic acid 2-hydroxypropyl as a hydroxyl group component. At least one kind of ester or the like is used as an essential component, and in some cases, at least one selected from unsaturated compounds such as acrylonitrile, vinyl chloride, (meth) acrylic acid, and alkyl (meth) acrylate (C ₁ -C ₁₂ ) ester. Polyvinylidene chloride-based polyol in which a part or all of the remaining carboxylic acid is neutralized by emulsion polymerization with a kind of unsaturated compound, and vinyl chloride and 2-hydroxyethyl (meth) acrylate as a hydroxyl group component. ester,
At least one kind of (meth) acrylic acid 2-hydroxypropyl ester or the like is used as an essential component, and in some cases, acrylonitrile, (meth) acrylic acid, (meth) acrylic acid (C ₁ -C ₁₂ ) alkyl ester, acrylamide, etc. Of at least one unsaturated compound selected from the above unsaturated compounds to form a copolymer by emulsion polymerization to neutralize a part or all of the remaining carboxylic acid; a polyvinyl chloride polyol; vinyl acetate in an aqueous polyvinyl alcohol solution. Emulsion-polymerized vinyl acetate polyol with a catalyst; aromatic, aliphatic and / or alicyclic diisocyanates or isocyanate oligomers derived from them, and (poly) ethylene glycol, (poly) propylene glycol, trimethylolpropane, penta Erislit, Sorbito A polyhydric alcohol such as alcohol or at least one alcohol compound selected from hydroxycarboxylic acids such as bishydroxypropionic acid and hydroxyacetic acid, and subjected to a urethanization reaction, and a part of the remaining carboxylic acid or All-neutralized urethane-based polyols; (meth) acrylic acid C ₁ -C ₁₂ alkyl ester, (meth) acrylic acid-2-hydroxyethyl ester and (meth) acrylic acid-2-hydroxypropyl ester as hydroxyl group components Etc. as an essential component and, in some cases, residual carvone of the copolymer containing at least one unsaturated compound selected from unsaturated compounds such as (meth) acrylic acid, styrene and acrylamide as a comonomer. Acrylate-based polyol in which some or all of the acid is neutralized; vinyl fluoride Alkylidene, vinyl fluoride, chlorotrifluoroethylene, tetrafluoroethylene, (meth) fluoro acrylic acid (C ₁ -C ₁₂
At least one kind of a fluorine-containing unsaturated compound such as alkyl) ester, and (meth) acrylic acid 2-hydroxyethyl ester as a hydroxyl group component, (meth) acrylic acid 2
-At least one of hydroxypropyl ester and the like as an essential component, and in some cases, (meth) acrylic acid C ₁ -C ₁₂ alkyl ester, (meth) acrylic acid, ethyl vinyl ether, hydroxybutyl vinyl ether, and styrene Fluorine copolymer-based polyol obtained by neutralizing a part or all of the remaining carboxylic acid of a copolymer having at least one compound selected from saturated compounds as a comonomer; styrene and butadiene, and (meth) acryl as a hydroxyl group component. Acid 2-hydroxyethyl ester, at least one kind of (meth) acrylic acid 2-hydroxypropyl ester, etc. as an essential component, and in some cases, (meth) acrylic acid, acrylonitrile,
Styrene-butadiene copolymer-based polyol obtained by neutralizing a part or all of the remaining carboxylic acid of the copolymer having at least one unsaturated compound selected from unsaturated compounds such as acrylamide as a comonomer; hydroxyl group and carboxyl at the terminal Examples thereof include a polybutadiene-based polyol having a group and neutralizing a part or all of a carboxyl group; and a urethane acrylate-based polyol obtained by forming a core-shell structure of the above-mentioned acrylate-based polyol and urethane-based polyol.

The average particle size of the polyol of the water-based polyol emulsion is 0.01 to 1.0 μm. 0.0
When it is less than 1 μm, the viscosity of the water-based polyol emulsion increases, and the use is limited to a low nonvolatile content concentration, which is not preferable. When it exceeds 1.0 μm, the stability of water dispersion of the water-based polyol emulsion is deteriorated, which is not preferable.

The hydroxyl value of the polyol used in the present invention is
It is 1 to 300 mg KOH / g. If it is less than 1 mgKOH / g, the number of crosslinking points in the coating composition will decrease,
It is not preferable because it causes a decrease in the curing rate of the aqueous coating composition and the brittleness of the coating formed therefrom. On the other hand, when it exceeds 300 mgKOH / g, on the contrary, the coating is too hard and brittle because the crosslinking points are too many, which is not preferable.

In the present invention, the equivalent ratio of isocyanate group / hydroxyl group of the aqueous polyol of the component (A) and the highly emulsifying polyisocyanate composition of the component (B) is 0.5 to 5.0,
It is preferably 1.0 to 3.0. Below 0.5,
It is not preferable because the number of crosslinking points in the coating composition is reduced, the curing rate of the aqueous coating composition is reduced, and the coating formed from the composition becomes brittle. 5.
When it exceeds 0, the coating becomes too hard and brittle, which is not preferable. The amount of water in the above-mentioned component (A), the aqueous polyol, is 5 to 90% by weight based on the total weight of the polyol, water and, in some cases, the organic solvent.

The component (A) may contain an organic solvent. As the solvent used here, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, methanol, ethanol, i- Propanol,
Alcohol compounds such as n-butanol, n-hexanol and 2-ethylhexanol, ketone compounds such as acetone and methyl ethyl ketone, ethyl acetate, acetic acid n-butyl, ethyl glycol acetate, methoxypropyl acetate and isoacetic acid-3-hydroxy-2. Examples thereof include ester compounds such as 2,4-trimethylpentyl, ethers such as butyl glycol, tetrahydrofuran, dioxane, and ethyl glycol ether.

When the aqueous polyol as the component (A) contains an organic solvent, the amount of the organic solvent is up to 50% by weight based on the total weight of the polyol, water and the organic solvent. The water-based coating composition containing the component (A) and the component (B) preferably has a pot life at 20 ° C. for 6 hours or more. The pot life is the time during which no significant increase in viscosity or foaming is observed in the water-based coating composition. It cannot be said that it can withstand practical use in less than 6 hours. This long pot life
This can be achieved by the interaction of the ionic surfactant coexisting with the introduced nonionic hydrophilic group.

When a fresh coating film having a thickness of 40 μm and coated with the above water-based coating composition was left to stand at 20 ° C. and 65% relative humidity (RH) for 24 hours, the gel fraction of the coating film was It is preferably 50% or more. If it is less than 50%, the water resistance is poor, which is not preferable. The reason why a coating film having a gel fraction of 50% or more can be achieved is that the reaction between water and isocyanate groups is suppressed when the highly emulsifying polyisocyanate composition is dispersed in water. The highly emulsifying polyisocyanate composition of the present invention, and the water-based coating composition,
If necessary, a pigment, a dispersion stabilizer, a viscosity modifier, a leveling agent, a light stabilizer, an antioxidant, an ultraviolet absorber, a filler, a plasticizer, a lubricant, a curing accelerating catalyst and the like can be added.

The highly emulsifiable polyisocyanate composition of the present invention is not only excellent in water dispersibility, but also exhibits high stability by suppressing the reaction between the terminal isocyanate group of polyisocyanate and water in a water dispersed state. Furthermore, a room temperature crosslinkable two-component water-based urethane coating composition obtained by combining the above-mentioned polyisocyanate composition as a main agent with an aqueous polyol as a main agent is excellent in pot life, and moreover, a coating film excellent in water resistance etc. Can be formed. Therefore,
Such a water-based coating composition is mainly useful as a water-based paint for construction, a water-based paint for automobiles, a water-based paint for household use, an adhesive, a building material, other coating agent, a sealing agent, and further, a cross-linking agent for an ink vehicle. ,
Curing agent in cast molding, resin component such as elastomer,
It can be used as a cross-linking agent such as urethane foam and a treating agent for fibers and fabrics.

[0046]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following examples and comparative examples. Various properties in the following examples and comparative examples were measured by the following methods. (1) Measurement of isocyanate group content rate: The isocyanate group content rate is defined as the content rate (% by weight) of the isocyanate group contained in the polyisocyanate composition. Regarding the isocyanate group content, about 2 g of the polyisocyanate composition used as a sample was precisely weighed, 20 ml of toluene and 20 ml of a 2N toluene solution of n-dibutylamine were added,
After standing for 15 minutes at room temperature, back titration was carried out using 1N hydrochloric acid, and the value was calculated from the following formula. A bromocresol green indicator was used as the indicator. Isocyanate group content (wt%) = (blank titer-sample titer) × 42 / [sample weight (g) × 100
0] × 100%. However, the blank titer is the titer when the above operation is performed without adding the polyisocyanate composition.

(2) Measurement of the content of nonionic hydrophilic group: The content of the nonionic hydrophilic group is determined by the hydrophilic polyisocyanate [(a) component; Base polyisocyanate having hydrophilic groups bonded thereto] is defined as the nonionic hydrophilic group content (% by weight). The nonionic hydrophilic group content is measured by first measuring the intensity of the absorption peak of the infrared absorption spectrum (wavenumber based on ether group: 1,100 cm ^-1 ) of the highly emulsifying polyisocyanate composition sample to obtain a highly emulsifying polyisocyanate composition. The weight (X) of the nonionic hydrophilic group in the isocyanate composition is determined. On the other hand, the weight (Y) of the ionic surfactant in the highly emulsifying polyisocyanate composition unit is measured using liquid chromatography. When the weight of the sample highly emulsifying polyisocyanate composition is Z, it can be calculated by the following formula.

(3) Measurement of the hydroxyl value of the polyol: The hydroxyl value is the KOH required to neutralize the acetic acid necessary for acetylating the free OH groups contained in 1 g of the polyol.
Is defined as the amount (mg) of The hydroxyl value is measured according to JIS-
Perform according to K0070. (4) Measurement of acid value of polyol: Acid value is polyol 1
KOH required to neutralize free fatty acids contained in g
Is defined as the amount (mg) of The acid value is measured by JIS-K
Perform according to 0070.

(5) Measurement of nonvolatile content: In the present invention,
The term "nonvolatiles" is used in connection with compounds that produce nonionic hydrophilic groups (such as polyethylene glycol monomethyl ether), ionic surfactants, aqueous polyols, and highly emulsifiable polyisocyanate compositions. The nonvolatile content (weight) was measured by precisely weighing about 1.5 g of the sample and measuring 10 at normal pressure.
It is defined as the residual amount (weight) after heating at 5 ° C. for 1 hour. (6) Measurement of viscosity of highly emulsifiable polyisocyanate composition: Viscosity is measured at 25 ° C. (mPa ·
s) is defined. Viscosity was measured by a digital viscometer (DVM-B type, Tokyo Keiki Co., Ltd., Japan) at 25 ° C.
Perform at 60 rpm.

(7) Measurement of weight average molecular weight of highly emulsifiable polyisocyanate composition: The sample to be measured was prepared by subjecting the polyisocyanate composition to tetrahydrofuran (THF).
The solution (concentration of 0.25% by weight) is used. The weight average molecular weight was determined using gel permeation chromatography (GPC). When the weight average molecular weight of GPC is less than 2,000 (column: G1000HXL, G2000HXL, G3000HX manufactured by Tosoh Corp.)
L, carrier: THF, detection method: differential refractometer, data processor: Tosoh Corp. CP-8000), and weight average molecular weight of 2000 or more (column: Tosoh Corp.)
Made G2000HXL, G4000HXL, G5000H
XL, carrier: THF, detection method: differential refractometer, data processor: Chromatocode manufactured by Tosoh Corporation
It was measured using r21).

(8) Evaluation of water dispersibility of highly emulsifiable polyisocyanate composition: The water dispersibility was determined by mixing the highly emulsifiable polyisocyanate composition and water at a weight ratio of 40:60, and mixing at 10 rpm at 600 rpm. The aqueous dispersion (O / W type) prepared by stirring for 1 minute was left at 20 ° C. for 8 hours, and the dispersion state at that time was visually evaluated. When no precipitation was observed at all, the water dispersibility was determined to be good. (9) Measurement of average particle size of polyol in aqueous polyol emulsion: The average particle size is Microtrack UP.
A particle size analyzer (manufactured by Leeds + Northrup, USA: particle size distribution meter) was used for measurement.

(10) Measurement of gel fraction: What is gel fraction?
A water-based coating composition prepared by adding a predetermined amount of a highly emulsifying polyisocyanate composition to an aqueous polyol emulsion and stirring the mixture at 600 rpm for 10 minutes is obtained by curing at 20 ° C. and 65% relative humidity (RH) for 24 hours. It is defined as the gel fraction of the coating film. The gel fraction was adjusted to about 0.1 g of the coating film obtained by curing by 2 g of 50 g of acetone at 20 ° C.
It was extracted for 4 hours and calculated from the following formula. Gel fraction = (remaining amount of solid content when coating film is extracted with acetone for 24 hours / coating film weight) × 100 (%)

Example 1 Polyethylene glycol monomethyl ether (nonionic hydrophilic group-forming compound, MP
G-081, nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd. and ammonium alkylbenzenesulfonate (ionic surfactant, Newcol 210, nonvolatile content 50% by weight) %, Manufactured by Nippon Emulsifier Co., Ltd.) so as to have a nonvolatile content weight ratio of 3: 1, and volatile components [water and solvent (methanol)] of Newcol 210 were removed by vacuum distillation at 120 ° C. and 20 Torr. . Hexamethylene diisocyanate (HDI) type biuret type polyisocyanate (Duranate 24A-100, manufactured by Asahi Chemical Industry Co., Ltd.) (base polyisocyanate) 1,000 g
Then, 200 g of a mixture of polyethylene glycol monomethyl ether obtained above and ammonium alkylbenzene sulfonate was mixed, and a urethanization reaction was carried out at 90 ° C. for 2 hours. The obtained highly emulsifying polyisocyanate composition was a pale yellow liquid and had a nonionic hydrophilic group of 13.0.
%, The ionic surfactant was 4.2% by weight, the isocyanate group content was 18.5% by weight, the weight average molecular weight was 1,000, and the viscosity was 3,200 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was good, and the residual ratio of isocyanate groups was 90% when the aqueous dispersion was left at 20 ° C. for 6 hours.

Example 2 Polyethylene glycol monomethyl ether (nonionic hydrophilic group-forming compound, MP
G-081, nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd., and sodium dialkylsulfosuccinate (ionic surfactant, Newcor 290M, nonvolatile content 7)
0 wt% (manufactured by Nippon Emulsifier Co., Ltd.) was mixed so as to have a nonvolatile content weight ratio of 2: 1, and volatile content [water and solvent (methanol)] of Newcol 290M was obtained by vacuum distillation at 120 ° C. and 20 Torr. I removed it. HDI type biuret type polyisocyanate (Duranate 24A-10
0, manufactured by Asahi Kasei Co., Ltd. (base polyisocyanate) (1,000 g) and 300 g of a mixture of polyethylene glycol monomethyl ether and sodium dialkylsulfosuccinate obtained above were mixed, and urethanization reaction was carried out at 90 ° C. for 2 hours. The obtained highly emulsifying polyisocyanate composition was a pale yellow liquid, containing 16.7% by weight of a nonionic hydrophilic group, 7.7% by weight of an ionic surfactant, and an isocyanate group content of 16.6. Weight%, weight average molecular weight 1,100, viscosity 4,100 mPa · s
(25 ° C). When this highly emulsifying polyisocyanate composition was dispersed in water, the dispersibility was good, and the residual ratio of isocyanate groups was 93% when the aqueous dispersion was left at 20 ° C. for 6 hours.

Example 3 Polyethylene glycol monomethyl ether (nonionic hydrophilic group-forming compound, nonvolatile content 100% by weight, average number of repeating units of ethylene oxide = 48.5) and ammonium polyoxyethylene nonylphenyl ether sulfonate (Ionic surfactant, Newcol 560SF, non-volatile content 50% by weight,
Nippon Emulsifier (manufactured by Nippon Emulsion Co., Ltd.) was mixed at a weight ratio of non-volatile components of 4: 1 and the volatile components [water and solvent (methanol)] of Newcol 560SF were removed by vacuum distillation at 120 ° C. and 20 Torr. HDI-based biuret type polyisocyanate (Duranate 24A-100, manufactured by Asahi Kasei Corporation) (base polyisocyanate) 1,00
0 g and 30 g of a mixture of polyethylene glycol monomethyl ether obtained above and ammonium polyoxyethylene nonylphenyl ether sulfonate were mixed,
The urethanization reaction was performed at 0 ° C. for 2 hours. The obtained highly emulsifying polyisocyanate composition was a pale yellow liquid, containing 2.3% by weight of a nonionic hydrophilic group, 0.6% by weight of an ionic surfactant, and an isocyanate group content of 21.6%. Weight%, weight average molecular weight 880, viscosity 2,400 mP
It was a * s (25 degreeC). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was good, and the residual ratio of isocyanate groups was 91% when the aqueous dispersion was left at 20 ° C. for 6 hours.

Example 4 Polyethylene glycol monomethyl ether (nonionic hydrophilic group-forming compound, MP
G-130, nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 9.4, Nippon Emulsifier Co., Ltd.
And sodium polyoxyethylene tridecyl ether sulfonate (ionic surfactant, Newcol 13
05SN, non-volatile content 30% by weight, manufactured by Nippon Emulsifier Co., Ltd.
The non-volatile components in a weight ratio of 1: 1 and
Newcol 13 by vacuum distillation at 20 ° C and 20 Torr
The volatile matter (water and solvent (methanol)) of 05SN was removed. HDI-based biuret type polyisocyanate (Duranate 24A-100, manufactured by Asahi Kasei Corporation) (base polyisocyanate) 1,000 g, and 400 g of a mixture of the polyethylene glycol monomethyl ether and polyoxyethylene nonylphenyl ether ammonium sulfonate obtained above. Were mixed and the urethane reaction was carried out at 90 ° C. for 2 hours. The obtained highly emulsifying polyisocyanate composition was a pale yellow liquid, containing 16.6% by weight of a nonionic hydrophilic group, 14.3% by weight of an ionic surfactant, and an isocyanate group content of 14.9. Weight%, weight average molecular weight 2,000, viscosity 18,000 mPa · s
(25 ° C). When this highly emulsifying polyisocyanate composition was dispersed in water, the dispersibility was good, and the residual rate of isocyanate groups was 78% when the aqueous dispersion was left at 20 ° C. for 6 hours.

Example 5 Polyethylene glycol monomethyl ether (Nonionic hydrophilic group-forming compound, MP
G-081, nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd.) and benzyl ammonium salt [ionic surfactant, Texnol R5 (50), nonvolatile content 50. % By weight, manufactured by Nippon Emulsifier Co., Ltd.] so as to have a nonvolatile content weight ratio of 1: 1 and subjected to vacuum distillation at 120 ° C. and 20 Torr for volatile components of texnol R5 (50) [water and solvent (methanol)]. Excluded. HDI-based biuret type polyisocyanate (Duranate 24A-100,
Asahi Chemical Industry Co., Ltd.) (base polyisocyanate)
1,000 g and 300 g of the mixture of polyethylene glycol monomethyl ether and benzyl ammonium salt obtained above were mixed, and a urethanization reaction was carried out at 90 ° C. for 2 hours. The obtained highly emulsifying polyisocyanate composition,
It is a pale yellow liquid with a nonionic hydrophilic group of 13.0% by weight, an ionic surfactant of 11.5% by weight, an isocyanate group content of 16.4% by weight, and a weight average molecular weight of 95.
The viscosity was 0 and the viscosity was 4,000 mPa · s (25 ° C.).
When this highly emulsifying polyisocyanate composition was dispersed in water, the dispersibility was good, and the residual rate of isocyanate groups was 88% when the aqueous dispersion was left at 20 ° C. for 6 hours.

Example 6 Polyethylene glycol monomethyl ether (nonionic hydrophilic group-forming compound, MP
G-081, nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd. and ammonium alkylbenzenesulfonate (ionic surfactant, Newcol 210, nonvolatile content 50% by weight) %, Manufactured by Nippon Emulsifier Co., Ltd.) so as to have a nonvolatile content weight ratio of 5: 2, and volatile components (water and solvent (methanol)) of Newcol 210 were removed by vacuum distillation at 120 ° C. and 20 Torr. . HDI isocyanurate type polyisocyanate (Duranate TPA-
100, manufactured by Asahi Chemical Industry Co., Ltd. (base polyisocyanate) (1,000 g) and 700 g of the mixture of polyethylene glycol monomethyl ether and ammonium alkylbenzenesulfonate obtained above were mixed, and a urethanization reaction was carried out at 120 ° C. for 2 hours. The obtained highly emulsifying polyisocyanate composition was a pale yellow liquid, containing 33.3% by weight of nonionic hydrophilic groups and 1% of ionic surfactant.
3.3% by weight, isocyanate group content 11.4% by weight, weight average molecular weight 1,400, viscosity 9,600 m
Pa · s (25 ° C.). When this highly emulsifying polyisocyanate composition was dispersed in water, the dispersibility was good, and the residual ratio of isocyanate groups was 82% when the aqueous dispersion was left at 20 ° C. for 6 hours.

(Example 7) Polyethylene glycol monomethyl ether (nonionic hydrophilic group-forming compound, MP
G-130, nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 9.4, Nippon Emulsifier Co., Ltd.
(Manufactured by K.K.) and sodium dialkylsulfosuccinate (ionic surfactant, Newcol 290M, nonvolatile content 70% by weight, manufactured by Nippon Emulsifier Co., Ltd.) were mixed at a nonvolatile content weight ratio of 2: 1, and 120 ° C. The non-volatile components [water and solvent (methanol)] of Newcol 290M were removed by vacuum distillation at 20 Torr. HDI isocyanurate type polyisocyanate (Duranate TPA-10
0, Asahi Kasei Kogyo Co., Ltd. (base polyisocyanate) (1,000 g) and 300 g of a mixture of polyethylene glycol monomethyl ether and sodium dialkylsulfosuccinate obtained above were mixed, and a urethanization reaction was carried out at 100 ° C. for 2 hours. The obtained highly emulsifying polyisocyanate composition was a pale yellow liquid, containing 16.7% by weight of a nonionic hydrophilic group, 7.7% by weight of an ionic surfactant, and having an isocyanate group content of 16.6. Weight%, weight average molecular weight 1,100, viscosity 3,000 mPa · s
(25 ° C). When this highly emulsifying polyisocyanate composition was dispersed in water, the dispersibility was good, and the residual rate of isocyanate groups was 88% when the aqueous dispersion was left at 20 ° C. for 6 hours.

Example 8 Polyethylene glycol monomethyl ether (Nonionic hydrophilic group-forming compound, MP
G-081, nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd., and sodium dialkylsulfosuccinate (ionic surfactant, Newcor 290M, nonvolatile content 7)
0% by weight, manufactured by Nippon Emulsifier Co., Ltd., was mixed so that the weight ratio of nonvolatile components was 3: 2, and the mixture was added at 120 ° C. and 20 Torr.
The volatile matter [water and solvent (methanol)] of Newcol 290M was removed by vacuum distillation. HDI urethane type polyisocyanate (Duranate E-402, Asahi Kasei Corporation) (base polyisocyanate) 1,
000 g and 150 g of a mixture of polyethylene glycol monomethyl ether obtained above and sodium dialkylsulfosuccinate were mixed, and a urethanization reaction was carried out at 100 ° C. for 2 hours. The obtained highly emulsifying polyisocyanate composition was a pale yellow liquid, containing 8.3% by weight of a nonionic hydrophilic group, 5.2% by weight of an ionic surfactant, and an isocyanate group content of 7.9. % By weight, weight average molecular weight 3,600, viscosity 15,000 mPa · s (25
℃). When this highly emulsifying polyisocyanate composition is dispersed in water, the dispersibility is good.
When left for 6 hours, the residual rate of isocyanate groups was 9
4%.

Example 9 Polyethylene glycol monomethyl ether (nonionic hydrophilic group-forming compound, MP
G-081, nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd., and sodium dialkylsulfosuccinate (ionic surfactant, Newcor 290M, nonvolatile content 7)
0% by weight, manufactured by Nippon Emulsifier Co., Ltd.) in a solid content weight ratio of 2:
The mixture was mixed so as to be 1, and the volatile component [water and solvent (methanol)] of Newcol 290M was removed by vacuum distillation at 120 ° C. and 20 Torr. HDI / isophorone diisocyanate (IPDI) mixed system biuret type polyisocyanate (Duranate 21S-75E, non-volatile content 75% ethyl acetate solution, manufactured by Asahi Kasei Kogyo KK) (base polyisocyanate) 1,000 g and polyethylene glycol obtained from the above Mix 250 g of a mixture of monomethyl ether and sodium dialkyl sulfosuccinate,
The urethane reaction was carried out at 90 ° C. for 5 hours. The obtained highly emulsifying polyisocyanate composition is a pale yellow liquid,
The nonionic hydrophilic group was 14.3% by weight, the ionic surfactant was 6.7% by weight, and the nonvolatile content was 84.2%.
Isocyanate group content at 100% non-volatile content is 1
3.4% by weight, weight average molecular weight 2,300, viscosity 1
It was 8,000 mPa · s (25 ° C.), the isocyanate group content was 11.3 wt% and the viscosity was 2,200 mPa · s (25 ° C.) in the state of containing the organic solvent.
When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was good, and the residual ratio of isocyanate groups was 90% when the aqueous dispersion was left at 20 ° C. for 6 hours.

Example 10 Polyethylene glycol monomethyl ether (Nonionic hydrophilic group-forming compound, M
PG-081, nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd. and sodium dialkylsulfosuccinate (ionic surfactant, Newcor 290M, nonvolatile content 7)
0 wt% (manufactured by Nippon Emulsifier Co., Ltd.) was mixed so as to have a nonvolatile content weight ratio of 2: 1, and volatile content [water and solvent (methanol)] of Newcol 290M was obtained by vacuum distillation at 120 ° C. and 20 Torr. I removed it. HDI type biuret type polyisocyanate (Duranate 24A-10
0, Asahi Kasei Kogyo Co., Ltd. (base polyisocyanate) (26 g) and 400 g of a mixture of polyethylene glycol monomethyl ether and sodium dialkylsulfosuccinate obtained above were mixed, and urethanization reaction was performed at 90 ° C. for 2 hours. 1,000 g of -100 was added, and urethanization reaction was performed at 90 ° C. for 2 hours. The obtained highly emulsifying polyisocyanate composition was a pale yellow liquid, containing 20.6% by weight of a nonionic hydrophilic group, 9.4% by weight of an ionic surfactant, and having an isocyanate group content of 15.0%. Wt%, weight average molecular weight is 1,3
00, the viscosity was 6,000 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was very good, and the residual ratio of isocyanate groups was 90% when the aqueous dispersion was left at 20 ° C. for 6 hours.

Example 11 Polyethylene glycol monomethyl ether (Nonionic hydrophilic group-forming compound, M
PG-081, nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd. and sodium dialkylsulfosuccinate (ionic surfactant, Newcor 290M, nonvolatile content 7)
0 wt% (manufactured by Nippon Emulsifier Co., Ltd.) was mixed so as to have a nonvolatile content weight ratio of 2: 1, and volatile content [water and solvent (methanol)] of Newcol 290M was obtained by vacuum distillation at 120 ° C. and 20 Torr. I removed it. HDI 1,000
g, 7.1 g of water, and 60 g of a mixture of polyethylene glycol monomethyl ether obtained above and sodium dialkylsulfosuccinate were mixed, and urethanization reaction and biuretization reaction were performed at 160 ° C. for 1 hour.

Using the falling film distillation apparatus, the first 0.
3 Torr (150 ° C), second time 0.2 Torr (15
(0 ° C.) to remove unreacted HDI. The obtained highly emulsifying polyisocyanate composition was a pale yellow liquid, yield 25.2%, nonionic hydrophilic group 16.1% by weight, ionic surfactant 7.4% by weight, isocyanate The group content was 17.6% by weight, the weight average molecular weight was 900, and the viscosity was 2,000 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was very good, and the residual rate of isocyanate groups was 91% when the aqueous dispersion was left at 20 ° C. for 6 hours.

Example 12 Polyethylene glycol monomethyl ether (Nonionic hydrophilic group-forming compound, M
PG-081, nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd. and sodium dialkylsulfosuccinate (ionic surfactant, Newcor 290M, nonvolatile content 7)
0 wt% (manufactured by Nippon Emulsifier Co., Ltd.) was mixed so as to have a nonvolatile content weight ratio of 2: 1 and the volatile components [water and solvent (methanol)] of Newcol 290M were removed by vacuum distillation at 120 ° C. and 20 Torr. It was HDI 1,000g
Then, 60 g of a mixture of polyethylene glycol monomethyl ether and sodium dialkylsulfosuccinate obtained above was mixed and subjected to urethanization reaction at 90 ° C. for 2 hours, and then the refractive index of the reaction solution was measured to be 1.4493. At 90 ° C., 0.05 g of tetramethylammonium caprate as an isocyanurate-forming catalyst was added. Four
After the lapse of time, when the refractive index of the reaction solution reached 1.4593 (that is, the difference Δ in the refractive index from that before the isocyanurate-forming reaction).
At a RI of 0.01), 0.2 g of phosphoric acid was added to stop the reaction.

Using the falling film distillation apparatus, the first 0.
3 Torr (150 ° C), second time 0.2 Torr (15
(0 ° C.) to remove unreacted HDI. The obtained highly emulsifying polyisocyanate composition was a pale yellow liquid, yield 28.2%, nonionic hydrophilic group 14.3% by weight, ionic surfactant 6.7% by weight, isocyanate The group content was 17.3% by weight, the weight average molecular weight was 950, and the viscosity was 2050 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was very good, and the residual rate of isocyanate groups was 91% when the aqueous dispersion was left at 20 ° C. for 6 hours.

Example 13 Polyethylene glycol monomethyl ether (Nonionic hydrophilic group-forming compound, M
PG-081, nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd. and sodium dialkylsulfosuccinate (ionic surfactant, Newcor 290M, nonvolatile content 7)
0 wt% (manufactured by Nippon Emulsifier Co., Ltd.) was mixed so as to have a nonvolatile content weight ratio of 2: 1, and volatile content [water and solvent (methanol)] of Newcol 290M was obtained by vacuum distillation at 120 ° C. and 20 Torr. I removed it. HDI 1,000
g and trifunctional polypropylene glycol (EXCENOL 8
40, manufactured by Asahi Glass Co., Ltd., 150 g, and 110 g of a mixture of polyethylene glycol monomethyl ether and sodium dialkylsulfosuccinate obtained above,
After carrying out the urethanization reaction at 90 ° C. for 2 hours, the refractive index of the reaction solution was measured and found to be 1.4496. 90 ° C
Then, 0.05 g of tetramethylammonium caprate as an isocyanurate-forming catalyst was added. After 4 hours, 0.2 g of phosphoric acid was added at the time when the refractive index of the reaction solution reached 1.4596 (that is, when the difference ΔRI in refractive index between before the isocyanurate-forming reaction became 0.01). The reaction was stopped.

Using the falling film distillation apparatus, the first 0.
3 Torr (150 ° C), second time 0.2 Torr (15
(0 ° C.) to remove unreacted HDI. The obtained highly emulsifying polyisocyanate composition was a pale yellow liquid, yield 46.2%, nonionic hydrophilic group 13.4% by weight, ionic surfactant 6.3% by weight, isocyanate The group content was 17.3 wt%, the weight average molecular weight was 1600, and the viscosity was 2000 mPa · s (25 ° C.). When this highly emulsifying polyisocyanate composition was dispersed in water, the dispersibility was very good, and the residual rate of isocyanate groups was 93% when the aqueous dispersion was left at 20 ° C. for 6 hours.

Example 14 Polyethylene glycol monomethyl ether (Nonionic hydrophilic group-forming compound, M
PG-081, non-volatile content 100% by weight, average number of ethylene oxide repeating units = 15.2, manufactured by Nippon Emulsifier Co., Ltd. and quaternary ammonium salt (ionic surfactant, Texnol SF, non-volatile content 100 weight) %, Manufactured by Nippon Emulsifier Co., Ltd., were mixed so that the nonvolatile content weight ratio was 3: 1. HDI-based biuret type polyisocyanate (Duranate 24A-100, manufactured by Asahi Chemical Industry Co., Ltd., Japan) (base polyisocyanate) (1000 g) and polyethylene glycol monomethyl ether obtained above and 200 g of a quaternary ammonium salt mixture, The urethane reaction was carried out at 90 ° C. for 2 hours. The obtained highly emulsifying polyisocyanate composition was a pale yellow liquid, containing 13.0% by weight of a nonionic hydrophilic group, 4.2% by weight of an ionic surfactant, and having an isocyanate group content of 1%.
8.7% by weight, weight average molecular weight 950, viscosity 2,8
It was 00 mPa · s (25 ° C.). When this highly emulsifying polyisocyanate composition was dispersed in water, the dispersibility was good, and the residual rate of isocyanate groups was 85% when the aqueous dispersion was left at 20 ° C. for 6 hours.

Example 15 To 100 g of the highly emulsifying polyisocyanate composition obtained in Example 1, 100 g of butyl acetate as an organic solvent was added. The obtained highly emulsifying polyisocyanate composition was a pale yellow liquid, containing 6.5% by weight of a nonionic hydrophilic group, 2.1% by weight of an ionic surfactant, and an isocyanate at a nonvolatile content of 100%. Group content is 18.4% by weight, weight average molecular weight is 100
0, the viscosity was 3,200 mPa · s (25 ° C.), the isocyanate content rate when the organic solvent was contained was 9.2 wt%, and the viscosity was 14 mPa · s (25 ° C.). When this highly emulsifying polyisocyanate composition was dispersed in water, the dispersibility was very good, and the residual ratio of isocyanate groups was 96% when the aqueous dispersion was left at 20 ° C. for 6 hours.

(Example 16) To 160 g of the highly emulsifiable polyisocyanate composition obtained in Example 2, 40 g of methoxypropyl acetate as an organic solvent was added. The obtained highly emulsifying polyisocyanate composition was a pale yellow liquid, containing 13.4% by weight of a nonionic hydrophilic group, 6.2% by weight of an ionic surfactant, and 100% of a nonvolatile content. The group content is 16.6% by weight, the weight average molecular weight is 1,100, and the viscosity is 4,100 mPa · s (25
C.), the isocyanate group content in the state of containing an organic solvent is 13.3% by weight, and the viscosity is 270 mPa · s.
(25 ° C). When this highly emulsifying polyisocyanate composition was dispersed in water, the dispersibility was very good, and the residual ratio of isocyanate groups was 94% when the aqueous dispersion was left at 20 ° C. for 6 hours.

Example 17 To 190 g of the highly emulsifying polyisocyanate composition obtained in Example 1, 10 g of diethylene glycol diacetate as an organic solvent was added. The obtained highly emulsifying polyisocyanate composition was a pale yellow liquid, containing 12.4% by weight of a nonionic hydrophilic group, 4.0% by weight of an ionic surfactant, and 10% by weight of non-volatile content.
The isocyanate group content at 0% is 18.4% by weight,
Weight average molecular weight is 1,000 and viscosity is 3,200 mPa.
-S (25 ° C), the isocyanate group content in the state containing the organic solvent was 17.6% by weight, and the viscosity was 2,300 mPa · s (25 ° C). When this highly emulsifying polyisocyanate composition was dispersed in water, the dispersibility was very good, and the residual ratio of isocyanate groups was 94% when the aqueous dispersion was left at 20 ° C. for 6 hours.

Example 18 To 160 g of the highly emulsifying polyisocyanate composition obtained in Example 2, 40 g of diethylene glycol diethyl ether as an organic solvent was added. The obtained highly emulsifying polyisocyanate composition,
It is a pale yellow liquid, containing 13.4% by weight of nonionic hydrophilic groups, 6.2% by weight of ionic surfactant, and 10% non-volatile content.
The isocyanate group content at 0% is 16.6% by weight,
Weight average molecular weight is 1,100, viscosity is 4,100 mPa.
・ S (25 ° C.), the isocyanate group content in the state containing an organic solvent is 13.3% by weight, and the viscosity is 3
It was 00 mPa · s (25 ° C.). When this highly emulsifiable polyisocyanate composition was dispersed in water, the dispersibility was remarkably good, and the residual ratio of isocyanate groups when the aqueous dispersion was left at 20 ° C. for 6 hours was 92%.

Example 19 Acrylate polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 20.9 / 17.4 / 2
6.0 / 34.8 / 0.9 (weight ratio) copolymer, hydroxyl value 160 mgKOH / g, acid value 6 mgKOH / g, glass transition temperature (Tg) 25 ° C; latex: non-volatile content 40
Weight%, pH adjusted to 5 with ammonia, average particle size 0.0
9 μm] and the highly emulsifying polyisocyanate composition obtained in Example 1 were mixed at an NCO / OH equivalent ratio of 0.5 to obtain an aqueous coating composition. The water-based coating composition had no increase in viscosity and no foaming even after standing at 20 ° C. for 8 hours. Using this coating composition, a thickness of 40μ
2m at 20 ℃ 65% relative temperature (RH)
After curing for 4 hours, a transparent coating film was obtained. The gel fraction was measured to be 79%, and no whitening of the coating film was observed even after immersion in water at 20 ° C. for 4 hours.

Example 20 Acrylate polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 17.9 / 32.1 / 4
4.6 / 4.5 / 0.9 (weight ratio) copolymer, hydroxide value 20 mgKOH / g, acid value 6 mgKOH / g, Tg10
° C; latex: non-volatile content 30% by weight, p with ammonia
H5 was adjusted and the average particle diameter was 0.08 μm] and the highly emulsifying polyisocyanate composition obtained in Example 2 were mixed at an NCO / OH equivalent ratio of 1.5 to obtain an aqueous coating composition.
The water-based coating composition had no increase in viscosity and no foaming even after standing at 20 ° C. for 8 hours. A coating film having a thickness of 40 μm is prepared using this coating composition, and the temperature is 20 ° C.
When cured at 65% RH for 24 hours, a transparent coating film was obtained. The gel fraction measured was 84%, and no whitening of the coating film was observed even after immersion in water at 20 ° C. for 4 hours.

(Example 21) Acrylate polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 9.2 / 44.0 / 45.
8 / 0.9 / 0.1 (weight ratio) copolymer, hydroxyl value 4m
gKOH / g, acid value 1 mgKOH / g, Tg 10 ° C .; latex: non-volatile content 40% by weight, pH adjusted to 5 with ammonia, average particle diameter 0.2 μm] and the highly emulsifying polyisocyanate composition obtained in Example 6 / OH equivalent ratio =
The mixture was mixed at 5.0 to obtain an aqueous coating composition. The water-based coating composition had no increase in viscosity and no foaming even after standing at 20 ° C. for 8 hours. A coating film having a thickness of 40 μm was prepared using this coating composition, and the temperature was 65% at 20 ° C.
When it was cured at RH for 24 hours, a transparent coating film was obtained. The gel fraction was measured to be 70%, and no whitening of the coating film was observed even after immersion in water at 20 ° C. for 4 hours.

Example 22 Fluorine-based polyol latex (polyol: hydroxide value 10 mgKOH / g, acid value 2)
mgKOH / g, Tg 0 ° C .; latex: non-volatile component 3
5% by weight, average particle diameter 0.1 μm) and the highly emulsifying polyisocyanate composition obtained in Example 2 were mixed at an NCO / OH equivalent ratio = 1.5 to obtain an aqueous coating composition. The water-based coating composition had no increase in viscosity and no foaming even after standing at 20 ° C. for 8 hours. A coating film having a thickness of 40 μm was prepared using this coating composition, and the coating film was prepared at 20 ° C.
After curing at% RH for 24 hours, a transparent coating film was obtained. The gel fraction measured was 77%, and no whitening of the coating film was observed even after immersion in water at 20 ° C. for 4 hours.

(Example 23) Acrylate polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 17.9 / 32.1 / 4
4.6 / 4.5 / 0.9 (weight ratio) copolymer, hydroxide value 20 mgKOH / g, acid value 6 mgKOH / g, Tg10
° C; latex: non-volatile content 30% by weight, p with ammonia
H5, average particle size 0.08 μm] and the highly emulsifying polyisocyanate composition obtained in Example 10 was added to NCO / OH.
Equivalent ratio = 1.5 was mixed to obtain an aqueous coating composition. The water-based coating composition had no increase in viscosity and no foaming even after standing at 20 ° C. for 8 hours. Using this coating composition, a coating film having a thickness of 40 μm was prepared.
When cured at 0 ° C. and 65% RH for 24 hours, a transparent coating film was obtained. The gel fraction measured was 84%, and no whitening of the coating film was observed even after immersion in water at 20 ° C. for 4 hours.

Example 24 Acrylate polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 17.9 / 32.1 / 4
4.6 / 4.5 / 0.9 (weight ratio) copolymer, hydroxide value 20 mgKOH / g, acid value 6 mgKOH / g, Tg10
° C; latex: non-volatile content 30% by weight, p with ammonia
H5, average particle size 0.08 μm] and the highly emulsifying polyisocyanate composition obtained in Example 11 was added to NCO / OH.
Equivalent ratio = 1.5 was mixed to obtain an aqueous coating composition. The water-based coating composition had no increase in viscosity and no foaming even after standing at 20 ° C. for 8 hours. Using this coating composition, a coating film having a thickness of 40 μm was prepared.
When cured at 0 ° C. and 65% RH for 24 hours, a transparent coating film was obtained. The gel fraction measured was 82%, and no whitening of the coating film was observed even after immersion in water at 20 ° C. for 4 hours.

(Example 25) Acrylate polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 17.9 / 32.1 / 4
4.6 / 4.5 / 0.9 (weight ratio) copolymer, hydroxide value 20 mgKOH / g, acid value 6 mgKOH / g, Tg10
° C; latex: non-volatile content 30% by weight, p with ammonia
H5, average particle size 0.08 μm] and the highly emulsifying polyisocyanate composition obtained in Example 13 was added to NCO / OH.
Equivalent ratio = 1.5 was mixed to obtain an aqueous coating composition. The water-based coating composition had no increase in viscosity and no foaming even after standing at 20 ° C. for 8 hours. Using this coating composition, a coating film having a thickness of 40 μm was prepared.
When cured at 0 ° C. and 65% RH for 24 hours, a transparent coating film was obtained. The gel fraction was 81% as measured, and no whitening of the coating film was observed even after immersion in water at 20 ° C. for 4 hours.

(Example 26) Acrylate polyol latex [Polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / -2- (dimethylamino) ethyl methacrylate = 6.3 / 31 9.9 / 32.5 / 23.1 / 6.2
(Weight ratio) of copolymer, hydroxyl value 100 mgKOH / g,
Tg 25 ° C .; latex: non-volatile content 45% by weight, pH adjusted to 5 with ammonia, average particle size 0.10 μm] and the highly emulsifying polyisocyanate composition obtained in Example 14 were NC.
An O / OH equivalent ratio = 1.5 was mixed to obtain an aqueous coating composition. The water-based coating composition had no increase in viscosity and no foaming even after standing at 20 ° C. for 8 hours. A coating film having a thickness of 40 μm was formed using this coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction measured is 84%, which is 20
No whitening of the coating film was observed even after immersion in water at ℃ for 4 hours.

(Example 27) Acrylate polyol latex [Polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 17.9 / 32.1 / 4
4.6 / 4.5 / 0.9 (weight ratio) copolymer, hydroxide value 20 mgKOH / g, acid value 6 mgKOH / g, Tg10
° C; latex: non-volatile content 30% by weight, p with ammonia
H5, average particle size 0.08 μm] and the highly emulsifying polyisocyanate composition obtained in Example 16 was added to NCO / OH.
Equivalent ratio = 1.5 was mixed to obtain an aqueous coating composition. The water-based coating composition had no increase in viscosity and no foaming even after standing at 20 ° C. for 8 hours. Using this coating composition, a coating film having a thickness of 40 μm was prepared.
When cured at 0 ° C. and 65% RH for 24 hours, a transparent coating film was obtained. The gel fraction was measured to be 80%, and no whitening of the coating film was observed even after immersion in water at 20 ° C. for 4 hours.

Example 28 An aqueous solution of polyvinyl alcohol as a polyol (polyol: hydroxyl value 300 m
gKOH / g; aqueous solution: non-volatile content 40% by weight) with the highly emulsifying polyisocyanate composition obtained in Example 1 in NCO /
The OH equivalent ratio = 0.5 was mixed to obtain a water-soluble coating composition. This water-soluble coating composition has a temperature of 20 ° C.
No viscosity increase or foaming was observed even after standing for a time. A coating film having a thickness of 40 μm was prepared using this water-soluble coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction measured was 91%, and no whitening of the coating film was observed even after immersion in water at 20 ° C. for 4 hours.

(Example 29) Aqueous solution of polyethylene glycol as polyol (polyol: hydroxyl value 20 m
gKOH / g; aqueous solution: non-volatile content 45% by weight) with the highly emulsifiable polyisocyanate composition obtained in Example 1 in NCO /
The OH equivalent ratio = 1.5 was mixed to obtain a water-soluble coating composition. This water-soluble coating composition has a temperature of 20 ° C.
No viscosity increase or foaming was observed even after standing for a time. A coating film having a thickness of 40 μm was prepared using this water-soluble coating composition and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. The gel fraction was 88% as measured, and no whitening of the coating film was observed even after immersion in water at 20 ° C. for 4 hours.

(Example 30) Acrylic polyol resin aqueous solution [polyol resin: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate = 22.2 / 65.6 / 6.7 / 5.5
(Weight ratio) copolymer, acid value 35 mgKOH / g, hydroxyl value 20 mgKOH / g; aqueous solution: non-volatile content 42% by weight]
The highly emulsifiable polyisocyanate composition obtained in Example 2 was mixed with NCO / OH equivalent ratio = 1.5 to obtain a water-soluble coating composition. This water-soluble coating composition,
Even when left at 20 ° C. for 8 hours, viscosity increase and foaming were not observed. Using this water-soluble coating composition, a thickness of 40
A μm coating film was formed and cured at 20 ° C. and 65% RH for 24 hours to obtain a transparent coating film. Measure the gel fraction 9
It was 0%, and whitening of the coating film was not observed even when immersed in water at 20 ° C. for 4 hours.

(Example 31) An aqueous solution of polyvinyl alcohol as a polyol (polyol: hydroxyl value 300 m
gKOH / g; aqueous solution: non-volatile content 40% by weight), the highly emulsifying polyisocyanate composition obtained in Example 2 was diluted with butyl acetate to a non-volatile content 75% by weight, and NCO / OH was added.
The mixture was mixed at an equivalence ratio of 0.5 to obtain a water-soluble coating composition. With this water-soluble coating composition, no increase in viscosity and no foaming were observed even after standing at 20 ° C. for 8 hours. When a coating film having a thickness of 40 μm was prepared using this water-soluble coating composition and cured at 20 ° C. and 65% RH for 24 hours,
A transparent coating film was obtained. The gel fraction measured is 89%,
No whitening of the coating film was observed even after immersion in water at 20 ° C. for 4 hours.

(Comparative Example 1) 150 g of polyethylene glycol monomethyl ether (nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 20.4) and isocyanurate type polyisocyanate (Duranate TPA-100, Asahi Chemical Industry Co., Ltd.) (Manufactured by) (base polyisocyanate) 1,000 g, and mixed at 100 ° C. for 2
The urethane reaction was carried out for an hour. The obtained polyisocyanate composition was a pale yellow liquid, containing 13.0% by weight of a nonionic hydrophilic group, 0% by weight of an ionic surfactant, an isocyanate group content of 18.7% by weight, and a weight average. The molecular weight is 1,300 and the viscosity is 2,800 mPa · s (25
℃). When this polyisocyanate composition was dispersed in water, the dispersibility was good, but when the aqueous dispersion was left at 20 ° C. for 4 hours, the residual rate of isocyanate groups was 0%.

Comparative Example 2 Polyethylene glycol monomethyl ether (MPG-081, non-volatile content 100% by weight, average number of ethylene oxide repeating units = 15.
Two, 200 g of Nippon Emulsifier Co., Ltd. and biuret type polyisocyanate (Duranate 24A-100,
Asahi Chemical Industry Co., Ltd.) (base polyisocyanate)
1,000 g was mixed and a urethanization reaction was carried out at 90 ° C. for 2 hours. The obtained polyisocyanate composition was a pale yellow liquid, containing 16.7% by weight of a nonionic hydrophilic group, 0% by weight of an ionic surfactant, an isocyanate group content of 18.3% by weight, and a weight average. The molecular weight was 1,200 and the viscosity was 2,300 mPa · s (25 ° C.). When this polyisocyanate composition was dispersed in water, the dispersibility was good, but the residual rate of isocyanate groups was 0% when the aqueous dispersion was left for 2 hours at 20 ° C.

Comparative Example 3 150 g of polyethylene glycol monomethyl ether (nonvolatile content 100% by weight, average number of ethylene oxide repeating units = 20.4) and isocyanurate type polyisocyanate (Duranate THA-100, Asahi Kasei Kogyo KK) (Manufactured by Japan) (base polyisocyanate) (1,000 g) and ricinoleic acid methyl ester (40 g) were mixed, and a urethanization reaction was carried out at 100 ° C. for 2 hours. The resulting polyisocyanate composition,
It is a pale yellow liquid and has a nonionic hydrophilic group of 12.6% by weight, an ionic surfactant of 0% by weight, an isocyanate group content of 16.7% by weight, and a weight average molecular weight of 1,50.
The viscosity was 0, and the viscosity was 2,300 mPa · s (25 ° C.).
When this polyisocyanate composition was dispersed in water, the dispersibility was good, but when the aqueous dispersion was left at 20 ° C. for 4 hours, the residual rate of isocyanate groups was 0%.

Comparative Example 4 Acrylate polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 17.9 / 32.1 / 44.
6 / 4.5 / 0.9 (weight ratio) copolymer, hydroxyl value 20
mgKOH / g, acid value 6 mgKOH / g, Tg10 ° C;
Latex: nonvolatile content 30% by weight, pH 5 with ammonia
The average particle size was adjusted to 0.08 μm] and the polyisocyanate composition obtained in Comparative Example 1 was used in an NCO / OH equivalent ratio = 1.5.
To obtain an aqueous coating composition. This aqueous coating composition solidified when left at 20 ° C. for 6 hours.
When a coating film having a thickness of 40 μm was prepared using this coating composition and cured at 20 ° C. and 65% RH for 24 hours,
A slightly hazy coating film was obtained. The gel fraction is 81
%, And the coating film was whitened when immersed in water at 20 ° C. for 4 hours.

Comparative Example 5 Acrylate polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 17.9 / 32.1 / 44.
6 / 4.5 / 0.9 (weight ratio) copolymer, hydroxyl value 20
mgKOH / g, acid value 6 mgKOH / g, Tg10 ° C;
Latex: nonvolatile content 30% by weight, pH 5 with ammonia
The average particle diameter was adjusted to 0.08 μm] and the polyisocyanate composition obtained in Comparative Example 2 was used in an NCO / OH equivalent ratio = 1.0.
To obtain an aqueous coating composition. This aqueous coating composition solidified when left at 20 ° C. for 6 hours.
When a coating film having a thickness of 40 μm was prepared using this coating composition and cured at 20 ° C. and 65% RH for 24 hours,
A transparent coating film was obtained. The gel fraction measured is 84%,
When it was immersed in water at 20 ° C. for 4 hours, the coating film was swollen and whitened.

Comparative Example 6 Acrylate polyol latex [polyol: styrene / methyl methacrylate / n-butyl acrylate / 2-hydroxymethyl acrylate / methacrylic acid = 17.9 / 32.1 / 44.
6 / 4.5 / 0.9 (weight ratio) copolymer, hydroxyl value 20
mgKOH / g, acid value 6 mgKOH / g, Tg10 ° C;
Latex: nonvolatile content 30% by weight, pH 5 with ammonia
The average particle diameter was adjusted to 0.08 μm] and the polyisocyanate composition obtained in Comparative Example 3 was used in an NCO / OH equivalent ratio = 1.0.
To obtain an aqueous coating composition. This aqueous coating composition solidified when left at 20 ° C. for 6 hours.
When a coating film having a thickness of 40 μm was prepared using this coating composition and cured at 20 ° C. and 65% RH for 24 hours,
A transparent coating film was obtained. The gel fraction measured is 86%,
When it was immersed in water at 20 ° C. for 4 hours, the coating film was swollen and whitened.

(Comparative Example 7) An aqueous solution of polyvinyl alcohol (hydroxide value 20 mgKOH / g) having a nonvolatile content of 40% and the polyisocyanate composition obtained in Comparative Example 2 were mixed at an NCO / OH equivalent ratio of 1.5 to prepare an aqueous solution. A coating composition was obtained. This water-soluble coating composition foamed at 20 ° C. for 3 hours, and an increase in viscosity was observed. A coating film having a thickness of 40 μm is prepared using this water-soluble coating composition,
When it was cured at 20 ° C. and 65% RH for 24 hours, a thin cloudy coating film was obtained. The gel fraction was measured to be 80%, and when immersed in water at 20 ° C. for 4 hours, the entire coating film became slightly white.

[0094]

INDUSTRIAL APPLICABILITY The highly emulsifying polyisocyanate composition of the present invention is not only excellent in water dispersibility, but also exhibits high stability in the water dispersed state by suppressing the reaction between the terminal isocyanate group of polyisocyanate and water. . Furthermore, a room temperature crosslinkable two-component water-based urethane coating composition obtained by combining the above-mentioned polyisocyanate composition as a main agent with an aqueous polyol as a main agent is excellent in pot life, and moreover, a coating film excellent in water resistance etc. Can be formed. Therefore, such a water-based coating composition is mainly useful as a water-based paint for construction, a water-based paint for automobiles, a water-based paint for household use, an adhesive, a building material, other coating agents, and a sealing agent. It can be used as a cross-linking agent, a curing agent in cast molding, a resin component such as an elastomer, a cross-linking agent such as urethane foam, a treatment agent for fibers and fabrics.

Claims (15)

[Claims] 1. At least one base polyisocyanate selected from the group consisting of (a) an aliphatic diisocyanate, an alicyclic diisocyanate, and a polyisocyanate having two or more terminal isocyanate groups derived therefrom, and A hydrophilic polyisocyanate comprising a nonionic hydrophilic group containing an average of 5 to 50 ethylene oxide repeating units bonded to the base polyisocyanate, wherein the hydrophilic group is one of the base polyisocyanate and the hydrophilic group. 2 to 50% by weight of the total weight of the hydrophilic polyisocyanate, and (b)
0.5 to the total weight of component (a) and component (b)
A polyisocyanate composition comprising 20% by weight of a substantially water-free ionic surfactant. 2. A polyisocyanate composition having a nonvolatile content of substantially 100%, having an isocyanate group content of 3 to 25% by weight, a weight average molecular weight of 350 to 10,000, and a viscosity of 50-20,000m
Pa * s (25 degreeC), The polyisocyanate composition of Claim 1 characterized by the above-mentioned. 3. The polyisocyanate composition according to claim 1, further comprising 1 to 50% by weight of an organic solvent based on the total weight of the polyisocyanate composition and the organic solvent. Stuff. 4. The organic solvent is at least one compound selected from the group consisting of polyethylene glycol di (C ₁ -C ₁₀ ) alkyl ether and polyethylene glycol dicarboxylate.
The polyisocyanate composition described. 5. The polyisocyanate composition according to claim 1, wherein the at least one diisocyanate is selected from the group consisting of hexamethylene diisocyanate and isophorone diisocyanate. 6. The base polyisocyanate is at least one selected from the group consisting of polyisocyanates each having a biuret structure, an isocyanurate structure, a urethane structure, a uretdione structure and an allophanate structure in the molecule. Claim 1 to
6. The polyisocyanate composition according to any one of 5 above. 7. The polyisocyanate composition according to claim 1, wherein the ionic surfactant is anionic. 8. The anionic surfactant is C ₁ -C.
Ammonium ₂₀ alkylbenzenesulfonate, sodium di (C ₁ -C ₂₀ alkyl) sulfosuccinate, sodium polyoxyethylene C ₆ -C ₃₀ aryl ether sulfonate, or polyoxyethylene C ₆ −
The polyisocyanate composition according to claim 7, which is at least one compound selected from the group consisting of ammonium C ₃₀ aryl ether sulfonate and sodium polyoxyethylene C ₁ -C ₂₀ alkyl ether sulfonate. 9. The polyisocyanate composition according to claim 1, wherein the ionic surfactant is a cationic surfactant. 10. The cationic surfactant is C _1-.
C ₂₀ alkyl trimethyl ammonium bromide, C ₁
At least one selected from the group consisting of -C ₂₀ alkylpyridinium bromide and imidazolinium laurate
10. Polyisocyanate composition according to claim 9, characterized in that it is a class of compounds. 11. A mixture of the polyisocyanate composition and water in a weight ratio of 40:60 with respect to water to obtain a mixture of 6 parts.
The aqueous dispersion obtained by stirring at 00 rpm for 10 minutes was added to 2
The polyisocyanate composition according to claim 1, which has a residual rate of unreacted isocyanate groups of 50% or more when left at 0 ° C. for 6 hours. 12. (A) Hydroxyl value 1 to 300 mg KOH /
An aqueous solution or emulsion of a polyol having g, and (B) a polyisocyanate composition according to any one of claims 1 to 11, wherein the equivalent ratio of the isocyanate group of component (B) to the hydroxyl group of component (A). (NCO
/ OH) is in the range of 0.5 to 5.0, and component (A)
And component (B) are provided separately from each other and are configured to be mixed at the time of use. 13. The polyol of the aqueous polyol emulsion is polyvinylidene chloride-based polyol, polyvinyl chloride-based polyol, vinyl acetate-based polyol, urethane-based polyol, acrylate-based polyol, fluorine copolymer-based polyol, styrene-butadiene copolymer-based polyol. 13. The water-based coating composition according to claim 12, which is at least one selected from the group consisting of a polybutadiene-based polyol, and a urethane acrylate-based polyol. 14. The water-based coating composition according to claim 12, wherein the polyol in the aqueous polyol emulsion is dispersed with an average particle diameter of 0.01 to 1.0 μm. 15. The coated fresh film having a thickness of 40 μm exhibits a gel fraction of 50% or more when left standing at 20 ° C. and 65% relative humidity for 24 hours. The water-based coating composition according to any one of 1 to 14.