JP3016234B2 - Self-emulsifying polyisocyanate mixture, and aqueous coating composition and aqueous adhesive composition using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a urethane-modified polymer of hexamethylene diisocyanate (hereinafter abbreviated as HDI) and an isophorone diisocyanate (hereinafter abbreviated as I).
The present invention relates to a self-emulsifying polyisocyanate mixture obtained from a polymer (hereinafter abbreviated as PDI) or a tolylene diisocyanate (hereinafter abbreviated as TDI) polymer, and an aqueous coating composition and an aqueous adhesive composition using the same.

[0002]

2. Description of the Related Art Paints, adhesives and coating agents containing organic solvents have adverse effects on human bodies, safety and health problems such as explosion and fire, and pollution problems such as air pollution. In order to improve these problems, water system development has been actively conducted in recent years. Conventionally, water-soluble polymer solutions and aqueous emulsions have been used, but these one-part systems often cannot exhibit the required physical properties, and generally a crosslinking agent is used to improve weather resistance and adhesion. . There are various reactions in the crosslinking system. Among them, examples of using a self-emulsifying polyisocyanate include JP-A-62-50373 and JP-A-61-291613. All of these use a self-emulsifying polyisocyanate into which a nonionic hydrophilic surfactant is introduced as a crosslinking agent. In particular, it is known to use an isocyanurate ring-containing self-emulsifying polyisocyanate modified with a hydrophilic surfactant for the purpose of improving the heat resistance, weather resistance and adhesion of a water-soluble resin and an aqueous emulsion.

[0003]

Conventionally, most self-emulsifying polyisocyanates used in fields requiring good appearance of coatings, such as paints and coatings, are non-yellow base isocyanates having good weather resistance. It is composed of only a modified isocyanate group (hereinafter abbreviated as NCO group) terminal HDI polymer. However, since the HDI polymer has a soft skeleton, when it is used as an additive for a water-soluble resin and an aqueous emulsion, it has a drawback that the coating film hardness is small and the drying speed is slow. Furthermore, the introduction of the hydrophilic surfactant increases the affinity for water, so that the NCO group easily reacts with water, resulting in a short working time. In addition, since HDI, which is a raw material, is more expensive than TDI or the like, which is a yellowing-type isocyanate, there is also a disadvantage that the product is necessarily expensive.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve such conventional problems, and as a result, have found that self-emulsifying polyisocyanates obtained from conventional NCO-terminated HDI polymers are: It has been found that mixing an NCO-terminated IPDI polymer having an isocyanurate group with a hard skeleton or an NCO-terminated TDI polymer having an isocyanurate group is effective for improving the coating film hardness and drying speed. . IPD with low reactivity with water
It has been found that the pot life can be extended when the I polymer is used. On the other hand, when an inexpensive TDI polymer is used, the cost of the product can be reduced.

That is, the present invention relates to an NCO-terminated HDI obtained by subjecting HDI to urethane modification with a dihydric alcohol, polymerizing and removing unreacted monomers to 1% by weight or less.
After polymerizing the polymer (a) and IPDI, the compounding ratio of the NCO-terminated IPDI polymer (b) having an isocyanurate group from which unreacted monomers have been removed to 1% by weight or less is 99: 1 to 50 by weight. : 50 mixture A (base isocyanate), 3 to 90 alkylene oxide units
And at least one active hydrogen group capable of reacting with the NCO group.
Nonionic hydrophilic surfactant having at least one nonionic hydrophilic surfactant and NC
Has at least one active hydrogen group that can react with O group
Compounds having at least 8 carbon atoms and / or raw materials
The sum of the carbon numbers of the fatty acid and the hydroxyl group-containing compound is 8 or more
A self-emulsifying polyisocyanate mixture having an average number of functional groups of 2.0 to 4.2 obtained by reacting the above fatty acid ester , wherein the dihydric alcohol component contains 0.1 to 15% by weight, 0.1 to 40% by weight of component, 0 to 30% by weight of component
It is a self-emulsifiable polyisocyanate mixture characterized Rukoto.

According to the present invention, HDI is modified by urethane with a dihydric alcohol, and after polymerization, unreacted monomer is removed by one.
The NCO-terminated HDI polymer (a) removed to less than 1% by weight and the TDI are polymerized, and the unreacted monomer is removed to 1% by weight or less.
The compounding ratio of the O-terminated TDI polymer (c) is 9 by weight.
A mixture B (base isocyanate) of 9: 1 to 70:30, 3 to 90 alkylene oxide units,
At least one active hydrogen group capable of reacting with the NCO group
Having a nonionic hydrophilic surfactant and an NCO group
Carbon having at least one active hydrogen group capable of reacting
Aliphatic compounds having a number of 8 or more and / or fatty acids as raw materials
And the total number of carbon atoms of the hydroxyl group-containing compound is 8 or more.
A self-emulsifying polyisocyanate mixture having an average number of functional groups of 2.0 to 5.0 obtained by reacting a fatty acid ester, wherein the dihydric alcohol component is contained in an amount of 0.1 to 15% by weight in the self-emulsifying polyisocyanate mixture. %, component 0.1 to 40% by weight, component 0 to 30 wt% der Turkey
And a self-emulsifying polyisocyanate mixture.

According to the present invention, the mixing ratio of the polymer (a) and the NCO-terminated TDI polymer (c) having an isocyanurate group from which unreacted monomers have been removed to 1% by weight or less is 98: 2 by weight. A self-emulsifying polyisocyanate mixture obtained by reacting the above with a mixture B (base isocyanate) of about 70:30, wherein the dihydric alcohol component according to claim 1 is contained in the self-emulsifying polyisocyanate mixture. 0.1-15% by weight, component 0.1-
The self-emulsifying type polyisocyanate mixture, wherein 40% by weight, components are 0 to 30% by weight, and the average number of functional groups is 2.0 to 5.0.

The present invention relates to an aqueous coating composition comprising the above-mentioned self-emulsifying polyisocyanate mixture, a water-soluble resin and / or an aqueous emulsion, and if necessary, an additive, wherein the self-emulsifying polyisocyanate mixture is provided. Of the water-soluble resin and / or the solid content of the aqueous emulsion 1
An aqueous coating composition characterized by a ratio of 0.5 to 100 parts by weight with respect to 00 parts.

The present invention is an aqueous adhesive composition comprising the above-mentioned self-emulsifying polyisocyanate mixture, a water-soluble resin and / or an aqueous emulsion, and if necessary, an additive. The aqueous adhesive composition is characterized in that the amount of the isocyanate mixture added is 0.5 to 100 parts by weight based on 100 parts of the solid content of the water-soluble resin and / or the aqueous emulsion.

The present invention provides an aqueous coating composition comprising the above-mentioned self-emulsifying polyisocyanate mixture, water and, if necessary, an additive, wherein the amount of the self-emulsifying polyisocyanate mixture is as follows: An aqueous coating composition characterized in that the weight ratio is 0.5 to 100 parts with respect to 100 parts of water.

The present invention provides an aqueous adhesive composition comprising the above-mentioned self-emulsifying polyisocyanate mixture, water and, if necessary, an additive, wherein the amount of the self-emulsifying polyisocyanate mixture is small. A water-based adhesive composition, wherein the weight ratio is 0.5 to 100 parts with respect to 100 parts of water.

The NCO-terminated HDI polymer (a) (hereinafter referred to as HD) in the self-emulsifying polyisocyanate mixture of the present invention.
I polymer (a)) is obtained by subjecting HDI to urethane modification with a dihydric alcohol, followed by isocyanuration or a polymerization catalyst for simultaneously proceeding with isocyanuration and uretdionation, and if necessary, The reaction is carried out using a co-catalyst, for example, a phenolic hydroxyl group-containing compound or an alcoholic hydroxyl group-containing compound. After reaching the target reaction rate, the reaction is stopped by adding a terminator such as phosphoric acid or methyl paratoluenesulfonate. The reaction temperature is usually in the range of 40 to 90 ° C. If free unreacted HDI monomer is present in the reaction mixture, it can be obtained by appropriate means, such as extraction with n-hexane or thin film distillation under a high vacuum of 0.01 to 0.1 Torr. Unreacted HDI monomer is removed to less than weight percent.

As the HDI polymer (a) of the present invention, an HDI polymer containing an isocyanurate group obtained by using an isocyanurate-forming catalyst can be used, or the isocyanurate-formation and uretdionization can be carried out simultaneously. An HDI polymer containing an isocyanurate group and a uretdione group can also be used by using a polymerization catalyst for proceeding. Also,
An HDI polymer containing an isocyanurate group and an HDI polymer containing an isocyanurate group and a uretdione group can be used in a mixture at an arbitrary ratio. Effective catalysts for isocyanuration include tetraalkylammonium and hydroxyethylammonium hydroxides, tertiary amines, alkyl-substituted ethylene imines, tertiary alkyl phosphines, metal salts of acetylacetone, alkyl carboxylic acids Metal salts of various organic acids such as alkali metal salts of Effective catalysts for simultaneously proceeding with isocyanuration and uretdionation are triethylphosphine, dibutylethylphosphine, tripropylphosphine, triisopropylphosphine, tributylphosphine, triisobutylphosphine, tritertiarybutylphosphine, and triamylphosphine. And phosphines such as trioctylphosphine, tribenzylphosphine and benzylmethylphosphine are preferred. These catalysts are used alone or, if necessary, in combination. When the viscosity of the self-emulsifying type polyisocyanate is large, dispersibility in water, a water-soluble resin or an aqueous emulsion is deteriorated, and workability is deteriorated. In such a case, it is preferable to reduce the viscosity of the self-emulsifying polyisocyanate by introducing a uretdione group having a lower molecular weight than an isocyanurate group.

The NCO-terminated IPDI polymer (b) (hereinafter referred to as I) in the self-emulsifying polyisocyanate mixture of the present invention.
In order to obtain the PDI polymer (b), a reaction is carried out using a polymerization catalyst for promoting isocyanuration and, if necessary, a cocatalyst. After reaching the target reaction rate, the reaction is stopped by adding a terminator such as phosphoric acid or methyl paratoluenesulfonate. The reaction temperature is usually 4
The range is 0 to 150 ° C. If free unreacted IPDI monomer is present in the reaction mixture, use appropriate means, such as extraction with n-hexane, or 0.0
By thin film distillation under a high vacuum of 1 to 0.1 Torr, 1
Unreacted IPDI monomer is removed to less than weight percent.

The NCO-terminated TDI polymer (c) (hereinafter referred to as TD) in the self-emulsifying polyisocyanate mixture of the present invention.
In order to obtain isocyanurate, it is necessary to use 2,4-TDI, 2,6-TDI, or a mixture of these in any ratio as a raw material to obtain isocyanurate. The reaction is carried out using a polymerization catalyst of the formula (1) and, if necessary, a cocatalyst. After reaching the target reaction rate, phosphoric acid,
The reaction is stopped by adding a terminating agent such as methyl paratoluenesulfonate. The reaction temperature is usually 40 to 90 ° C.

Effective isocyanuration catalysts used to obtain IPDI polymer (b) or TDI polymer (c) include tetraalkylammonium and hydroxyethylammonium hydroxides, tertiary amines, alkyls Metal salts of various organic acids such as substituted ethylene imines, tertiary alkyl phosphines, metal salts of acetylacetone, and alkali metal salts of alkyl carboxylic acids. Examples of the cocatalyst used as necessary include a phenolic hydroxyl group-containing compound and an alcoholic hydroxyl group-containing compound. When it is desired to improve the compatibility with the skeleton of the water-soluble resin or the aqueous emulsion to further improve the gloss and the sharpness, the IPDI polymer (b) or the TDI polymer (c)
The dihydric alcohol used for the synthesis of the HDI polymer (a) may be introduced.

In order to obtain the HDI polymer (a), the IPDI polymer (b) and the TDI polymer (c), inert solvents commonly used in the polyurethane industry, such as toluene, xylene, swazol (Cosmo Oil Co., Ltd.) Aromatic solvents such as aromatic hydrocarbon solvents manufactured by the company), aromatic solvents such as Solvesso (aromatic hydrocarbon solvents manufactured by Exxon Chemical), ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethyl acetate, butyl acetate, Ester solvents such as isobutyl acetate, glycol ether ester solvents such as ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, and ethyl-3-ethoxypropionate; tetrahydrofuran , Dioxane and other ether solvents It is also possible to use one or two or more. By using a solvent, the viscosity of the solution after the reaction can be adjusted to a viscosity according to the use conditions. As a preferred solvent, a polyisocyanate mixture is used by adding it to a water-soluble resin or an aqueous emulsion.
It is a polar solvent that can be dispersed or compatible with water, such as an ester or an ether. When a polar solvent is contained, the polyisocyanate mixture has a lower viscosity, so that it is easily dispersed in a water-soluble resin and / or an aqueous emulsion.
The solvent used during the synthesis is removed by an operation such as distillation if unnecessary.

The mixing ratio of the HDI polymer (a) and the IPDI polymer (b) for obtaining the mixture A, which is the base isocyanate of the self-emulsifying polyisocyanate, is 99: 1 to 50:50 by weight. Preferably 98: 2-45:
55, more preferably 95: 5 to 35:65. By using the non-yellowing IPDI polymer (b),
High hardness and quick drying can be achieved without impairing the weather resistance. When the blending amount of the IPDI polymer (b) is small, the high hardness and the quick-drying property, which are the objects of the present invention, cannot be obtained, and the effect of extending the pot life due to the mild reactivity of the NCO group of the IPDI can be obtained. I can't. On the other hand, when the blending amount is large, the viscosity of the self-emulsifying polyisocyanate increases, and the workability deteriorates.

The mixing ratio of the HDI polymer (a) and the TDI polymer (c) to obtain a mixture B which is a base isocyanate of a self-emulsifying polyisocyanate is 99: 1 to 70:30 by weight, Preferably 98: 2 to 75: 3
5, more preferably 95: 5 to 80:20. TD
I is less expensive than non-yellowing HDI.
By using the polymer (c), the cost reduction of the originally expensive non-yellowing polyisocyanate can be achieved. When the blending amount of the TDI polymer (c) is small, the high hardness and the quick drying property, which are the objects of the present invention, cannot be obtained. On the other hand, when the blending amount is large, the weather resistance decreases.

The dihydric alcohol introduced into the HDI polymer (a) used for obtaining the self-emulsifying type polyisocyanate of the present invention includes 1,3-butanediol, neopentyl glycol, 2,2-diethyl-1 , 3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentaneddiol, 2-ethyl-1,3-hexanediol,
2-n-hexadecane-1,2-ethylene glycol,
2-n-eicosan-1,2-ethylene glycol, 2
-N-octacosan-1,2-ethylene glycol, hydrogenated bisphenol A, dipropylene glycol, 3-
Hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2-dimethylpropionate; and the like, preferably 1,3-butanediol, 2-n-butyl-2.
And those having a side chain such as -ethyl-1,3-propanediol. These molecular weights are 62-3000,
Preferably it is 100-1000. Also, two or more of the above dihydric alcohols can be used in combination.

This dihydric alcohol has a hydrocarbon group in the molecular skeleton and has good compatibility with the skeleton portion of the aqueous resin, so that it has good gloss and sharpness when blended and formed into a film. Becomes In addition, since the dihydric alcohol is bifunctional, it is introduced not at the terminal of the self-emulsifying polyisocyanate molecule but at the center of the molecular chain, and thus acts more effectively. Furthermore, since glycol is hydrophobic, it also contributes to an improvement in the stability of NCO groups in water or an aqueous resin, as in the case of an aliphatic compound described later. In the case of producing the HDI polymer (a), the reaction of isocyanuration and uretdione formation is smoothly carried out without producing a partially gelled product (polymer) due to a catalytic effect of a urethane bond from a dihydric alcohol. proceed.

The amount of the dihydric alcohol introduced into the HDI polymer (a) is 0.1 to 15% by weight, preferably 0.1% by weight, as the component amount in the self-emulsifying polyisocyanate mixture.
It is in the range of 3 to 10% by weight, more preferably 0.5 to 5% by weight. If the amount of the dihydric alcohol introduced is too small, problems such as poor compatibility with the aqueous resin and partial gelation during synthesis may occur. On the other hand, if too large, isocyanurate structure and uretdione structure generated after polymerization,
In addition, the characteristics of the mixed IPDI polymer (b) and TDI polymer (c) cannot be sufficiently exhibited, and high hardness, weather resistance and heat resistance cannot be improved.

Examples of the nonionic hydrophilic surfactant having an active hydrogen group capable of reacting with an NCO group for obtaining the self-emulsifying polyisocyanate mixture of the present invention include polyalkylene ether alcohols and polyoxyalkylene fatty acid esters. Is mentioned. The active hydrogen compound used as an initiator in the production of the polyalkylene ether alcohol includes, for example, methanol, n-butanol, cyclohexanol, phenol, ethylene glycol,
Examples include propylene glycol, aniline, trimethylolpropane, glycerin and the like. Among these, in consideration of dispersion stability, it is preferable to use a short-chain alcohol since the hydrophilicity becomes higher. In addition, examples of the fatty acid used for producing the polyoxyalkylene fatty acid ester include acetic acid, propionic acid, and butyric acid. Among these, in consideration of dispersion stability, it is preferable to use a lower fatty acid because the hydrophilicity becomes higher. The polyalkylene ether alcohol, polyoxyalkylene fatty acid ester, etc. has 3 to 90 polyether chains, preferably 5 to 5 polyether chains.
It is composed of 0, more preferably 8 to 20 alkylene oxide units. The alkylene oxide units may be all ethylene oxide units, or may be mixed alkylene oxide units containing at least 70% or more of ethylene oxide units. The ionic surfactant often affects the reactivity of the isocyanate and the coloring and deterioration of the coating film. Depending on the ionicity of the aqueous resin, a precipitate or an aggregate may be generated. Therefore, it is necessary to use a nonionic surfactant.

The content of the hydrophilic surfactant component in the self-emulsifying polyisocyanate mixture of the present invention is from 0.1 to 0.1%.
It is 40% by weight, preferably 0.5 to 30% by weight, more preferably 1 to 20% by weight. If the amount of the hydrophilic surfactant introduced is too small, the water dispersibility of the modified polyisocyanate deteriorates, and sedimentation and the like tend to occur. On the other hand, if the amount of the hydrophilic surfactant introduced is too large,
Since the affinity between the modified polyisocyanate and water becomes too strong, the stability of NCO groups in water deteriorates.
When the amount of the hydrophilic surfactant introduced is large, at least one active hydrogen group capable of reacting with a dihydric alcohol or NCO group is used.
It is possible to balance hydrophilicity by increasing the amount of the aliphatic compound or fatty acid ester having 8 or more carbon atoms, but the NCO content of the polyisocyanate mixture decreases, and the weather resistance of the coating film decreases. Cannot be improved.

Aliphatic compounds and / or aliphatic esters having at least one active hydrogen group capable of reacting with the NCO group and having 8 or more carbon atoms have too large a hydrophilic property and have a high NCO content in water and aqueous resins. Introduced when the stability of the group is impaired. The aliphatic compound and / or fatty acid ester is
After reacting with the polyisocyanate, the lipophilic chain portion causes the reaction between the unreacted NCO groups present in the vicinity and the water molecules present around it to cause steric hindrance or surface chemistry based on the lipophilicity. It is considered that it is suppressed. Therefore, it is more effective for the lipophilic chain to have a certain length, and it is desirable that the number of carbon atoms is 8 or more, preferably 12 or more. Further, it is preferable that the site of the active hydrogen group that reacts with the NCO group exists not near the terminal but near the center of the main chain.

Aliphatic compounds having at least one active hydrogen group capable of reacting with an NCO group and having 8 or more carbon atoms include octyl alcohol, caprylic alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl. Alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, cinnamyl alcohol and the like. Further, as the aliphatic ester having at least one active hydrogen group capable of reacting with the NCO group, a fatty acid ester in which the total number of carbon atoms of a fatty acid and an alcohol as raw materials is 8 or more can be mentioned. Fatty acids as the raw materials include α-oxypropionic acid, oxysuccinic acid, dioxysuccinic acid, ε-oxypropane-1,2,3-tricarboxylic acid, hydroxyacetic acid, α-hydroxybutyric acid, hydroxystearic acid, ricinoleic acid, Sinoelaidic acid, ricinostearolic acid, salicylic acid, mandelic acid and the like can be mentioned, and examples of the alcohol include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol and butyl alcohol.

The content of the aliphatic compound and / or fatty acid ester in the self-emulsifying polyisocyanate mixture of the present invention is 0 to 30% by weight, preferably 0 to 25% by weight, more preferably 0 to 20% by weight. is there. If the amount of the aliphatic compound and / or fatty acid ester introduced is too large, the dispersion stability decreases.

If the amount of the dihydric alcohol, hydrophilic surfactant, aliphatic compound and / or aliphatic ester introduced is too large, the NC of the relatively modified polyisocyanate becomes too high.
The O content is reduced, the characteristics of the isocyanurate structure and the uretdione structure cannot be sufficiently exhibited, and the reduction in viscosity and the improvement in weather resistance cannot be achieved. Therefore, the upper limit of the amount of modification of the polyisocyanate with a dihydric alcohol, a hydrophilic surfactant, an aliphatic compound or an aliphatic ester should be such that the average number of NCO functional groups becomes 2.0 or more. The NCO content of the self-emulsifying polyisocyanate mixture of the present invention is 5 to 25% by weight, preferably 6 to 25% by weight.
It is 24.5%, more preferably 7 to 24%. NCO
If the content is too small, the effect of addition becomes small, which is not preferable.

The self-emulsifying polyisocyanate mixture of the present invention is blended with a water-soluble resin and / or an aqueous emulsion to form a water-based paint (including a water-based coating agent) for metals, woodwork, plastics and inorganic materials, and an adhesive. In addition, it can be used as a fiber treating agent such as a sealer, ink or fiber, glass fiber, or a sizing agent. The effects of these additions include superior coating film properties, heat resistance,
Examples include water resistance, solvent resistance, and improved adhesion. Also,
In the self-emulsifying polyisocyanate of the present invention, when a hydrophobic chain having an appropriate length is introduced in consideration of the balance with the hydrophilic chain, the reaction between the NCO group and water in water is suppressed by the introduced hydrophobic chain. Therefore, these performance improvement effects continue for a longer time and with a high degree of stability. In particular, when an NCO-terminated IPDI polymer is used, water and NC
The effect is greater because the reaction of the O group is small. The self-emulsifying polyisocyanate mixture may be dispersed in water, diluted with a solvent, or added directly.

The water-soluble resin used in the present invention includes:
Polyvinyl alcohol, water-soluble ethylene-vinyl acetate copolymer,
Polyethylene oxide, water-soluble acrylic resin, water-soluble epoxy resin, water-soluble cellulose derivative, water-soluble polyester and water-soluble lignin derivative, water-soluble fluorine resin,
Water-soluble silicone resins and the like can be mentioned.

The aqueous emulsion used in the present invention includes all the so-called latex and emulsion. For example, styrene butadiene copolymer latex, acrylonitrile butadiene copolymer latex, methyl methacrylate butadiene copolymer latex, chloroprene latex, rubber latex such as polybutadiene latex, polyacrylate latex, polyvinylidene chloride latex,
Examples thereof include polybutadiene latex, or those obtained by carboxyl-modified these latexes, polyvinyl chloride emulsion, urethane acrylic emulsion, silicone acrylic emulsion, vinyl acetate acrylic emulsion, urethane emulsion, and acrylic emulsion. Fluorine emulsions with excellent weather resistance and stain resistance are poor in solvent resistance due to non-crosslinking, but by using the self-emulsifying polyisocyanate of the present invention, the weather resistance, stain resistance and solvent resistance are improved. Etc. are further improved.

The water-soluble resin and / or aqueous emulsion used in the present invention does not contain active hydrogen groups capable of reacting with NCO groups, or even if it contains a small amount thereof, a self-emulsifying polyisocyanate. Is a water-soluble resin and / or
Alternatively, it reacts with water in the aqueous emulsion to form a polyurea compound, and forms a hard and tough coating film, thereby improving weather resistance. Further, the NCO group reacts with the active hydrogen group present on the surface of the adherend, so that the adhesion is also improved. On the other hand, when a water-soluble resin and / or aqueous emulsion containing many active hydrogen groups that can react with NCO groups at room temperature is used, the active hydrogen groups in the polymer and the NCO groups in the self-emulsifying polyisocyanate react. To form a crosslinked structure,
Weather resistance and solvent resistance are further improved. When baking at a high temperature, the uretdione group is dissociated and an NCO group is generated, so that the effect of addition is more remarkable as compared with the case of using at normal temperature. Therefore, it is more preferable that the water-soluble resin and / or the aqueous emulsion contain active hydrogen groups that can react with NCO groups.

In the aqueous coating composition and the aqueous adhesive composition of the present invention, the amount of the self-emulsifying polyisocyanate added to the water-soluble resin and / or the aqueous emulsion is 100 parts by weight of the solid content of the water-soluble resin and / or the aqueous emulsion. 0.5 to 100 parts by weight, preferably 1 to 6 parts by weight
0 parts, more preferably 5 to 40 parts.

The self-emulsifying polyisocyanate mixture of the present invention can be processed into an aqueous dispersion by mixing with water. This dispersion can be used as an aqueous paint (including an aqueous coating agent), an aqueous sealer, or an aqueous adhesive such as paper, wood material, plastic, metal material, and inorganic material. In the aqueous coating composition and the aqueous adhesive composition of the present invention, the mixing ratio of water and the self-emulsifying polyisocyanate composition is 100
To 200 parts by weight of self-emulsifying polyisocyanate
Parts, preferably 10 to 100 parts, more preferably 20 to 5 parts
0 parts. This dispersion is considered to be a coating or adhesive with very good adhesion because the NCO groups that are present relatively stably even after being dispersed in water react with the active hydrogen present on the surface of these substrates. Can be Further, a considerable amount of time has elapsed since the dispersion in water, and the dispersion in which the NCO groups have disappeared is also stably present as an emulsion having a particle size of about 0.1 to 0.3 μm. Since the film mainly composed of the urea compound obtained by drying becomes hard and tough, it can be used in the form of a film or sheet or as a paint (coating agent) for various substrates. When importance is attached to the adhesion to the base material, it is preferable to use in a state where the NCO group exists.

The coatings (including coating agents) and adhesives containing the self-emulsifying polyisocyanate of the present invention and a water-soluble resin and / or an aqueous emulsion may be added, if necessary, to a commonly used aqueous two-component system. Agents and auxiliaries can be used. For example, pigments, dispersion stabilizers, viscosity modifiers, leveling agents, anti-gelling agents, light stabilizers, antioxidants, ultraviolet absorbers, heat resistance improvers, inorganic and organic fillers, plasticizers, lubricants, antistatics Agents, reinforcing materials and catalysts can be added. The above-mentioned additives and auxiliaries can also be used in the water-based paint, water-based coating agent and water-based adhesive containing the self-emulsifying type polyisocyanate and water of the present invention.

[0036]

The self-emulsifying polyisocyanate of the present invention has a soft skeleton by mixing an HDI polymer with an IPDI polymer having a hard skeleton isocyanurate group or a TDI polymer having an isocyanurate group. High hardness could be imparted to the self-emulsifying polyisocyanate. Further, by using a non-yellowing type IPDI polymer, high hardness and quick drying can be achieved without prolonging the weather resistance, and the pot life can be extended. Also, by using a TDI polymer, it is possible to achieve a cost reduction of a non-yellowing polyisocyanate which is originally expensive, and at the same time, it does not require sufficient weather resistance, but a field where some weather resistance is required. It became possible to expand to.

[0037]

EXAMPLES Next, examples of the present invention and comparative examples will be described in detail, but the present invention is not limited to these examples. Unless otherwise specified, “parts” and “%” in Examples and Comparative Examples mean “parts by weight” and “% by weight”, respectively.

[Production Example of Self-Emulsifying Polyisocyanate Mixture] Production Example of HDI Polymer Production Example 1 300 parts of HDI, 2-n was added to a reactor equipped with a stirrer, thermometer, nitrogen seal tube and cooler. -Butyl-2-ethyl-
2.3 parts of 1,3-propanediol was charged, the inside of the reactor was replaced with nitrogen, and the reaction temperature was 60 to 70 ° C. while stirring.
And reacted at the same temperature for 3 hours. When the NCO content of the reaction solution at this time was measured, it was 49.1%. Next, 0.3 parts of tributylphosphine was added as a catalyst, and uretdionation and isocyanuration were carried out at the same temperature for 8 hours. After 0.33 parts of methyl paratoluenesulfonate was added to the reaction solution to stop the reaction, unreacted HDI was removed by thin-film distillation at 120 ° C. and 0.01 Torr. The obtained liquid is a pale yellow transparent liquid with NCO
The content was 22.3%, the viscosity was 99 cP / 25 ° C., the HDI monomer content was 0.4%, the number of functional groups was 2.3, the dihydric alcohol content was 3.0%, and the yield was 25%. Also, FT-
NCO, uretdione IR and ¹³ C-NMR,
It was confirmed that an isocyanurate group and a urethane group were present. The HDI polymer containing the uretdione dimer / isocyanurate cyclic trimer is referred to as a-1.

Production Example 2 300 parts of HDI and 2.4 parts of 1,3-butanediol were charged into a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a condenser, and the inside of the reactor was purged with nitrogen. Then, the mixture was heated to a reaction temperature of 80 ° C. with stirring, and reacted at the same temperature for 2 hours. When the NCO content of the reaction solution at this time was measured, it was 48.8.
%Met. Next, potassium caprate 0.0
6 parts, 0.3 parts of phenol as a co-catalyst were added,
Was carried out for 4.5 hours. 0.042 parts of phosphoric acid as a terminator was added to the reaction solution, and the mixture was stirred at the same temperature for 1 hour.
Removed by thin film distillation at Torr. The obtained liquid was a pale yellow transparent liquid having an NCO content of 21.1% and a viscosity of 2200 c.
P / 25 ° C., HDI monomer content 0.4%, number of functional groups 3.7, dihydric alcohol content 2.5%, yield 3
2%. The presence of an NCO group, an isocyanurate group and a urethane group was confirmed by FT-IR and ¹³ C-NMR, but no uretdione group was confirmed. The HDI polymer containing the isocyanurate cyclic trimer is a
-2.

Production Example 3 In a reactor equipped with a stirrer, thermometer, nitrogen seal tube and cooler, 300 parts of HDI, 2,2,4-trimethyl-1,2
5.0 parts of 3-pentanediol was charged, the inside of the reactor was replaced with nitrogen, and the mixture was heated to a reaction temperature of 60 to 70 ° C. with stirring, and reacted at the same temperature for 3 hours. When the NCO content of the reaction solution at this time was measured, it was 48.2%. Next, 0.3 parts of tributylphosphine was added as a catalyst,
The uretdionation and isocyanuration reactions were performed at the same temperature for 8 hours. 0.33 parts of methyl paratoluenesulfonate was added to the reaction solution to stop the reaction.
DI was removed by thin film distillation at 120 ° C. and 0.01 Torr. The obtained liquid is a pale yellow transparent liquid having an NCO content of 2
2.0%, viscosity 120cP / 25 ° C, HDI monomer content 0.3%, number of functional groups 2.3, dihydric alcohol content 6.
3% and the yield was 26%. Also, FT-I
From R and ¹³ C-NMR, NCO group, uretdione group,
It was confirmed that an isocyanurate group and a urethane group were present. The HDI polymer containing the uretdione dimer / isocyanurate cyclic trimer is designated as a-3.

Production Example 4 300 parts of HDI, neopentyl glycol 1.0 were added to a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube, and a cooler.
Then, the reactor was purged with nitrogen, heated to a reaction temperature of 80 ° C. with stirring, and reacted at the same temperature for 2 hours.
When the NCO content of the reaction solution at this time was measured,
It was 9.5%. Next, 0.06 parts of potassium caprate as a catalyst and 0.3 parts of phenol as a co-catalyst were added,
The isocyanurate-forming reaction was performed at 60 ° C. for 4.5 hours.
0.042 parts of phosphoric acid was added to this reaction solution as a terminator,
After stirring at the same temperature for 1 hour, unreacted HDI was
Removed by thin film distillation at 0.01 Torr. The obtained liquid was a pale yellow transparent liquid having an NCO content of 21.2% and a viscosity of 2
300 cP / 25 ° C., HDI monomer content 0.4%, number of functional groups 3.6, dihydric alcohol content 1.1%,
The yield was 30%. FT-IR and ¹³ C-N
MR confirmed the presence of NCO, isocyanurate and urethane groups, but no uretdione groups. The HDI polymer containing this isocyanurate cyclic trimer is designated as a-4.

Fruit of self-emulsifying polyisocyanate mixture
施例 Example 1 HDI modified product a-1 70 parts of an isocyanurate group-containing IPDI polymer (IPDI-T-1890: NCO
A polyoxyethylene methyl ether (having a hydroxyl value of 14) was used in an amount of 30 parts with a content of 17.0% and manufactured by Daicel Huls.
0, ethylene oxide unit 9, 16 parts by Toho Chemical Industry Co., Ltd.), and the mixture was reacted for 3 hours while maintaining the temperature at 75 ° C., and the NCO content was 16.4% and the viscosity was 810 c.
P / 25 ° C, free isocyanate monomer content 0.5
%, The number of functional groups is 2.4, the dihydric alcohol content is 1.8%,
A pale yellow, transparent, self-emulsifying polyisocyanate (D) having a hydrophilic surfactant content of 13.7% was obtained.

Examples 2 to 9 and Comparative Examples 1 to 3 The obtained self-emulsifying polyisocyanate mixture was used in the order of E, F, G, H, I, J, K, L, M,
Named N, O. In addition, the isocyanurate group-containing T
C-2030 (NCO content 8.0% as a DI polymer,
The viscosity was 1,000 cP / 25 ° C., the solid content was 50%, manufactured by Nippon Polyurethane Industry Co., Ltd., and ricinoleic acid methyl ester (hydroxyl value: 160, manufactured by Ito Oil) was used as an aliphatic ester. Further, 500 parts of water was added to 100 parts of the obtained self-emulsifying polyisocyanate, and the dispersion which was well mixed with a laboratory mixer was evaluated for NCO remaining time. The raw materials used, their contents and the results are shown in Table 1,
It is shown in Table 2.

[0044]

[Table 1]

[0045]

[Table 2]

IPDI for self-emulsifying polyisocyanate
By introducing the polymer in a well-balanced manner, the stability of the NCO group was increased without impairing the workability, and the pot life was extended.

[Preparation of Water-Based Paint and Evaluation of Coating Film] Production of Urethane Emulsion A (Aqueous Emulsion Containing Active Hydrogen Groups Reactable at Room Temperature) A stirrer, thermometer, nitrogen seal tube, and cooler were attached. Nipporan 980N (polycarbonate-based polyol, molecular weight 2000, manufactured by Nippon Polyurethane Industry) 46
1.1 parts, 150.1 parts of IPDI, and 0.06 parts of dibutyltin dilaurate were charged and reacted for 2 hours while maintaining the temperature at 75 ° C. to obtain a reaction solution having an NCO content of 6.0%. Next, the reaction solution was cooled to 40 ° C., and 29.6 parts of dimethylolpropionic acid and 252.8 parts of acetone were added and reacted for 3 hours to obtain a reaction solution having an NCO content of 1.8%. Further, 273.2 parts of acetone, 30.3 parts of isophoronediamine, and 2.4 parts of monoethanolamine were added to the reaction solution, and the mixture was reacted for 20 minutes. Add water 1
562.5 parts were added, and the mixture was stirred at a high speed to perform phase inversion. Acetone is distilled off from this solution to obtain a viscosity of 100 cP / 25.
A urethane emulsion having a solid content of 30.1% was obtained.
This urethane emulsion is referred to as emulsion A.

Production of Urethane Emulsion B (Aqueous Emulsion Containing No Active Hydrogen Groups Reactable at Room Temperature) Nipporan 981 (polycarbonate polyol, Nipporan 981) was placed in a reactor equipped with a stirrer, thermometer, nitrogen seal tube, and condenser. Molecular weight 1000, manufactured by Nippon Polyurethane Industry) 31
7.2 parts, 133.4 parts of IPDI, and 0.08 part of dibutyltin dilaurate were charged and reacted for 2 hours while raising the temperature and maintaining the temperature at 75 ° C. to obtain a reaction solution having an NCO content of 5.2%. Next, polyoxyethylene methyl ether (hydroxyl value 80, manufactured by Nippon Emulsifier Industry) was added to the reaction solution,
The reaction was performed for 3 hours to obtain a reaction solution having an NCO content of 4.6%.
After further cooling the reaction solution to 25 ° C., acetone 47
4.8 parts and 45.2 parts of isophoronediamine were added to give 2
The reaction was performed for 0 minutes. To this solution was added 1231.3 parts of water, and the mixture was stirred at high speed to cause phase inversion. Acetone was distilled off from this solution to obtain a viscosity of 700 cP / 25 ° C. and a solid content of 27.9%.
Was obtained. This urethane emulsion is referred to as emulsion B.

Example 10: 80 parts of urethane emulsion A, TiO ₂ (white pigment)
18 parts, auxiliary (0.5% FS antifoam 013B
Bismar YK-1 containing (Antifoaming agent, manufactured by Dow Corning)
(Dispersion / thickening agent, manufactured by Toho Chemical Industry Co., Ltd.), and the auxiliary in the following Examples and Comparative Examples shows the contents thereof.) 2 parts were blended, and the self-emulsifying polyisocyanate 5 obtained in Example 1 was further added. The mixture was stirred and mixed with a glass rod and easily dispersed. This dispersion was applied to an aluminum plate treated with a surface treatment agent using a bar coater so as to have a dry coating of 30 to 40 μm. Example 11 80 parts of urethane emulsion B, TiO ₂ (white pigment)
18 parts and 2 parts of an auxiliary agent were blended, and 5 parts of the self-emulsifying polyisocyanate obtained in Example 1 was further added thereto. The mixture was stirred and mixed with a glass rod, and easily dispersed. Using this dispersion, coating was carried out in the same manner as in Example 8. Example 12 Acrylic emulsion A (solid content 50%, viscosity 300c)
P / 25 ° C, trade name WA-1015ND, manufactured by Asia Industries) 53 parts, TiO ₂ (white pigment) 18 parts, auxiliary agent 2 parts,
27 parts of water were added, and 5 parts of the self-emulsifying polyisocyanate obtained in Example 1 was further added. The mixture was stirred and mixed with a glass rod, and easily dispersed. Using this dispersion, coating was carried out in the same manner as in Example 8. Example 13 80 parts of urethane emulsion A, TiO ₂ (white pigment)
18 parts and 2 parts of an auxiliary agent were blended, and 5 parts of the self-emulsifying polyisocyanate obtained in Example 5 was further added, followed by stirring and mixing with a glass rod. Using this dispersion, coating was carried out in the same manner as in Example 8. Example 14 80 parts of urethane emulsion B, TiO ₂ (white pigment)
18 parts and 2 parts of an auxiliary agent were blended, and 5 parts of the self-emulsifying type polyisocyanate obtained in Example 5 was further added. The mixture was stirred and mixed with a glass rod to be easily dispersed. Using this dispersion, coating was carried out in the same manner as in Example 8. Example 15 Acrylic emulsion A53 parts, TiO ₂ (white pigment)
Example 5 was blended with 18 parts, 2 parts of an auxiliary agent, and 27 parts of water.
5 parts of the self-emulsifying polyisocyanate obtained in the above was added, and the mixture was stirred and mixed with a glass rod, whereby it was easily dispersed. Using this dispersion, coating was carried out in the same manner as in Example 8.

Comparative Example 4 80 parts of urethane emulsion A, TiO ₂ (white pigment)
18 parts and an auxiliary agent of 2 parts were blended, and 5 parts of the self-emulsifying type polyisocyanate obtained in Comparative Example 1 was added, and the mixture was coated in the same manner as in Example 8. Comparative Example 5 80 parts of urethane emulsion B, TiO ₂ (white pigment)
18 parts and an auxiliary agent of 2 parts were blended, and 5 parts of the self-emulsifying type polyisocyanate obtained in Comparative Example 1 was added, and the mixture was coated in the same manner as in Example 8. Comparative Example 6 Acrylic emulsion A53 parts, TiO ₂ (white pigment)
18 parts, 2 parts of an auxiliary agent and 27 parts of water were blended, and Comparative Example 1 was further added.
5 parts of the self-emulsifying type polyisocyanate obtained in the above was added and the coating was carried out in the same manner as in Example 8. Comparative Example 7 80 parts of urethane emulsion A, TiO ₂ (white pigment)
18 parts and an auxiliary agent of 2 parts were blended, and 5 parts of the self-emulsifying polyisocyanate obtained in Comparative Example 3 was added, and the mixture was coated in the same manner as in Example 8. Comparative Example 8 80 parts of urethane emulsion B, TiO ₂ (white pigment)
18 parts and an auxiliary agent of 2 parts were blended, and 5 parts of the self-emulsifying polyisocyanate obtained in Comparative Example 3 was added, and the mixture was coated in the same manner as in Example 8. Comparative Example 9 Acrylic emulsion A53 parts, TiO ₂ (white pigment)
18 parts, auxiliary (dispersing agent, thickener, defoaming agent, etc.) 2 parts, water 2
7 parts were blended, and 5 parts of the self-emulsifying polyisocyanate obtained in Comparative Example 3 was added, and the mixture was coated in the same manner as in Example 8.

[Evaluation of coating film]
After the coating of Comparative Examples 4 to 9, drying was performed at 80 ° C. for 20 minutes.
Water resistance, gloss, pencil hardness,
The weather resistance (gloss retention%, yellowing degree ΔYI) and the curing and drying time when left at room temperature were evaluated. For water resistance, the coated surface was immersed in tap water at 20 ° C. for one day, and the state of the coated surface was examined. Pencil hardness is J
Performed according to IS K5400. The weather resistance was measured by a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.) under the conditions of a black panel temperature of 63 ± 3 ° C. and a spraying time of 120 minutes for 18 minutes, and a gloss retention (%) after 2000 hours according to JIS K 5400. And the degree of yellowing (ΔYI) were measured. The curing and drying time when left at room temperature is JIS K54
Performed according to 00. Examples 10 to 15 and Comparative Examples 4 to 9
Table 3 shows the evaluation of the coating film No.

[0052]

[Table 3]

IPDI to self-emulsifying polyisocyanate
By introducing the polymer and the isocyanurate group-containing TDI polymer in a well-balanced manner, the hardness of the coating film was increased and the curing and drying time was shortened without impairing the weather resistance. The evaluation of water resistance was good in each case.

[Evaluation of Adhesive Strength] Example 16 A polyurethane molded product having a thickness of 3 mm by RIM, FR
P, ABS, and bond steel plate were degreased with trichloroethylene, and a mixture of 100 parts of the acrylic emulsion A and 10 parts of the self-emulsifying polyisocyanate obtained in Example 3 was applied thereon so that the dry film thickness became 40 to 50 μm. . Then, the plate is preliminarily dried at 80 ° C. for 5 minutes.
^It was left at 80 ° C. for 10 minutes under pressure bonding at ² . 24 at 25 ° C
After leaving for a period of time, each plate is cut to a width of 25 mm.
According to 6854, the adhesive strength (kg / 25 mm) was measured under the condition of a tensile speed of 100 mm / min. Table 4 shows the results. Example 17 The same method as in Example 16 was evaluated using a mixture of 100 parts of the acrylic emulsion A and 5 parts of the self-emulsifying polyisocyanate obtained in Example 8. Table 4 shows the results. Comparative Example 10 The same method as in Example 16 was evaluated using a mixture of 100 parts of the acrylic emulsion A and 5 parts of the self-emulsifying polyisocyanate obtained in Comparative Example 1. Table 4 shows the results.

[0055]

[Table 4]

Adhesion strength was increased by introducing an isocyanurate group-containing IPDI polymer or an isocyanurate group-containing TDI polymer into a self-emulsifying polyisocyanate.

[Evaluation of Coating Properties of Aqueous Dispersion] Example 18 100 parts of water was added to 30 parts of the self-emulsifying type polyisocyanate obtained in Example 2, and the mixture was stirred and mixed with a glass rod to be easily dispersed. After 1 hour from the dispersion, the mixture was applied on a scalpel plate and allowed to stand at room temperature for 1 hour and then at 80 ° C. for 3 hours.
Hold for hours. Example 19 100 parts of water was added to 30 parts of the self-emulsifying polyisocyanate obtained in Example 4, and the mixture was stirred and mixed with a glass rod. Example 18 was prepared using this dispersion.
A coating film was prepared in the same manner as described above. Example 20 100 parts of water was added to 30 parts of the self-emulsifying polyisocyanate obtained in Example 7, and the mixture was stirred and mixed with a glass rod. Example 18 was prepared using this dispersion.
A coating film was prepared in the same manner as described above. Comparative Example 11 100 parts of water was added to 30 parts of the self-emulsifying polyisocyanate obtained in Comparative Example 1, and a coating film was formed in the same manner as in Example 16 by using a dispersion mixed by stirring with a glass rod. did. Comparative Example 12 100 parts of water was added to 30 parts of the self-emulsifying type polyisocyanate obtained in Comparative Example 3, and a coating film was formed in the same manner as in Example 16 by using a dispersion mixed by stirring with a glass rod. did.

The state and adhesion of the coating films of Examples 18 to 20 and Comparative Examples 11 and 12 were evaluated. The state of the coating film was visually observed. Adhesion is JIS K54
According to No. 00, a cross-cut tape method was used. Table 5 shows the results.

[0059]

[Table 5]

By introducing a well-balanced IPDI polymer containing an isocyanurate group or a TDI polymer containing an isocyanurate group into a self-emulsifying polyisocyanate, the state and adhesion of the coating film were improved.

[Preparation and Evaluation of Aqueous Adhesive Composition] Example 21 100 parts of water and a self-emulsifying polyisocyanate mixture obtained in Example 6 in a lauan veneer having a size of 2.5 cm × 10 cm × 3.0 mm Apply 100 parts of the blended liquid at 200 g / m
^2. After applying so that the application area is 2.5 cm × 2.5 cm, lauan veneers of the same type are superimposed on each other so as to prevent air bubbles from entering, and pressed at 10 kg / cm ² for 2 hours at room temperature.
It was left at 20 ° C. for 10 minutes. After standing at 25 ° C for 24 hours,
With Tensilon UTM-500 manufactured by Orientec Co., Ltd., the normal adhesive strength (kg / cm ² ) and the heat resistant adhesive strength (120 ° C. × 24) at a pulling speed of 2 mm / min.
Time). Table 6 shows the results. Example 22 Using the dispersion of 100 parts of the self-emulsifying polyisocyanate obtained in Example 9 and 100 parts of water, a coating film was formed in the same manner as in Example 21. Table 6 shows the results. Comparative Example 13 A coating film was formed in the same manner as in Example 21 using a dispersion of 100 parts of the self-emulsifying polyisocyanate obtained in Comparative Example 1 and 100 parts of water. Table 6 shows the results.

[0062]

[Table 6]

By introducing an isocyanurate group-containing IPDI polymer or an isocyanurate group-containing TDI polymer into the self-emulsifying polyisocyanate, the adhesive strength was increased.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ identification symbol FI C09D 175/04 C09D 175/04 C09J 175/04 C09J 175/04 (58) Investigated field (Int.Cl. ⁷ , DB name) C08G 18 / 00,18 / 10 C08G 18 / 65,18 / 79 C08L 75/04-75/12 C09D 5/00 C09D 175/04-175/12 C09J 175/04-175/12

Claims (6)

(57) [Claims] 1. A urethane-modified hexamethylene diisocyanate by a dihydric alcohol, after polymerizing the isocyanate group-terminated hexamethylene diisocyanate polymer to remove unreacted monomers up to 1 wt% or less (a) Lee
After the polymerization of sophorone diisocyanate, the unreacted monomer is removed to 1% by weight or less, and the compounding ratio of the isocyanurate-terminated isophorone diisocyanate polymer (b) having an isocyanurate group is 99: 1 to 50:
For 50 mixtures A (base isocyanate), 3-90
Alkylene oxide units and isocyanate groups
Having at least one active hydrogen group capable of reacting with
Nionic hydrophilic surfactant and isocyanate group
Carbon having at least one active hydrogen group capable of reacting
Aliphatic compounds having a number of 8 or more and / or fatty acids as raw materials
And the total number of carbon atoms of the hydroxyl group-containing compound is 8 or more.
A self-emulsifying polyisocyanate mixture having an average number of functional groups of 2.0 to 4.2 obtained by reacting a fatty acid ester , wherein the dihydric alcohol component is contained in an amount of 0.1 to 15% by weight in the self-emulsifying polyisocyanate mixture. %, component 0.1 to 40% by weight, component 0 to 30 wt% der Turkey
And a self-emulsifying polyisocyanate mixture. 2. An isocyanate group-terminated hexamethylene diisocyanate polymer (a) obtained by subjecting hexamethylene diisocyanate to urethane modification with a dihydric alcohol, polymerizing, and removing unreacted monomers to 1% by weight or less .
After the polymerization of rearylene diisocyanate, the unreacted monomer is removed to 1% by weight or less, and the compounding ratio of the isocyanurate group-terminated tolylene diisocyanate polymer (c) having an isocyanurate group is 99: 1 to 70:30 by weight.
Of mixture B (base isocyanate) of 3 to 90
Alkylene oxide unit and isocyanate group
Nonio having at least one responsive active hydrogen group
Reacts with hydrophilic hydrophilic surfactants and isocyanate groups
Carbon atoms having at least one active hydrogen group
8 or more aliphatic compounds and / or
Fatty oil whose sum of carbon number of droxyl group-containing compound is 8 or more
A self-emulsifying polyisocyanate mixture having an average number of functional groups of 2.0 to 5.0 obtained by reacting a fatty acid ester, wherein the dihydric alcohol component is contained in an amount of 0.1 to 15% by weight in the self-emulsifying polyisocyanate mixture. %, Component is 0.
1 to 40 wt%, the self-emulsifiable polyisocyanate mixture component and wherein 0 to 30 wt% der Rukoto. 3. An aqueous coating composition comprising the self-emulsifying polyisocyanate mixture according to claim 1 or 2, a water-soluble resin and / or an aqueous emulsion, and if necessary, an additive. A water-soluble resin and / or a water-based coating composition, wherein the amount of the polyisocyanate mixture is 0.5 to 100 parts by weight based on 100 parts of the solid content of the water-soluble resin and / or the aqueous emulsion. object. 4. An aqueous adhesive composition comprising the self-emulsifying polyisocyanate mixture according to claim 1 or 2, a water-soluble resin and / or an aqueous emulsion, and optionally an additive. Wherein the amount of the self-emulsifying polyisocyanate mixture is 0.5 to 100 parts by weight relative to 100 parts of the solid content of the water-soluble resin and / or the aqueous emulsion. Composition. 5. An aqueous coating composition comprising the self-emulsifying polyisocyanate mixture according to claim 1 and water and optionally an additive, wherein the self-emulsifying polyisocyanate mixture is added. Quantity is water 1
The water-based coating composition is characterized in that the weight ratio is 0.5 to 100 parts with respect to 00 parts. 6. An aqueous adhesive composition comprising the self-emulsifying polyisocyanate mixture according to claim 1 or 2 and water and optionally an additive, wherein the self-emulsifying polyisocyanate mixture comprises Addition amount is water 1
The water-based adhesive composition, wherein the weight ratio is 0.5 to 100 parts with respect to 00 parts.