JP6679905B2 - Method for producing emulsifying / dispersing agent, and method for producing water-emulsifying / dispersing composition - Google Patents

Description

  The present invention relates to an emulsifying / dispersing agent comprising an allophanate-modified isocyanate and having excellent emulsifying properties and stability, a water-emulsifying isocyanate curing agent and a water-emulsifying curable composition using the same.

  Conventionally, in an aqueous (curable) composition used as an adhesive or a paint, as a polyisocyanate component, an aqueous polyisocyanate or a hydrophobic polyisocyanate is emulsified and dispersed in water with an isocyanate group-containing nonionic compound. And is known to be used. Specifically, for example, a polyisocyanate composition in which a hydrophobic polyisocyanate is water-dispersed with a vinyl polymer containing a nonionic group and an isocyanate group, and an aqueous curable composition are known (for example, see Patent Document 1). . When such a vinyl-based polymer is produced, there is a problem that an environmental load occurs because an organic solvent is used in the production process. Further, there is known an emulsifying / dispersing agent in which a monohydric alcohol containing a hydrophobic group and a monofunctional alcohol containing a nonionic hydrophilic group are simultaneously urethane-reacted with an organic diisocyanate, and then allophanate-reacted (for example, see Patent Document 2). However, the emulsifying / dispersing agents described therein have the problems of odor and short pot life.

JP-A-2002-194045 JP, 2004-195385, A

  In recent years, in the field of water-based adhesives, paints, etc., compared to organic solvent-based adhesives, paints, etc., it is easy to emulsify and disperse so as to be efficient and easy to work without sacrificing coating film physical properties. It is desired to be stable over a long period of time. The object of the present invention is to remove the free organic diisocyanate by distillation without using an organic solvent, further having an improved pot life, to emulsify the main component consisting of an organic polyisocyanate and a polymer compound used therefor. It is to provide an emulsifying / dispersing agent for dispersing.

  The present invention has been found as a result of extensive studies to solve the above problems. That is, the present invention includes the following embodiments (1) to (11).

(1) A method for producing an emulsifying / dispersing agent obtained by the following steps.
First step: a step of reacting the organic diisocyanate (a) with the nonionic hydrophilic group-containing monofunctional alcohol (b) in the presence of an allophanate catalyst.
Second step: a step of adding a catalyst poison to stop the allophanatization reaction.
Third step: a step of removing the free organic diisocyanate (a) by distillation.
Fourth step: a step of reacting the allophanate-modified isocyanate obtained from the third step with the hydrophobic group-containing monoalcohol (c) in the presence of an allophanate catalyst.
Fifth step: a step of adding a catalyst poison to stop the allophanatization reaction.

  (2) The method for producing an emulsifying / dispersing agent according to (1) above, wherein the organic diisocyanate (a) is hexamethylene diisocyanate.

  (3) The method for producing an emulsifying / dispersing agent according to (1) or (2) above, wherein the content of the free organic diisocyanate (a) is 0.5% by mass or less.

(4) The emulsifying / dispersing agent according to any one of (1) to (3), wherein the nonionic hydrophilic group-containing monofunctional alcohol (b) is represented by the following (Formula 1). Manufacturing method.
^{R 1 -O - (- R 2} -O-) n-H ··· ( Equation 1)
(However, R ¹ represents an alkyl group, R ² represents an alkylene group containing an ethylene group in an amount of 30 mol% or more, and n represents an integer of 1 or more.)

  (5) The emulsification / dispersion according to any of (1) to (4) above, wherein the hydrophobic group-containing monoalcohol (c) is an alkyl monoalcohol having 1 to 20 carbon atoms. Method of manufacturing agent.

  (6) The molar ratio of the nonionic hydrophilic group-containing monofunctional alcohol (b) / hydrophobic group-containing monoalcohol (c) is (b) / (c) = 10/90 to 90/10. The method for producing the emulsifying / dispersing agent according to any one of (1) to (5) above.

  (7) The amount of the nonionic hydrophilic group-containing monofunctional alcohol (b) used is 10 to 60% by mass in the total amount of the above (a), (b), and (c). The method for producing the emulsifying / dispersing agent according to any one of (1) to (6) above.

  (8) A method for producing a water-emulsified or water-dispersed isocyanate curing agent, which comprises emulsifying or dispersing an organic polyisocyanate in water, which is described in any of (1) to (7) above. A method for producing a water-emulsified or water-dispersed isocyanate curing agent, characterized by using the emulsification / dispersant obtained by the method for producing an emulsification / dispersion agent.

  (9) A method for producing a water emulsified or water dispersion, which comprises emulsifying or dispersing a hydroxyl group-containing compound or a hydroxyl group-free compound in water, any of the above (1) to (7) An emulsifying / dispersing agent obtained by the method for producing an emulsifying / dispersing agent described in 1. is used for water emulsification or a method for producing an aqueous dispersion.

  (10) A method for producing a water emulsified or water dispersion, which comprises emulsifying or dispersing a composition containing an organic polyisocyanate and a hydroxyl group-containing compound or a hydroxyl group-free compound in water, A method for producing an emulsifying / dispersing agent obtained by the method for producing an emulsifying / dispersing agent according to any one of (1) to (7) above, wherein the emulsifying / dispersing agent is used.

  (11) A water-emulsified or water-dispersed isocyanate curing agent obtained by the method for producing a water-dispersed isocyanate curing agent according to (8) above, and a hydroxyl group-containing compound or a hydroxyl group-free compound. A method for producing a water-emulsifiable or water-dispersible curable composition, which is characterized.

  According to the present invention, it is possible to provide an emulsifying / dispersing agent excellent in the ability to emulsify and disperse a main agent and a curing agent and a pot life, and a water-emulsified polyisocyanate curing agent and a water-emulsifying curable composition using the same. Became. Therefore, the water-emulsified polyisocyanate curing agent and the water-emulsifiable curable composition of the present invention are paints, adhesives, various binders, printing inks, recording magnetic media, coating agents, sealing agents, elastomers, sealing agents, synthetic leather. It can be applied to a wide range of foams, foam fillers for civil engineering, etc.

  Hereinafter, the present invention will be described in detail.

  Examples of the organic diisocyanate (a) used in the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate and 2,2 ′. -Diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4 '-Diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3 Aromatic diisocyanates such as 3'-dimethoxydiphenyl-4,4'-diisocyanate; hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, Aliphatic diisocyanates such as lysine diisocyanate and trioxyethylene diisocyanate; araliphatic diisocyanates such as xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate and tetramethylxylylene diisocyanate; isophorone diisocyanate, hydrogenated tolylene diisocyanate, Alicyclic rings such as hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethyl xylene diisocyanate Diisocyanate, and the like. Any of these may be used alone or in combination of two or more. In the present invention, considering the weather resistance of the emulsifying / dispersing agent to be obtained, aliphatic diisocyanates and alicyclic diisocyanates are preferable, and hexamethylene diisocyanate is particularly preferable.

  Examples of the nonionic hydrophilic group-containing monofunctional alcohol (b) include polyoxyalkylene glycol monoalkyl ether and polyoxyalkylene fatty acid ester monoalcohol. Any of these may be used alone or in combination of two or more. Of these, polyoxyalkylene glycol monoalkyl ether is preferable. The "emulsifying ability" refers to the ability to emulsify not only the emulsifying / dispersing agent itself but also the substance to be emulsified.

  Examples of the initiator for producing the polyoxyalkylene glycol monoalkyl ether include methanol, n-butanol and the like. Of these, lower alcohols are preferable because they have higher hydrophilicity. In addition, examples of the fatty acid used for producing the polyoxyalkylene fatty acid ester monoalcohol include acetic acid, propionic acid, and butyric acid. Of these, it is preferable to use a lower fatty acid because it has higher hydrophilicity.

  The polyether chains present in the polyoxyalkylene glycol monoalkyl ether, polyoxyalkylene fatty acid ester monoalcohol, etc. are generally 3 to 90, preferably 5 to 30, and particularly preferably 8 to 10 alkylene oxides. The unit is preferably a unit containing at least 70% or more of ethylene oxide units in all alkylene oxide units, and most preferably all ethylene oxide units.

  Examples of the hydrophobic group-containing monoalcohol (c) used in the present invention include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, pentadecanol, cetyl. Aliphatic monoalcohols such as alcohol, heptadecanol, stearyl alcohol, nonadecanol, oleyl alcohol, isomers thereof, alicyclic monoalcohols such as cyclohexanol and methylcyclohexanol, and aromatic aliphatic monoalcohols such as benzyl alcohol. , Α-oxypropionic acid, oxysuccinic acid, ε-oxypropane-1,2,3-tricarboxylic acid, hydroxyacetic acid, α-hydroxybutyric acid, hydroxystearic acid, Shinoru acid, ricinelaidic acid, ricinoleate stearolic acid, salicylic acid, esters monoalcohols obtained from hydroxycarboxylic acid and monoalcohols described above, such as mandelic acid and the like. Any of these may be used alone or in combination of two or more. In the present invention, considering the ease of handling as a raw material, the emulsifying property of the obtained emulsifying / dispersing agent itself, the emulsifying ability and the viscosity, etc., an alkyl monoalcohol having 1 to 20 carbon atoms is preferable, Alkyl monoalcohols are more preferred.

  As the allophanatization catalyst used in the present invention, a zirconium salt of carboxylic acid can be preferably exemplified. Examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, caproic acid, octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, saturated aliphatic carboxylic acids such as 2-ethylhexanoic acid, cyclohexanecarboxylic acid, cyclopentane. Saturated monocyclic carboxylic acids such as carboxylic acids, saturated multicyclic carboxylic acids such as bicyclo [4.4.0] decane-2-carboxylic acid, mixtures of the above carboxylic acids such as naphthenic acid, oleic acid, linoleic acid, linolene Acids, unsaturated aliphatic carboxylic acids such as soybean oil fatty acid and tall oil fatty acid, aromatic aliphatic carboxylic acids such as diphenylacetic acid, monocarboxylic acids such as aromatic carboxylic acids such as benzoic acid and toluic acid, phthalic acid, isophthalic acid , Terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, Pinic acid, pimelic acid, suberic acid, curtaconic acid, azelaic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α, Examples thereof include polycarboxylic acids such as β-diethylsuccinic acid, maleic acid, fumaric acid, trimellitic acid and pyromellitic acid. Any of these may be used alone or in combination of two or more. In the present invention, a particularly preferable allophanate-forming catalyst is a monocarboxylic acid zirconium salt having 10 or less carbon atoms. By using this allophanatization catalyst, a substantially colorless emulsifying / dispersing agent can be obtained relatively easily without using a cocatalyst or the like.

  Next, a specific procedure for producing the emulsifying / dispersing agent in the present invention will be described.

The present invention comprises the following steps.
First step: a step of reacting the organic diisocyanate (a) with the nonionic hydrophilic group-containing monofunctional alcohol (b) in the presence of an allophanate catalyst.
Second step: a step of adding a catalyst poison to stop the allophanatization reaction.
Third step: a step of removing the free organic diisocyanate (a) by distillation.
Fourth step: a step of reacting the allophanate-modified isocyanate obtained from the third step with the hydrophobic group-containing monoalcohol (c) in the presence of an allophanate catalyst.
Fifth step: a step of adding a catalyst poison to stop the allophanatization reaction.

  The first step consists of a urethanization reaction and an allophanate formation reaction. The specific procedure is as follows. An organic diisocyanate (a) and a nonionic hydrophilic group-containing monofunctional alcohol (b) are charged in an excess amount of isocyanate groups with respect to hydroxyl groups, and a urethanization reaction is performed at 20 to 100 ° C. After the reaction, the allophanatization reaction is carried out at 70 to 150 ° C. in the presence of the allophanatization catalyst until the urethane group is substantially absent.

  Here, "the amount of excess isocyanate groups with respect to hydroxyl groups" means that, when the raw materials are charged, the isocyanate groups are excessive with respect to the hydroxyl groups, and the molar ratio of the isocyanate groups to the hydroxyl groups is isocyanate group / hydroxyl group. = 8 or more is preferable, and 10-50 is especially preferable.

  The reaction temperature of the urethanization reaction is 20 to 120 ° C, preferably 50 to 100 ° C. A known urethanization catalyst can be used in the urethanization reaction. Specific examples thereof include organic metal compounds such as dibutyltin dilaurate and dioctyltin dilaurate, organic amines such as triethylenediamine and triethylamine, and salts thereof.

  The reaction time of the urethanization reaction is generally 10 hours or less, preferably 1 to 5 hours, although it varies depending on the presence or absence of a catalyst, the type, and the reaction temperature.

  When the urethanization reaction is completed, the allophanate reaction is performed. The allophanatization reaction is carried out at a reaction temperature of 70 to 150 ° C., preferably 80 to 130 ° C., by adding the above-mentioned allophanate formation catalyst. If the reaction temperature is too low, allophanate groups are not generated so much, and the emulsifying ability of the obtained emulsifying / dispersing agent may be reduced. When such an emulsifying / dispersing agent is used as the organic polyisocyanate curing agent, the emulsification tends to be insufficient. If the reaction temperature is too high, the resulting emulsifying / dispersing agent is unnecessarily heated, which may cause coloring.

  In the present invention, the urethanization reaction and the allophanate reaction can be carried out simultaneously. In this case, the organic diisocyanate (a) and the nonionic hydrophilic group-containing monofunctional alcohol (b) were charged in an amount such that the isocyanate group was excessive with respect to the hydroxyl group, and the presence of the allophanatization catalyst at 70 to 150 ° C. The urethanization reaction and the allophanate formation reaction are simultaneously performed below.

  The amount of the allophanatization catalyst used varies depending on its type, but is preferably 0.0005 to 1% by mass, more preferably 0.001 to 0.1% by mass, based on the total amount of (a) and (b). . When the amount of the catalyst used is less than 0.0005% by mass, the reaction takes a long time, and coloring due to heat history may occur. On the other hand, when the amount of the catalyst used exceeds 1% by mass, it becomes difficult to control the reaction, and a side reaction such as a dimerization reaction (uretdione formation reaction) or a trimerization reaction (isocyanurate formation reaction) may occur. When such an emulsifying / dispersing agent is used, problems such as a shortened pot life of the paint may occur.

  The reaction time varies depending on the kind and addition amount of the catalyst and the reaction temperature, but is generally within 10 hours, preferably 1 to 5 hours.

  At this time, an organic solvent can be used if necessary. Examples of the organic solvent include aliphatic hydrocarbon-based organic solvents such as n-hexane and octane, alicyclic hydrocarbon-based organic solvents such as cyclohexane and methylcyclohexane, and ketone-based organic solvents such as acetone, methylethylketone, methylisobutylketone, and cyclohexanone. , Ester-based organic solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, etc. Glycol ether ester type organic solvent, ether type organic solvent such as diethyl ether, tetrahydrofuran, dioxane, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide, dioctane Halogenated aliphatic hydrocarbon organic solvents such as Roetan, N- methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, polar aprotic solvents such as hexamethylphosphoric phosphonyl amides. The organic solvent may be used alone or in combination of two or more.

  The second step is a step of adding a catalyst poison after the allophanatization reaction to stop the allophanatization reaction. The timing of adding the catalyst poison is not particularly limited as long as it is after the allophanate-forming reaction, but when thin film distillation is performed in the method of removing the free organic diisocyanate (a) in the third step, after the allophanate reaction and thin film distillation are performed. It is preferred to add the catalyst poison before. This is to prevent side reactions from occurring due to heat during thin film distillation.

  Examples of the catalyst poison include known acids such as inorganic acids such as phosphoric acid and hydrochloric acid, organic acids having a sulfonic acid group, a sulfamic acid group and the like, esters thereof, acyl halides and the like.

  The third step is a step of removing the free organic diisocyanate (a). Examples of the method for removing the free organic diisocyanate include known methods such as distillation, reprecipitation, and extraction. When the distillation method, especially the thin film distillation method is used, it is not necessary to use a solvent or the like, and thus it is preferable. In addition, as preferable conditions for thin film distillation, pressure is 0.1 kPa or less and temperature is 100 to 200 ° C, and particularly preferable conditions are pressure: 0.05 kPa or less and temperature: 120 to 180 ° C.

  The fourth step is a step of urethanization reaction and allophanate reaction. The specific procedure is to charge the allophanate-modified polyisocyanate obtained in the third step and the hydrophobic group-containing monoalcohol (c) in an amount such that the isocyanate groups of the allophanate-modified polyisocyanate are in excess with respect to the hydroxyl groups. After the urethanization reaction is carried out at 20 to 100 ° C., the allophanatization reaction is carried out at 70 to 150 ° C. in the presence of the allophanatization catalyst until the urethane group is substantially absent.

  The fifth step is a step of adding a catalyst poison after the allophanatization reaction to stop the allophanatization reaction. The timing of adding the catalyst poison is not particularly limited as long as it is after the allophanatization reaction.

  The content of the nonionic hydrophilic group-containing monofunctional alcohol (b) in the thus-obtained allophanate-modified polyisocyanate (emulsifying / dispersing agent) is 10 to 60% by mass, preferably 20 to 50% by mass. If the content of the nonionic hydrophilic group-containing monofunctional alcohol (b) exceeds this range, the emulsification and dispersibility will be insufficient.

  In the use of the emulsifying / dispersing agent of the present invention, examples of the organic polyisocyanate to be dispersed include urethane modified products, isocyanurate modified products, and allophanate modified products of organic diisocyanates.

  In the use of the emulsifying / dispersing agent of the present invention, the compounding amount of the emulsifying / dispersing agent for emulsifying and dispersing the above-mentioned organic polyisocyanate in water is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the organic polyisocyanate, To 500 parts by mass is more preferable, and 50 to 300 parts by mass is the most preferable.

  Examples of the polymer compound as a main agent used in the water-emulsifiable / dispersion curable composition of the present invention include those which are liquid at room temperature and have no solubility or affinity in water. Alternatively, it is also possible to use a water-soluble resin and / or an aqueous emulsion having a solubility or a certain affinity with water. These polymer compounds preferably contain active hydrogen that reacts with an isocyanate group in the molecule, and particularly preferably contain two or more active hydrogens. Even when the polymer compound does not contain active hydrogen capable of reacting with an isocyanate group or contains only a small amount, finally the water-emulsified / dispersed polyisocyanate curing agent reacts with water to form a polyurea compound. , A hard and tough coating film. Further, the isocyanate group reacts with the active hydrogen (group) existing on the surface of the adherend, so that the adhesion is also improved. However, when a polymer compound containing active hydrogen capable of reacting with an isocyanate group at room temperature is used, the active hydrogen in the polymer compound reacts with the isocyanate group in the water-emulsified / dispersed polyisocyanate curing agent to form a crosslinked structure. Therefore, the weather resistance and solvent resistance are further improved.

  Specifically, for example, saturated or unsaturated polyester polyol, polycaprolactone polyol, saturated or unsaturated fatty acid-modified alkyd polyol, aminoalkyd polyol, polycarbonate polyol, acrylic polyol, polyether polyol, epoxy polyol, fluorine-containing polyol, and further Examples thereof include saturated or unsaturated polyester resin, polycaprolactone resin, fatty acid-modified alkyd resin, aminoalkyd resin, polycarbonate resin, acrylic resin, polyether resin, epoxy resin, polyurethane resin, cellulose acetate butyrate resin, and fluorine-containing resin.

  As the water-soluble resin, for example, polyvinyl alcohol, polyethylene oxide, water-soluble ethylene-vinyl acetate copolymer, water-soluble acrylic resin, water-soluble epoxy resin, water-soluble cellulose derivative, water-soluble polyester, water-soluble lignin derivative, water-soluble Examples thereof include fluororesins and water-soluble silicone resins.

  The water-based emulsion includes so-called latex and all that are expressed as an emulsion, for example, styrene-butadiene copolymer latex, acrylonitrile-butadiene copolymer latex, methylmethacrylate-butadiene copolymer latex, chloroprene latex, polybutadiene latex and the like. Rubber latex, polyacrylic acid ester latex, polyvinylidene chloride latex, polybutadiene latex, or these latex modified with carboxyl, polyvinyl chloride emulsion, urethane acrylic emulsion, silicone acrylic emulsion, vinyl acetate acrylic emulsion, polyurethane Examples thereof include emulsions and acrylic emulsions.

  Among these, acrylic polyols, acrylic resins, water-soluble acrylic resins, acrylic emulsions, urethane acrylic emulsions, and polyurethane emulsions are particularly preferable from the viewpoints of coating properties such as gloss and weather resistance and adhesive strength.

  The number average molecular weight of the polymer compound as the main agent is preferably 1000 to 1,000,000, more preferably 10,000 to 100,000.

  In the use of the emulsifying / dispersing agent of the present invention, the compounding amount of the emulsifying / dispersing agent that emulsifies and disperses the organic polyisocyanate and the polymer compound as the main component in water is 10 to 1000 parts by mass with respect to 100 parts by mass of the organic polyisocyanate. Parts are preferred, 20 to 500 parts by mass are more preferred, and 50 to 300 parts by mass are most preferred.

  In the water-emulsifiable / dispersible curable composition of the present invention, when a polymer compound containing active hydrogen is used as the polymer compound, the water-emulsified / dispersed isocyanate curing agent contains isocyanate groups in the curing agent and the active hydrogen content as a main component is high. The molar ratio with the active hydrogen group in the molecular compound is preferably 9: 1 to 1: 9, more preferably 6: 4 to 4: 6.

  In the water emulsification / dispersion curable composition of the present invention, the mixing method of water, the emulsification / dispersant, the organic polyisocyanate and the polymer compound is as follows. The organic polyisocyanate is emulsified and dispersed in water by the agent, and the polymer compound as the main agent is mixed and emulsified and dispersed therein.First, the polymer compound as the main agent is emulsified in water by the emulsifying / dispersing agent, Examples thereof include a method of dispersing, mixing an organic polyisocyanate therein, and emulsifying and dispersing. A preferred method is a method in which an organic polyisocyanate is first emulsified and dispersed in water with an emulsifying / dispersing agent, and then a polymer compound is mixed therein to emulsify and disperse.

  The compounding ratio of water to the emulsifying / dispersing agent and the organic polyisocyanate (curing agent) is preferably such that the total amount of the emulsifying / dispersing agent and the organic polyisocyanate (curing agent) is 0.1 with respect to 100 parts by mass of water. To 500 parts by mass, more preferably 1 to 100 parts by mass, most preferably 3 to 50 parts by mass. The mixing ratio of water to the emulsifying / dispersing agent, the organic polyisocyanate (curing agent), and the polymer compound (main agent) is 100 parts by mass of water, and the emulsifying / dispersing agent and the organic polyisocyanate (curing agent). And the polymer compound (main agent) are preferably 0.1 to 500 parts by mass, more preferably 1 to 100 parts by mass, and most preferably 3 to 50 parts by mass. The water emulsifying / dispersing isocyanate curing agent or the water emulsifying / dispersing curable composition remains stable even after emulsification and dispersion. In addition to the main agent, the isocyanate group reacts with active hydrogen (group) present on the surface of the substrate to be applied, so that the paint or adhesive has very good adhesion. In addition, even after a considerable amount of time has passed after the emulsification and dispersion and the isocyanate groups have disappeared, the emulsion remains stable as an emulsion with a particle size of about 0.05 to 5 μm and is obtained by drying at room temperature or by heat drying. Since the coating film is hard and tough, it can be used in the form of a film or sheet or as a coating agent for various base materials. When importance is attached to the adhesion to the substrate, it is preferable to use it in the state where the isocyanate group is present.

  In the present invention, the emulsifying / dispersing agent, the water emulsifying / dispersing isocyanate curing agent, the water emulsifying / dispersion curable composition, if necessary, for example, an antioxidant, an ultraviolet absorber, a pigment, a dye, a flame retardant, Additives such as an anti-hydrolysis agent, a lubricant, a plasticizer, a filler, and a storage stabilizer can be appropriately added.

  Further, the water-emulsifiable / dispersion curable composition of the present invention can be applied by a conventional coating method conventionally used, and for coating, an airless spray machine, an air spray machine, an electrostatic coating machine, dipping, or a roll. A coater, knife coater, brush, etc. can be used.

  Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Application Examples, etc., but the present invention is not construed as being limited thereto. In addition, "%" means "mass%" in a manufacture example, a manufacture comparative example, etc.

[Manufacture of allophanate emulsifying / dispersing agent]
<Manufacturing Example 1>
830 g of hexamethylene diisocyanate and 170 g of methoxypolyethylene glycol (molecular weight about 400) were placed in a 1 L reactor equipped with a stirrer, a thermometer, a cooler and a nitrogen gas introduction tube, and a urethanization reaction was carried out at 90 ° C. for 2 hours. It was When the reaction product was analyzed by FT-IR, the hydroxyl group had disappeared. Next, 0.36 g of zirconium 2-ethylhexanoate was charged and allowed to undergo an allophanate formation reaction at 90 ° C. for 3 hours. When the reaction product was analyzed by FT-IR and ¹³ C-NMR, the urethane group had disappeared. Next, 0.1 g of phosphoric acid was charged, a termination reaction was performed at 50 ° C. for 1 hour, and free hexamethylene diisocyanate was removed by thin film distillation to obtain an allophanate-modified isocyanate having an isocyanate content of 10.7% (NCO -1). A urethanation reaction was carried out at 90 ° C. for 2 hours in a reactor having a capacity of 1 L equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introducing tube, with NCO-1 of 728 g and isopropanol of 272 g. When the reaction product was analyzed by FT-IR, the hydroxyl group had disappeared. Next, 0.36 g of zirconium 2-ethylhexanoate was charged and allowed to undergo an allophanate formation reaction at 90 ° C. for 3 hours. When the reaction product was analyzed by FT-IR and ¹³ C-NMR, the urethane group had disappeared. Next, 0.1 g of phosphoric acid was charged, and a termination reaction was performed at 50 ° C. for 1 hour. Thus, an isocyanate content 3.3%, a viscosity at 25 ° C. of 8700 mPa · s, and an analysis by GPC measurement revealed that an emulsifying / dispersing agent EA-1 having a free hexamethylene diisocyanate content of 0.1% was obtained. The pot life was 23 hours.

<Manufacturing Example 2>
800 g of hexamethylene diisocyanate and methoxypolyethylene glycol (molecular weight about 400) were put into a 1 L reactor equipped with a stirrer, a thermometer, a cooler and a nitrogen gas introducing tube, and a urethanization reaction was carried out at 90 ° C. for 2 hours. When the reaction product was analyzed by FT-IR, the hydroxyl group had disappeared. Next, 0.36 g of zirconium 2-ethylhexanoate was charged and allowed to undergo an allophanate formation reaction at 90 ° C. for 3 hours. When the reaction product was analyzed by FT-IR and ¹³ C-NMR, the urethane group had disappeared. Next, 0.1 g of phosphoric acid was charged, a termination reaction was performed at 50 ° C. for 1 hour, and free hexamethylene diisocyanate was removed by thin film distillation to obtain an allophanate-modified isocyanate having an isocyanate content of 10.6% (NCO -2). A urethanation reaction was carried out at 90 ° C. for 2 hours at 730 g of NCO-2 and 270 g of 2-ethylhexanol in a 1 L reactor equipped with a stirrer, a thermometer, a cooler and a nitrogen gas introduction tube. When the reaction product was analyzed by FT-IR, the hydroxyl group had disappeared. Next, 0.36 g of zirconium 2-ethylhexanoate was charged and allowed to undergo an allophanate formation reaction at 90 ° C. for 3 hours. When the reaction product was analyzed by FT-IR and ¹³ C-NMR, the urethane group had disappeared. Next, 0.1 g of phosphoric acid was charged, and a termination reaction was performed at 50 ° C. for 1 hour. Thus, an isocyanate content 3.0%, a viscosity at 25 ° C. of 6500 mPa · s, and an analysis by GPC measurement revealed that an emulsifying / dispersing agent EA-2 containing 0.1% of free hexamethylene diisocyanate was obtained. The pot life was 23 hours.

<Production Comparative Example 1>
In a 1 L reactor equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introducing tube, 510 g of hexamethylene diisocyanate, 95 g of isopropanol, 395 g of methoxypolyethylene glycol (molecular weight about 400) and urethane at 90 ° C. for 2 hours. The chemical reaction was carried out. When the reaction product was analyzed by FT-IR, the hydroxyl group had disappeared. Next, 0.36 g of zirconium 2-ethylhexanoate was charged and allowed to undergo an allophanate formation reaction at 90 ° C. for 3 hours. When the reaction product was analyzed by FT-IR and ¹³ C-NMR, the urethane group had disappeared. Next, 0.1 g of phosphoric acid was charged, and a termination reaction was performed at 50 ° C. for 1 hour. Thus, an isocyanate content 3.3%, a viscosity at 25 ° C. of 10000 mPa · s, and an analysis by GPC gave an emulsifying / dispersing agent EA-3 containing 1% of free hexamethylene diisocyanate. The pot life was 12 hours.

<Production Comparative Example 2>
500g of hexamethylene diisocyanate, 100g of isopropanol, 400g of methoxy polyethylene glycol (molecular weight about 400), and urethane for 2 hours at 90 ° C in a 1L reactor equipped with a stirrer, a thermometer, a cooler and a nitrogen gas introduction tube. The chemical reaction was carried out. When the reaction product was analyzed by FT-IR, the hydroxyl group had disappeared. Next, 0.36 g of zirconium 2-ethylhexanoate was charged and allowed to undergo an allophanate formation reaction at 90 ° C. for 3 hours. When the reaction product was analyzed by FT-IR and ¹³ C-NMR, the urethane group had disappeared. Next, 0.1 g of phosphoric acid was charged, and a termination reaction was performed at 50 ° C. for 1 hour. Thus, an isocyanate content 2.4%, a viscosity at 25 ° C. of 160000 mPa · s, and an analysis by GPC measurement revealed that an emulsifying / dispersing agent EA-4 having a free hexamethylene diisocyanate content of 0.1% was obtained. No odor was confirmed, but it was neither emulsified nor dispersed in water due to its high viscosity.

  The methods for measuring the analytical values in Production Examples 1 and 2 and Production Comparative Examples 1 and 2 are as follows.

[Isocyanate content]
Measured according to JIS K1603.

[Analysis of functional groups]
The presence or absence thereof is judged by the peak intensity of each functional group of FT-IR (AVATAR-360 manufactured by Thermo Fisher) and ¹³ C-NMR (JNM-ECX400 manufactured by JEOL Ltd.).

[Free hexamethylene diisocyanate content]
Calculated from the area ratio of the peak of hexamethylene diisocyanate of GPC (Tosoh HLC-8120).

[Evaluation of pot life]
5 g of each emulsifying / dispersing agent EA-1 to 4 obtained in Production Examples 1 and 2 and Production Comparative Examples 1 and 2 and an isocyanurate modified product of hexamethylene diisocyanate (Tosoh Corp. Coronate HXLV, isocyanate content = 23). (3%) and 90 g of water were rapidly stirred at 2000 rpm for 30 seconds using a homomixer, and the time until the isocyanate group disappeared was measured.

[Emulsification / dispersion evaluation and odor confirmation]
4 g of each emulsifying / dispersing agent EA-1 to 3 obtained in Production Examples 1 and 2 and Production Comparative Example 1 and an isocyanurate-modified hexamethylene diisocyanate (Tosoh Coronate HXLV, isocyanate content = 23.3%). 6 g and 90 g of water were stirred at 2000 rpm for 30 seconds at high speed using a homomixer, emulsified and dispersed, and the presence or absence of odor of hexamethylene diisocyanate was examined.

  In the emulsification test, there was no odor in the products using Production Examples EA-1 and EA-2, but the odor was confirmed in Production Comparative Example EA-3. This is probably because free hexamethylene diisocyanate was not distilled and removed during the production process of EA-3. Production Comparative Example EA-4 had no odor but did not emulsify or disperse in water due to its high viscosity.

Claims (10)

Obtained from the following steps, emulsifying agents, or manufacturing method of dispersing agent.
First step: a step of reacting an organic diisocyanate (a) with a nonionic hydrophilic group-containing monofunctional alcohol (b) represented by the following (formula 1) in the presence of an allophanate catalyst.
^{R 1 -O - (- R 2} -O-) n-H ··· ( Equation 1)
(However, R ¹ represents an alkyl group, R ² represents an alkylene group containing an ethylene group in an amount of 30 mol% or more, and n represents an integer of 1 or more.)
Second step: a step of adding a catalyst poison to stop the allophanatization reaction.
Third step: a step of removing the free organic diisocyanate (a) by distillation.
Fourth step: a step of reacting the allophanate-modified isocyanate obtained from the third step with the hydrophobic group-containing monoalcohol (c) in the presence of an allophanate catalyst.
Fifth step: a step of adding a catalyst poison to stop the allophanatization reaction. The organic diisocyanate (a), characterized in that hexamethylene diisocyanate, emulsifying agent according to claim 1, or a manufacturing method of a dispersing agent. Characterized in that the free organic diisocyanates (a) is not more than 0.5 mass%, emulsifying agent according to claim 1 or 2, or a manufacturing method of a dispersing agent. The hydrophobic group-containing monoalcohol (c), characterized in that an alkyl monoalcohol having 1 to 20 carbon atoms, emulsifying agent according to any one of claims 1 to 3, or dispersant Production method. The nonionic hydrophilic group-containing monofunctional alcohol (b) / hydrophobic group-containing monoalcohol (c) has a molar ratio of (b) / (c) = 10/90 to 90/10, emulsifying agent according to any one of claims 1 to 4, or a manufacturing method of a dispersing agent. The amount of the nonionic hydrophilic group-containing monofunctional alcohol (b) used is 10 to 60% by mass in the total amount of the above (a), (b), and (c). emulsifying agent according to any one of claims 1 to 5, or a manufacturing method of a dispersing agent. Emulsifying an organic polyisocyanate in water, or dispersed was water, characterized by comprising emulsification, or a method of producing a water-dispersible isocyanate curing agent, emulsifying agent according to any one of claims 1 to 6, or emulsifying agent obtained by the production method of dispersing agent, or water-emulsifiable, which comprises using a dispersing agent, or method of producing a water-dispersible isocyanate curing agent. Emulsifying a hydroxyl group-containing compound or hydroxyl-free compound in water, or water emulsification dispersion is not characterized by comprising, or a method for producing a water dispersion according to any one of claims 1 to 6 emulsifying agents, or emulsifying agent obtained by the production method of dispersing agent, or dispersant water emulsion, which comprises using, or method for producing a water dispersion. A method for producing a water emulsified or water dispersion, which comprises emulsifying or dispersing a composition containing an organic polyisocyanate and a compound containing a hydroxyl group or a compound not containing a hydroxyl group in water. or emulsifying agent according to any one of 6, or emulsifying agent obtained by the production method of dispersing agent, or water-emulsifiable, which comprises using a dispersing agent, or a manufacturing method of the aqueous dispersion. Water emulsified according to claim 7 , or water containing the water-dispersed isocyanate curing agent obtained by the method for producing a water-dispersed isocyanate curing agent, and a hydroxyl group-containing compound or a hydroxyl group-free compound. A method for producing an emulsified or water-dispersible curable composition.