JP2017066338A - Manufacturing method of emulsifier and dispersant and manufacturing method of water emulsification and water dispersion composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide organic polyisocyanate without using an organic solvent, with free organic diisocyanate removed by distillation and having improved pot life, a manufacturing method of an emulsifier and dispersant for emulsifying and dispersing a main agent consisting of a polymer compound using the same and a manufacturing method of water emulsification and water dispersion composition.SOLUTION: The problem is solved by obtaining an allophanate-modified isocyanate emulsifier and dispersant which is an emulsifier and dispersant containing organic diisocyanate (a), hydrophobic group-containing monoalcohol (b) and hydrophilic group-containing monofunctional alcohol (c) as monomer units by a specific manufacturing method.SELECTED DRAWING: None

Description

  The present invention relates to an emulsifying / dispersing agent excellent in emulsifiability and stability thereof composed of allophanate-modified isocyanate, a water emulsifying isocyanate curing agent and a water emulsifying curable composition using the same.

  Conventionally, aqueous (curable) compositions used as adhesives and paints are emulsified and dispersed in water with an isocyanate group-containing nonionic compound as an aqueous polyisocyanate or hydrophobic polyisocyanate as a polyisocyanate component. And is known to be used. Specifically, for example, a polyisocyanate composition in which a hydrophobic polyisocyanate is dispersed in water with a nonionic group and an isocyanate group-containing vinyl polymer, and an aqueous curable composition are known (for example, see Patent Document 1). . When such a vinyl polymer is produced, an organic solvent is used in the production process, resulting in a problem that an environmental load is generated. Also known is an emulsifying / dispersing agent in which a hydrophobic group-containing monoalcohol and a nonionic hydrophilic group-containing monofunctional alcohol are simultaneously urethanated and then allophanatized to an organic diisocyanate (see, for example, Patent Document 2). However, the emulsifying / dispersing agents described in these publications have a problem that odor and pot life are short.

JP 2002-194045 A JP 2004-195385 A

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

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

(1) A method for producing an emulsifier / dispersant obtained from the following steps.
First step: a step of reacting the organic diisocyanate (a) with a hydrophobic group-containing monoalcohol (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 free organic diisocyanate (a) by distillation.
Fourth step: A step of reacting the allophanate-modified isocyanate obtained from the third step with a nonionic hydrophilic group-containing monofunctional alcohol (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 free organic diisocyanate (a) is 0.5% by mass or less.

  (4) The emulsification / dispersion according to any one of (1) to (3) above, wherein the hydrophobic group-containing monoalcohol (b) is an alkyl monoalcohol having 1 to 20 carbon atoms. Manufacturing method.

(5) The emulsifying / dispersing agent according to any one of (1) to (4) above, wherein the nonionic hydrophilic group-containing monofunctional alcohol (c) is represented by the following (formula 1): R ¹ —O — (— R ² —O—) n—H (Formula 1)
(However, R ¹ represents an alkyl group, R ² represents an alkylene group containing 30 mol% or more of an ethylene group. N represents an integer of 1 or more.)

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

  (7) The amount of the nonionic hydrophilic group-containing monofunctional alcohol (c) used is 10 to 60% by mass in the total amount of the above (a), (b), and (c). The method for producing an 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, wherein the organic polyisocyanate is emulsified or dispersed in water, and is described in any one of (1) to (7) above. A method for producing a water-emulsified or water-dispersed isocyanate curing agent, comprising using an emulsifier / dispersant obtained by the method for producing an emulsifier / dispersant.

  (9) A method for producing a water-emulsified or water-dispersed product comprising emulsifying or dispersing a hydroxyl group-containing compound or a hydroxyl group-free compound in water, wherein any of (1) to (7) above A method for producing a water emulsification or water dispersion, comprising using the emulsification / dispersant obtained by the method for producing an emulsification / dispersing agent according to claim 1.

  (10) A method for producing a water emulsion or a water dispersion, comprising 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 a water emulsion or a water dispersion, wherein the emulsion / dispersant obtained by the method for producing an emulsion / dispersant according to any one of (1) to (7) is used.

  (11) It contains water emulsification obtained by the method for producing water emulsification or water-dispersed isocyanate curing agent described in (8) above, or water-dispersed isocyanate curing agent, and a hydroxyl group-containing compound or a hydroxyl group-free compound. A method for producing a water-emulsified or water-dispersed curable composition.

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

  The present invention will be described in detail below.

  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; aromatic aliphatic 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 tetramethylxylene diisocyanate Diisocyanate, and the like. Any of these may be used alone or in admixture of two or more. In the present invention, aliphatic diisocyanate and alicyclic diisocyanate are preferable, and hexamethylene diisocyanate is particularly preferable in consideration of the weather resistance of the resulting emulsifier / dispersant.

  Examples of the hydrophobic group-containing monoalcohol (b) include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, pentadecanol, cetyl alcohol, heptadecanol. , Stearyl alcohol, nonadecanol, oleyl alcohol, aliphatic monoalcohols such as isomers thereof, alicyclic monoalcohols such as cyclohexanol and methylcyclohexanol, araliphatic monoalcohols such as benzyl alcohol, and α -Oxypropionic acid, oxysuccinic acid, ε-oxypropane-1,2,3-tricarboxylic acid, hydroxyacetic acid, α-hydroxybutyric acid, hydroxystearic acid, ricinoleic acid, ricin Elaidic 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 admixture of two or more. In the present invention, considering the ease of handling as a raw material, the emulsifying property of the resulting emulsifying / dispersing agent itself, emulsifying ability, viscosity, etc., alkyl monoalcohols having 1 to 20 carbon atoms are preferred, and those having 1 to 13 carbon atoms are preferred. More preferred are alkyl monoalcohols. The “emulsifying ability” refers to the ability to emulsify not only the emulsifying / dispersing agent itself but also the product to be emulsified together.

  Examples of the nonionic hydrophilic group-containing monofunctional alcohol (c) used in the present invention include polyoxyalkylene glycol monoalkyl ether and polyoxyalkylene fatty acid ester monoalcohol. Any of these may be used alone or in admixture of two or more. Of these, polyoxyalkylene glycol monoalkyl ether is preferred.

  Examples of the initiator for producing the polyoxyalkylene glycol monoalkyl ether include methanol and n-butanol. Among these, it is preferable to use a lower alcohol because the hydrophilicity is higher. Examples of the fatty acid used for the production of the polyoxyalkylene fatty acid ester monoalcohol include acetic acid, propionic acid, butyric acid, and the like. Among these, it is preferable to use a lower fatty acid because it has higher hydrophilicity.

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

  A preferred example of the allophanatization catalyst used in the present invention is a zirconium salt of a carboxylic acid. Examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, caproic acid, octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, 2-ethylhexanoic acid and other saturated aliphatic carboxylic acids, cyclohexanecarboxylic acid, and cyclopentane. Saturated monocyclic carboxylic acids such as carboxylic acids, saturated polycyclic 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, linolenic acid Acids, unsaturated aliphatic carboxylic acids such as soybean oil fatty acid and tall oil fatty acid, araliphatic 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, kurtaconic 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 admixture of two or more. A particularly preferred allophanatization catalyst in the present invention is a monocarboxylic acid zirconium salt having 10 or less carbon atoms. By using this allophanatization catalyst, an emulsifying / dispersing agent having substantially no color can be obtained relatively easily without using a promoter or the like.

  Next, a specific production procedure of 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 a hydrophobic group-containing monoalcohol (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 free organic diisocyanate (a) by distillation.
Fourth step: A step of reacting the allophanate-modified isocyanate obtained from the third step with a nonionic hydrophilic group-containing monofunctional alcohol (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 allophanatization reaction. Specifically, the organic diisocyanate (a) and the hydrophobic group-containing monoalcohol (b) are urethanated at a temperature of 20 to 100 ° C. after adding an excess amount of the isocyanate group to the hydroxyl group. The allophanatization reaction is carried out at 70 to 150 ° C. in the presence of the allophanatization catalyst until substantially no urethane group is present.

  Here, the “amount of isocyanate group in excess with respect to the hydroxyl group” means that the isocyanate group becomes excessive with respect to the hydroxyl group when the raw material is charged, and the molar ratio of isocyanate group to hydroxyl group is isocyanate group / hydroxyl group. = 8 or more is preferable, and 10 to 50 is particularly preferable.

  The reaction temperature of the urethanization reaction is 20 to 120 ° C, preferably 50 to 100 ° C. In the urethanization reaction, a known urethanization catalyst can be used. 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 varies depending on the presence / absence and type of the catalyst and the reaction temperature, but is generally within 10 hours, preferably 1 to 5 hours.

  When the urethanization reaction is completed, an allophanatization reaction is performed. The allophanatization reaction is carried out by adding the above-mentioned allophanate catalyst and setting the reaction temperature to 70 to 150 ° C, preferably 80 to 130 ° C. When the reaction temperature is too low, allophanate groups are not generated so much, and the emulsifying ability of the resulting emulsifying / dispersing agent may be lowered. When such an emulsifying / dispersing agent is used for the organic polyisocyanate curing agent, emulsification tends to be insufficient. When 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 allophanatization reaction can be performed simultaneously. In this case, the organic diisocyanate (a) and the hydrophobic group-containing monoalcohol (b) are charged in an amount that makes the isocyanate group excessive with respect to the hydroxyl group, and in the presence of the allophanate catalyst at 70 to 150 ° C. The urethanization reaction and the allophanatization reaction are performed simultaneously.

  The amount of allophanate catalyst used varies depending on the 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 thermal 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 dimerization reaction (uretodione reaction) or a trimerization reaction (isocyanurate reaction) may occur and are obtained. When using an emulsifying / dispersing agent, problems such as shortening the pot life of the paint may occur.

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

  At this time, an organic solvent can be used as necessary. Examples of organic solvents include aliphatic hydrocarbon organic solvents such as n-hexane and octane, alicyclic hydrocarbon organic solvents such as cyclohexane and methylcyclohexane, and ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ester 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 organic solvents, diethyl ether, tetrahydrofuran, dioxane and other ether organic solvents, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide, dichloride Halogenated aliphatic hydrocarbon organic solvents such as Roetan, N- methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, polar aprotic solvents such as hexamethylphosphoric phosphonyl amides. The said organic solvent can use together 1 type, or 2 or more types.

  The second step is a step of adding the catalyst poison after the allophanate reaction to stop the allophanate reaction. The catalyst poisoning time is not particularly limited as long as it is after the allophanatization reaction. However, when thin film distillation is performed in the method of removing free organic diisocyanate (a) in the third step, after the allophanate reaction and thin film distillation. 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 inorganic acids such as phosphoric acid and hydrochloric acid, organic acids having a sulfonic acid group, a sulfamic acid group and the like, and esters thereof, known substances such as acyl halides.

  The third step is a step of removing free organic diisocyanate (a). As a method for removing free organic diisocyanate, known methods such as distillation, reprecipitation, extraction and the like can be mentioned, and it is preferable to use a distillation method, particularly a thin film distillation method, because it is not necessary to use a solvent. Further, preferable conditions for thin film distillation are pressure: 0.1 kPa or less, temperature: 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 allophanatization reaction. Specifically, the allophanate-modified polyisocyanate obtained in the third step and the nonionic hydrophilic group-containing monofunctional alcohol (c) are charged in an amount in which the isocyanate group of the allophanate-modified polyisocyanate is excessive with respect to the hydroxyl group. Then, after the urethanization reaction at 20 to 100 ° C., the allophanatization reaction is carried out at 70 to 150 ° C. in the presence of the allophanatization catalyst until substantially no urethane group is present.

  The fifth step is a step of stopping the allophanatization reaction by adding a catalyst poison after the allophanatization reaction. The addition timing of 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 (c) in the allophanate-modified polyisocyanate (emulsifier / dispersant) thus obtained is 10 to 60% by mass, preferably 20 to 50% by mass. When the content of the nonionic hydrophilic group-containing monofunctional alcohol (c) exceeds this range, emulsification and dispersibility become insufficient.

  In the use of the emulsifying / dispersing agent of the present invention, examples of the organic polyisocyanate to be emulsified 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 amount of the emulsifying / dispersing agent for emulsifying and dispersing the organic polyisocyanate in water is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the organic polyisocyanate. -500 mass parts is still more preferable, and it is most preferable that it is 50-300 mass parts.

  Examples of the polymer compound as the main agent used in the water emulsification / dispersion curable composition of the present invention include liquids at room temperature that are not soluble or compatible with water. Alternatively, it is also possible to use a water-soluble resin and / or an aqueous emulsion having solubility or a certain degree of affinity for water. These polymer compounds preferably contain active hydrogen that reacts with an isocyanate group in the molecule, and particularly those containing two or more active hydrogens. Even if the polymer compound does not contain active hydrogen that can react with isocyanate groups or contains little hydrogen, the water-emulsified / dispersed polyisocyanate curing agent eventually reacts with water to become a polyurea compound. It becomes a hard and tough coating film. Moreover, since an isocyanate group reacts with the active hydrogen (group) existing on the surface of the adherend, adhesion is also improved. However, when a polymer compound containing active hydrogen that can react 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, weather resistance, solvent resistance and the like are further improved.

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

  Examples of the water-soluble resin include 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 A fluororesin, a water-soluble silicone resin, etc. are mentioned.

  Examples of water-based emulsions include what are called latexes and emulsions. For example, styrene butadiene copolymer latex, acrylonitrile butadiene copolymer latex, methyl methacrylate butadiene copolymer latex, chloroprene latex, polybutadiene latex, etc. Rubber latex, polyacrylate ester latex, polyvinylidene chloride latex, polybutadiene latex, or carboxyl-modified latex of these latexes, polyvinyl chloride emulsion, urethane acrylic emulsion, silicone acrylic emulsion, vinyl acetate acrylic emulsion, polyurethane An emulsion, an acrylic emulsion, etc. are mentioned.

  Of these, acrylic polyols, acrylic resins, water-soluble acrylic resins, acrylic emulsions, urethane acrylic emulsions, and polyurethane emulsions are particularly preferable in terms of coating performance such as gloss and weather resistance, and adhesive strength.

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

  In the use of the emulsifying / dispersing agent of the present invention, the blending amount of the emulsifying / dispersing agent for emulsifying and dispersing 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. Part is preferable, 20-500 mass parts is still more preferable, and it is most preferable that it is 50-300 mass parts.

  In the water emulsification / dispersion curable composition of the present invention, when using a polymer compound containing active hydrogen in the molecule, the isocyanate group in the water emulsification / dispersion isocyanate curing agent and the content of active hydrogen as the main component are 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 blending method of water, the emulsification / dispersant, the organic polyisocyanate, and the polymer compound is blended with all the raw materials as they are, and emulsified and dispersed. An organic polyisocyanate is emulsified and dispersed in water by an agent, and a polymer compound as a main ingredient is blended and emulsified and dispersed therein, and the polymer compound as a main ingredient is first emulsified in water by an emulsifier / dispersant. Examples thereof include a method of dispersing, emulsifying and dispersing by mixing organic polyisocyanate therein. A preferred method is a method in which an organic polyisocyanate is first emulsified and dispersed in water using an emulsifying / dispersing agent, and then a polymer compound is blended and emulsified and dispersed therein.

  The blending ratio of water, the emulsifying / dispersing agent, and the organic polyisocyanate (curing agent) is preferably 0.1 with respect to 100 parts by mass of water. -500 mass parts, More preferably, it is 1-100 mass parts, Most preferably, it is 3-50 mass parts. The mixing ratio of water to the emulsifying / dispersing agent, organic polyisocyanate (curing agent) and polymer compound (main agent) is 100 parts by weight of the emulsifying / dispersing agent and organic polyisocyanate (curing agent). The total amount of the polymer compound (main agent) is 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. This water-emulsified / dispersed isocyanate curing agent or water-emulsified / dispersed curable composition is stably present after emulsification and dispersion. Since the isocyanate group also reacts with active hydrogen (group) present on the surface of the base material to be applied in addition to the main agent, it becomes a paint or adhesive with very good adhesion. In addition, even after a considerable time has passed after emulsification and dispersion and the isocyanate group has disappeared, it is stably present as an emulsion state having a particle size of about 0.05 to 5 μm, and can be obtained by drying at room temperature or heating. 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 substrates. In addition, when importance is attached to adhesiveness with a base material, it is preferable to use it in the state in which an isocyanate group exists.

  In the emulsifying / dispersing agent, water emulsifying / dispersing isocyanate curing agent, water emulsifying / dispersing curable composition in the present invention, for example, an antioxidant, an ultraviolet absorber, a pigment, a dye, a flame retardant, Additives such as hydrolysis inhibitors, lubricants, plasticizers, fillers, and storage stabilizers can be appropriately blended.

  Furthermore, the water emulsification / dispersion curable composition of the present invention can be applied by a conventional coating method conventionally used. An airless spray machine, an air spray machine, an electrostatic coating machine, an immersion, a roll A coater, knife coater, brush or the like can be used.

  Hereinafter, the present invention will be described in more detail with reference to synthesis examples and application examples, but the present invention should not be construed as being limited thereto. In the production examples, production comparison examples, etc., “%” means “mass%”.

[Production of allophanate emulsifier / dispersant]
<Production Example 1>
Urethane reaction was performed at 90 ° C. for 2 hours at 950 g of hexamethylene diisocyanate and 50 g of isopropanol in a reactor of 1 L 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 allophanated 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 added, and a stop 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 19.2% (NCO -1). A volume of 1 L reactor equipped with a stirrer, thermometer, cooler and nitrogen gas inlet tube: NCO-1 (600 g), methoxypolyethylene glycol (molecular weight of about 400) 400 g, and urethanization reaction 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 allophanated 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 added, and a stop reaction was performed at 50 ° C. for 1 hour. Thus, when analyzed by GPC measurement with an isocyanate content of 3.3%, a viscosity of 8700 mPa · s at 25 ° C., an emulsifying / dispersing agent EA-1 having a free hexamethylene diisocyanate of 0.1% was obtained. The pot life was 23 hours.

<Production Example 2>
A urethanization reaction was performed at 90 ° C. for 2 hours at 880 g of hexamethylene diisocyanate and 120 g of 2-ethylhexanol in a reactor of 1 L 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 allophanated 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 added, and a stop 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 14.4% (NCO -2). A capacity of 1L reactor equipped with stirrer, thermometer, cooler and nitrogen gas inlet tube: 700g of NCO-2, 300g of methoxypolyethylene glycol (molecular weight about 400), and urethanization reaction 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 allophanated 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 added, and a stop reaction was performed at 50 ° C. for 1 hour. Thus, when analyzed by GPC measurement with an isocyanate content of 3.3%, a viscosity of 6500 mPa · s at 25 ° C., an emulsifier / dispersant EA-2 having a free hexamethylene diisocyanate of 0.1% was obtained. The pot life was 23 hours.

<Production Comparative Example 1>
Volume with a stirrer, thermometer, condenser and nitrogen gas inlet tube: In a 1 L reactor, 510 g of hexamethylene diisocyanate, 95 g of isopropanol, 395 g of methoxypolyethylene glycol (molecular weight about 400), urethane at 90 ° C. for 2 hours The 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 allophanated 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 added, and a stop reaction was performed at 50 ° C. for 1 hour. Thus, when analyzed by GPC measurement with an isocyanate content of 3.3%, a viscosity at 25 ° C. of 10,000 mPa · s, an emulsifier / dispersant EA-3 having 1% of free hexamethylene diisocyanate was obtained. The pot life was 12 hours.

<Production Comparative Example 2>
Volume with a stirrer, thermometer, condenser and nitrogen gas inlet tube: 500 g of hexamethylene diisocyanate, 100 g of isopropanol, 400 g of methoxypolyethylene glycol (molecular weight about 400), urethane at 90 ° C. for 2 hours in a 1 L reactor The 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 allophanated 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 added, and a stop reaction was performed at 50 ° C. for 1 hour. Thus, when analyzed by GPC measurement with an isocyanate content of 2.4%, a viscosity at 25 ° C. of 160000 mPa · s, an emulsifier / dispersant EA-4 having 0.1% free hexamethylene diisocyanate was obtained. Odor was not confirmed, but it was not emulsified or dispersed in water due to its high viscosity.

  The measurement method of each analytical value in Production Examples 1 and 2 and Production Comparative Examples 1 and 2 is as follows.

[Isocyanate content]
Measured according to JIS K1603.

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

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

[Evaluation of pot life]
5 g of each emulsifier / dispersant 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 (Coronate HXLV manufactured by Tosoh Corporation, isocyanate content = 23) 3%) and 90 g of water were stirred at 2000 rpm for 30 seconds at a high speed using a homomixer, and the time until the isocyanate group disappeared was measured.

[Emulsification / dispersion evaluation and odor confirmation]
4 g of each emulsifying and dispersing agent EA-1 to 3 obtained in Production Examples 1 and 2 and Production Comparative Example 1 and an isocyanurate modified product of 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 of odor of hexamethylene diisocyanate was examined.

  In the emulsification test, there was no odor for those using Production Examples EA-1 and EA-2, but the odor was confirmed for those of Production Comparative Example EA-3. This seems to be because free hexamethylene diisocyanate was not distilled and removed in the production process of EA-3. Production Comparative Example EA-4 had no odor but was not emulsified / dispersed in water due to its high viscosity.

Claims (11)

A method for producing an emulsifying / dispersing agent obtained from the following steps.
First step: a step of reacting the organic diisocyanate (a) with a hydrophobic group-containing monoalcohol (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 free organic diisocyanate (a) by distillation.
Fourth step: A step of reacting the allophanate-modified isocyanate obtained from the third step with a nonionic hydrophilic group-containing monofunctional alcohol (c) in the presence of an allophanate catalyst.
Fifth step: a step of adding a catalyst poison to stop the allophanatization reaction. The method for producing an emulsifying / dispersing agent according to claim 1, wherein the organic diisocyanate (a) is hexamethylene diisocyanate. The method for producing an emulsifying / dispersing agent according to claim 1 or 2, wherein the free organic diisocyanate (a) is 0.5 mass% or less. The method for producing an emulsifying / dispersing agent according to any one of claims 1 to 3, wherein the hydrophobic group-containing monoalcohol (b) is an alkyl monoalcohol having 1 to 20 carbon atoms. The method for producing an emulsifying / dispersing agent according to any one of claims 1 to 4, wherein the nonionic hydrophilic group-containing monofunctional alcohol (c) is represented by the following (formula 1).
R ¹ —O — (— R ² —O—) n—H (Formula 1)
(However, R ¹ represents an alkyl group, R ² represents an alkylene group containing 30 mol% or more of an ethylene group. N represents an integer of 1 or more.) The molar ratio of the hydrophobic group-containing monoalcohol (b) / nonionic hydrophilic group-containing monofunctional alcohol (c) is (b) / (c) = 10/90 to 90/10, A method for producing an emulsifying / dispersing agent according to any one of claims 1 to 5. The amount of the nonionic hydrophilic group-containing monofunctional alcohol (c) used is 10 to 60% by mass in the total amount of the above (a), (b), and (c), A method for producing an emulsifying / dispersing agent according to any one of claims 1 to 6. A method for producing a water-emulsified or water-dispersed isocyanate curing agent comprising emulsifying or dispersing an organic polyisocyanate in water, wherein the emulsifying / dispersing agent according to any one of claims 1 to 7 is used. A method for producing a water-emulsified or water-dispersed isocyanate curing agent, comprising using an emulsifier / dispersant obtained by the production method. A method for producing a water-emulsified or water-dispersed product comprising emulsifying or dispersing a hydroxyl group-containing compound or a hydroxyl group-free compound in water, wherein the emulsification method according to any one of claims 1 to 7 is used. A method for producing a water emulsion or a water dispersion, comprising using an emulsifier / dispersant obtained by a method for producing a dispersant. A method for producing a water emulsion or a water dispersion, comprising emulsifying or dispersing a composition containing an organic polyisocyanate and a hydroxyl group-containing compound or a hydroxyl group-free compound in water, wherein: A method for producing a water emulsification or water dispersion, comprising using the emulsification / dispersant obtained by the method for producing an emulsification / dispersing agent according to any one of 1 to 7. Water comprising the water emulsification or water-dispersed isocyanate curing agent obtained by the method for producing a water-emulsification or water-dispersed isocyanate curing agent according to claim 8, and a hydroxyl group-containing compound or a hydroxyl group-free compound. A method for producing an emulsified or water-dispersed curable composition.