KR100942404B1 - Two-component curable aqueous urethane-alkyd resin composition and use thereof - Google Patents

Abstract

Provided is a two-liquid curable aqueous resin composition capable of effectively expressing both characteristics of a polyurethane resin and an alkyd resin in a short time. A two-liquid curable aqueous resin composition containing a polyurethane alkyd resin emulsion (A) having an active hydrogen atom in a molecule and a curing agent (B) composed of a polyisocyanate that can be dispersed in the emulsion (A) is prepared. The composition further contains a metal dryer (C), and the alkyd resin component of the polyurethane alkyd resin emulsion (A) may contain an unsaturated fatty acid as a structural unit. The hardener (B) may be a dispersible polyisocyanate obtained by reaction with a surface active or dispersible component having an active hydrogen atom reactive with polyisocyanate and an isocyanate group.

Description

2-liquid curable aqueous urethane alkyd resin composition and use thereof {TWO-COMPONENT CURABLE AQUEOUS URETHANE-ALKYD RESIN COMPOSITION AND USE THEREOF}

The present invention consists of a polyurethane alkyd resin emulsion and a polyisocyanate curing agent that can be dispersed in the emulsion, and is a two-component curable aqueous resin composition useful as an aqueous coating agent (aqueous paint such as woodworking paints and automotive paints) and an aqueous primer. (The composition for coating etc.) and its use.

Polyurethane resins are widely used for various paints, adhesives, and various coating agents because of their excellent adhesion, wear resistance, impact resistance and mechanical strength to substrates. As such a polyurethane resin paint, an organic solvent-based polyurethane resin paint obtained by dissolving a polyurethane resin in an organic solvent is known. However, the organic solvent does not necessarily have a good effect on the human body or the environment, and there is also a risk of ignition. Therefore, while the interest in the sanitary environment has recently increased, the development of an aqueous polyurethane resin coating composed of an aqueous polyurethane resin dispersion in which a polyurethane resin is dispersed in water, in place of the organic solvent-based polyurethane resin coating, is rapidly progressing. It is becoming.

Alkyd resins, on the other hand, have good glossiness and water resistance on the surface of coating films, have a thick film feel, and are inexpensive, and have therefore been widely used for industrial and general purpose applications since ancient times. For example, emulsification of alkyd resin is also considered in order to use it widely for the use of various coating materials, adhesive agents, various coating agents, etc. In particular, urethane alkyd resin emulsions in which urethane resins have been complexed have been developed in order to provide added values such as weather resistance and solvent resistance.

For example, JP 6-299117 A (Patent Document 1) discloses a resin (A) having an hydroxyl group of 30 to 250 and an oxycarboxyl obtained by reacting dry oil or semi-dry oil and / or their fatty acids as essential components. A coating composition for water-based synthetic resin combination paints comprising an aqueous resin obtained by reacting an acid (B), another hydroxyl compound (C), an organic isocyanate compound (D), a pigment, and a drying agent is disclosed. In this document, chain elongation is carried out after urethanization and water dispersion, using an alkyd resin obtained by a transesterification reaction of a (semi) dry oil and pentaerythritol. Such a composition is capable of crosslinking at room temperature, has good dryness, thickness, brush coating property, and no ester bond adjacent to a carboxyl group, and is excellent in hydrolysis resistance. However, since substantially a long time is required for the crosslinking reaction, a high hardness coating film cannot be obtained in a short time, and the degree of improvement in water resistance, moisture heat resistance, and solvent resistance is also low.

In addition, Japanese Unexamined Patent Application Publication No. Hei 6-329892 (Patent Document 2) discloses an alkyd resin (A) having a hydroxyl group of 30 to 250, an oxycarboxylic acid (B), an organic isocyanate (C), and other hydroxyl compounds (D There is disclosed a thermosetting aqueous resin composition comprising an aqueous resin and a curing agent obtained by reacting. This document describes that a coating film having high hardness and various durability can be formed by curing an alkyd resin similar to the patent document 1 with a curing agent such as an amino resin or a block isocyanate. However, in this composition, since amino resin and block isocyanate are used as a hardening | curing agent, baking is essential and a high hardness coating film is not obtained at normal temperature.

In addition, in the case of applying an organic top coating material including a urethane-based coating material to an inorganic material adherend such as slate, concrete, mortar, etc., in order to secure stronger adhesion, a moisture-curable polyurethane resin or the like is used. It was necessary to mix | blend a large amount of organic solvents for the purpose of improving impregnation property and further coating workability. Although primers containing such a large amount of organic solvents are excellent in coating workability and coating performance after curing, problems such as adverse effects on the health of workers and adverse effects on the environment due to volatilization of the organic solvents in operation have been pointed out, and thus, aqueous The appearance of primer compositions is expected.

Patent Document 1: Japanese Patent Application Laid-Open No. 6-299117 (claims, paragraph number [0047], Example)

Patent Document 2: Japanese Patent Application Laid-open No. Hei 6-329892 (claims, paragraph number [0034], Example)

Disclosure of Invention

Problems to be Solved by the Invention

Accordingly, an object of the present invention is to provide a two-liquid curable aqueous resin composition capable of effectively expressing the properties of both a polyurethane resin and an alkyd resin in a short time.

Another object of the present invention is to provide a two-liquid curable aqueous resin composition which is excellent in mechanical properties such as hardness and abrasion resistance, and also high in water resistance, moist heat resistance and solvent resistance.

Still another object of the present invention is to provide a two-liquid curable aqueous resin composition which is excellent in compatibility between the main agent and the curing agent and also excellent in the feeling of thickness and coating workability in forming a coating film even when a polyurethane alkyd resin emulsion is used as the main agent. .

Another object of the present invention is to provide a two-liquid curable aqueous resin composition capable of adjusting the alkyd resin component in the urethane component at any ratio and controlling the coating film properties.

Still another object of the present invention is to provide a two-liquid curable aqueous resin composition having excellent adhesion to inorganic material adherends such as slate, concrete, mortar, and the like, and excellent adhesion to top coat materials and durability.

Another object of the present invention is to provide a two-liquid curable aqueous resin composition (or paint) which is mainly useful as woodworking paint, automotive paint, aqueous primer and the like. Means to solve the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, when the polyurethane alkyd resin emulsion which has an active hydrogen atom in a molecule | numerator, and the specific polyisocyanate as a hardening | curing agent are combined, the characteristics of both a polyurethane resin and an alkyd resin can be effectively made in a short time. It was found that the two-liquid curable aqueous resin composition having high mechanical resistance such as hardness, abrasion resistance, and water resistance, high moist heat resistance, and high solvent resistance was obtained, and thus, the present invention was completed.

That is, the aqueous resin composition (two-liquid curable aqueous resin composition) of the present invention is a polyurethane alkyd resin emulsion (A) having an active hydrogen atom in a molecule and a curing agent (B) composed of polyisocyanate that can be dispersed in the emulsion (A). ). The polyurethane alkyd resin emulsion (A) may be an emulsion obtained by the reaction of an alkyd resin having a hydroxyl value of 30 to 250 and a polyisocyanate. The active hydrogen atom of a polyurethane alkyd resin emulsion (A) may be derived from a hydroxyl group, for example. The said composition further contains a metal dryer (C), and the alkyd resin component of a polyurethane alkyd resin emulsion (A) may contain unsaturated fatty acid as a structural unit. The polyurethane alkyd resin emulsion (A) may further contain the (meth) acryl component which has a polymeric group. Moreover, the hardening | curing agent (B) may be dispersible polyisocyanate obtained by reaction with the surface active or dispersible component which has active active hydrogen atom reactive with respect to polyisocyanate and an isocyanate group. Moreover, the said surfactant or dispersible component can be comprised by at least 1 sort (s) chosen from the compound group which consists of a compound which has a nonionic surfactant and at least an ethylene oxide chain. In addition, the ratio of the hardening | curing agent (B) with respect to the said polyurethane alkyd resin emulsion (A) may be about 0.3-4 (equivalent ratio) as an isocyanate group / active hydrogen atom in solid content conversion. This composition can usually be cured at room temperature.

The present invention also includes a two-liquid curable aqueous coating containing a polyurethane alkyd resin emulsion (A) having an active hydrogen atom in a molecule and a curing agent (B) composed of a polyisocyanate that can be dispersed in the emulsion (A).

The present invention also includes a two-liquid curable aqueous primer containing a polyurethane alkyd resin emulsion (A) having an active hydrogen atom in a molecule and a curing agent (B) composed of a polyisocyanate that can be dispersed in the emulsion (A). This aqueous primer composition is excellent in adhesiveness and durability to inorganic material adherends such as slate, concrete and mortar. Moreover, it is also excellent in adhesiveness and durability with top coat materials, such as a waterproofing material, a flooring material, and a sealing material, which exhibit the excellent adherend protection effect after hardening.

In addition, in this specification, a "(meth) acrylic-type monomer" or "(meth) acrylic-component" not only generically an acryl-type monomer and a methacryl-type monomer, but also a polymerizable monomer (styrene or vinyl) which has a polymerizable unsaturated bond. Toluene, etc.) may be used.

Effects of the Invention

In this invention, since the hardening agent comprised from the specific polyurethane alkyd resin emulsion and the specific polyisocyanate is combined, the characteristic of both a polyurethane resin and an alkyd resin can be expressed effectively in a short time. Moreover, while being excellent in mechanical properties, such as hardness and abrasion resistance, water resistance, moist heat resistance, and solvent resistance can also be improved. Moreover, even if a polyurethane alkyd resin emulsion is used as a subject, it is excellent in compatibility of a main body and a hardening | curing agent, and also excellent in the sense of thickness and coating workability in coating-film formation. Moreover, the alkyd resin component in a urethane component can be adjusted in arbitrary ratios, and coating-film characteristics can be controlled. Therefore, the two-liquid curable aqueous resin composition of the present invention is useful as an aqueous paint such as woodwork paint, automotive paint, and aqueous primer.

Detailed description of the invention

The two-liquid curable aqueous resin composition of the present invention contains a polyurethane alkyd resin emulsion (A) having an active hydrogen atom in a molecule thereof and a curing agent (B) composed of a polyisocyanate that can be dispersed in the emulsion (A). In addition to the adhesion to, the coating properties (particularly high hardness) and water resistance are excellent.

[Polyurethane Alkyd Resin Emulsion (A)]

The polyurethane alkyd resin emulsion (A) has an active hydrogen atom (such as a hydrogen atom of a hydroxyl group) in a molecule, and at least an alkyd resin as a compound (polyol component) having an active hydrogen atom reactive with a polyisocyanate and an isocyanate group It is obtained by reaction with. In this invention, the hydroxyl value of an alkyd resin is about 30-200, The alkyd resin which has such a hydroxyl value is used as a polyol component of a polyurethane alkyd resin emulsion. Furthermore, in addition to an alkyd resin, you may use the other component which has an active hydrogen atom reactive with an isocyanate group. The said active hydrogen atom is an alkyd resin, the modified polyisocyanate which has an active hydrogen atom, a chain extender, and another component, at least What is necessary is just to originate from one component.

(1) alkyd resin

The alkyd resin may be a polyester (oil free alkyd resin) obtained by condensation reaction between a polycarboxylic acid containing a long-chain aliphatic polycarboxylic acid and a polyol, but is preferably a polyester (oil-modified alkyd resin) obtained by using an oil or fat and a fatty acid. Do.

Alkyd resins, also referred to as oil modified polyesters, include at least one oil component selected from polyesters, oils and saturated or unsaturated higher fatty acids obtained by the reaction of a polyol with at least one oil component selected from fats and saturated or unsaturated higher fatty acids. Polyester obtained by reaction of a polyol and polycarboxylic acid, etc. are contained. In addition, these reactions include not only an esterification reaction but also a transesterification reaction (for example, transesterification reaction of fats and oils (triglyceride etc.) and a polyol).

(Polyol)

Examples of the polyol include various polyols used in the production of polyesters, for example, aliphatic diols [alkane diols (ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, neopentyl glycol, 1,6-hexanediol, 2,2-diethyl-1,3-propanediol, 3,3-dimethylolheptane, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,18-octa decanediol, such as the C _{2 - 22} alkanediol), alkene diol (2-butene-1,4-diol, 2,6-dimethyl-1-octene-3,8-diol and the like), poly-C _{2 -4} alkylene Glycol (diethylene glycol, triethylene glycol, polyethylene glycol having an average molecular weight of about 150 to 4000, dipropylene glycol, polypropylene glycol having an average molecular weight of about 150 to 4000, polytetramethylene ether glycol, etc. having an average molecular weight of about 150 to 4000, etc.) , Cycloaliphatic diols (1,4 -Cyclohexanediol, 1,4-cyclohexanedimethanol cycloalkane diols such as methanol, acids, hydrogenated, such as hydrogenated bisphenol A, bisphenols, or a C _{2 - 4} alkylene oxide adduct and the like), aromatic diol (Reggio benzene such Rezin diols, xylylene glycol and the like aromatic aliphatic diols, bis-hydroxy ethylene polyester diols such as terephthalate, bisphenol a, bisphenol S, bisphenol such as bisphenol F, or a C ₂ of ₄ alkylene Oxide adducts), trivalent or higher polyols [aliphatic polyols (glycerine, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, 2-methyl-2-hydroxymethyl-1,3-propanediol , 2,4-dihydroxy-3- (hydroxymethyl) pentane, 2,2-bis (hydroxymethyl) -3-butanol, such as an aliphatic C _{3 - 24-triol,} pentaerythritol, dipentaerythritol Pentaerythritols, etc.), sugar alcohols (D-sorbitol, xylitol, D-mannitol) Etc.) can be exemplified. These polyols can be used individually or in combination of 2 or more types. Among them, aliphatic polyols such as trivalent or higher polyols, for example, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, are preferable.

(Oil component)

The oil component contains fats, saturated or unsaturated fatty acids. As fats and oils, for example, vegetable oil (cotton seed oil, linseed oil, castor oil, dehydrated castor oil, soybean oil (safflower oil), soybean oil, rice bran oil, corn oil, sesame oil, sunflower oil, sugar sugar oil, asami oil, rapeseed oil, peanut Oil, palm oil, palm oil, kaypok oil, tonsil oil, olive oil, tall oil, eggplant oil, paulownia oil, etc., animal oil (Uji, pork, sunny place, goat, marge, chicken, turkey, etc.), fish oil (herring oil, Gaza) Brown rice, cod oil, chamseo oil, hariba oil, carp oil, trout oil, catfish oil), or hydrogenated oils thereof. These fats and oils can be used individually or in combination of 2 or more types. Among these fats and oils, vegetable oils, in particular, dry oils such as linseed oil, eggplant oil, paulownia oil, dehydrated castor oil, soybean oil, cottonseed oil, soybean oil, corn oil, sesame oil, rapeseed oil, unsweetened oil such as sugar oil, palm oil, Undrying oils, such as palm oil, are preferable.

As a saturated fatty acid, For example, linear or branched, such as caprylic acid, capric acid, pelagonic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, etc. And chain saturated C _8-24 fatty acids. As an unsaturated fatty acid, For example, linear or branched, such as myristic acid, palmitoleic acid, petroleic acid, oleic acid, basonic acid, linoleic acid, linolenic acid, eleostearic acid, gartrenic acid, arachidonic acid, erucic acid, etc. And chain unsaturated C _8-24 fatty acids. These fatty acids may have substituents, such as a hydroxyl group. As a fatty acid which has a hydroxyl group, the ricinoleic acid, savinic acid, dioxystearic acid etc. which are main components of castor oil are mentioned, for example. The fatty acid may be a fatty acid obtained by saponification or the like from the oil or fat, and for example, a fatty acid obtained from dehydrated castor oil, dehydrated castor oil, linseed oil, soybean oil, soybean oil, palm oil (for example, dehydrated). Castor oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, soybean oil fatty acid, palm oil fatty acid and the like). These saturated or unsaturated fatty acids can be used individually or in combination of 2 or more types. Among these fatty acids, unsaturated fatty acids such as fatty acids (oleic acid, linoleic acid, linolenic acid, and the like) obtained from dry oil or semi-dry oil, and high diene fatty acids are preferable. Among these fatty acids, fatty acids containing a large amount of saturated fatty acids such as fatty acids (lauric acid, capric acid, caprylic acid, myristic acid, etc.) obtained from undried oil, and palm oil fatty acids can suppress coloring of the resin. It is preferable at the point which can be used.

In particular, when an oil component having an unsaturated bond, such as dry oil, semi-dry oil or unsaturated fatty acid, is used as the oil component, the unsaturated bonds contained in these oil components react with oxygen in the air to cause an oxidative curing reaction to cure. A better coating film can be formed.

Such oxidation-hardening reaction normally reacts gradually using oxygen in air, but in order to accelerate | stimulate this reaction, you may add the metal dryer or desiccant (C) mentioned later further. That is, by combining the polyurethane alkyd resin emulsion (A) having the alkyd resin component modified with unsaturated fatty acid and the metal drier (C), a coating film having excellent properties such as hardness can be formed in a short time.

(Polycarboxylic acid)

As polycarboxylic acid, various polycarboxylic acids used for manufacture of polyester, for example, aromatic dicarboxylic acid or its anhydride (terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, etc.), alicyclic dica Leric acid or anhydrides thereof (tetrahydrophthalic acid, tetrahydro phthalic anhydride, hexahydrophthalic acid, hexahydro phthalic anhydride, methyltetrahydrophthalic acid, hept anhydride, hymic anhydride, etc.), aliphatic dicarboxylic acid or anhydrides thereof ( C4-20 alkanedicarboxylic acid such as succinic acid, succinic acid, adipic acid, azaline acid, sebacic acid, itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride Acids, etc.), trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, methylcyclohexericarboxylic acid, or carboxylic acids thereof La can be exemplified such as alkyl esters. These polycarboxylic acids can be used individually or in combination of 2 or more types. Among these polycarboxylic acids, aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid are commonly used.

In preparation of alkyd resin, you may add to the said fatty acid and polycarboxylic acid as a carboxylic acid component further, for example, you may use aromatic monocarboxylic acids, such as benzoic acid and p-t-butylbenzoic acid.

Such an alkyd resin can be produced by a conventional method, for example, a fatty acid method using fatty acids as a raw material, or a monoglyceride method which performs a transesterification reaction using a fat or oil as a raw material. In the fatty acid method, for example, a fatty acid, a polyol, and a polycarboxylic acid may be injected, and the esterification reaction may be performed at about 220 to 250 ° C. for about 6 to 10 hours. In esterification, you may add very small amount of esterification catalysts, such as monon- butyl tin oxide, for example. The proportion of the esterification catalyst is, for example, 0.00001 to 0.1 parts by weight, preferably 0.0001 to 0.01 parts by weight based on 100 parts by weight of the oil component. Moreover, in order to remove the condensed water in esterification reaction, you may use the inert solvent (aromatic hydrocarbons, such as toluene and xylene) azeotropic with water.

In the monoglyceride method, for example, the reaction is carried out for 2 to 3 hours at about 230 to 250 ° C in the presence of an alkali catalyst while stirring the fats and oils and the polyol, followed by the polyol and polycarboxylic acid as necessary. May be injected and esterification may be performed at about 220 to 250 ° C. In the transesterification reaction, for example, a very small amount of basic catalysts such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium acetate, lithium acetate and the like may be added.

The ratio (weight ratio) of the total amount of the oil component, the polyol component, and the polycarboxylic acid to the ratio of each component in the alkyd resin is the former / the latter = 10/1 to 1/5, preferably 5/1. -1/3, More preferably, it is about 4/1-1/1 (especially 3/1-1.5 / 1).

The proportion of the polyol component is, for example, 5 to 200 parts by weight, preferably 10 to 100 parts by weight, more preferably 15 to 70 parts by weight (particularly 20 to 50 parts by weight) based on 100 parts by weight of the oil component. to be.

The proportion of the polycarboxylic acid is, for example, 0 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight (particularly 10 to 40 parts by weight) based on 100 parts by weight of the oil component. )

Alkyd resin may have a hydroxyl group and / or a carboxyl group, but since it is used as a polyol component, it usually has at least a hydroxyl group. Alkyd resin may have a hydroxyl group in a branched chain, and may have it in both terminal. Typically, at least both ends have hydroxyl groups.

The hydroxyl value (KOHmg / g) of an alkyd resin is 30-250, Preferably it is 40-230, More preferably, it is about 50-220 (especially 60-200).

(2) polyisocyanate

The polyisocyanate is not particularly limited as long as it has two or more isocyanate groups in the molecule, and polyisocyanates commonly used in the production of polyurethane and the like, for example, aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, And low molecular weight polyisocyanates such as aromatic polyisocyanates, prepolymers, isocyanurates, trions, and derivatives and modified substances of these polyisocyanates.

In addition, "polyisocyanate" is a general term of the compound which has a some isocyanate group in a molecule | numerator, derivatives and modified substances obtained from low molecular polyisocyanates, such as diphenylmethane diisocyanate, tolylene diisocyanate, and xylylene diisocyanate, and these polyisocyanates , Prepolymer, and the like. The term "polyisocyanate derivative" is a generic term for a compound obtained from a low molecular polyisocyanate and includes a modified product, a prepolymer, and the like. A "polyisocyanate modified body" means the reactant which modified | denatured low molecular polyisocyanate and a prepolymer.

As said aliphatic polyisocyanate, diisocyanate (for example, trimethylene diisocyanate, 1,2-propylene diisocyanate, tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2, 3- butylene diisocyanate, 1,3) -butyl diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 2,4,4 or 2,2,4-trimethyl hexamethylene diisocyanate, such as a C _{2 - 16} alkanediyl diisocyanate, 2,6-diimide SOCCIA NATO Methylcaproate, etc.), polyisocyanate (for example, lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatodecane, 1,8-diisocyanato-4 -isocyanatomethyl-octane, 1,3,6- teuriyi SOCCIA NATO hexane, 2,5,7- trimethyl-1,8-diimide SOCCIA NATO-5-isocyanate, such as methyl NATO octane C _{6 - 20} alkanes triisocyanate Etc) And the like.

As said alicyclic polyisocyanate, diisocyanate (for example, 1, 3- cyclopentane diisocyanate, 1, 4- cyclohexane diisocyanate, 1, 3- cyclohexane diisocyanate, 3-isocyanatomethyl-3) , 5,5-trimethylcyclohexyl isocyanate (common name: isophorone diisocyanate), 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexane Diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane (common name: hydrogenated xylylene diisocyanate) or mixtures thereof, norbornane diisocyanate, etc., polyisocyanate (eg, 1 , 3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo [ 2.2.1] heptane, 2- (3-isocyanatopropyl) -2,6- (Isocyanatomethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo [2.2.1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2.2.1] heptane, 6- (2-isocyanatoethyl) -2-iso Cyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2.2.1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanato Propyl) -bicyclo [2.2.1] -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo [2.2.1] heptane Triisocyanates, such as these), etc. are mentioned.

As said aromatic aliphatic polyisocyanate, diisocyanate (for example, 1, 3- or 1, 4- xylylene diisocyanate or its mixture, (omega), (omega) '-diisocyanato- 1, 4- diethyl benzene, 1 , 3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or mixtures thereof), polyisocyanate (for example, 1,3,5 And triisocyanates such as -triisocyanatomethylbenzene).

As said aromatic polyisocyanate, diisocyanate (for example, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'- diphenylmethane diisocyanate, 1, 5- naphthalene diisocyanate, 2,4'-) Or 4,4'-diphenylmethane diisocyanate or mixtures thereof, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, 4,4'-toluidine diisocyanate, 4,4'-diphenylether diisocyanate Triisocyanates such as polyisocyanate (for example, triphenylmethane-4,4 ', 4' '-triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanate toluene, For example, tetraisocyanate, such as 4,4'- diphenylmethane-2,2 ', 5,5'- tetraisocyanate, etc. are mentioned.

As a derivative of polyisocyanate, 2,4 obtained by reaction of the dimer, trimer (isocyanurate ring containing polyisocyanate), biuret, allophanate, carbon dioxide gas, and the said polyisocyanate monomer of the said polyisocyanate, for example. Polyisocyanates, carbodiimide, ureddione, polymethylenepolyphenylpolyisocyanates (crude MDI, polymeric MDI), crude TDI, etc., having a, 6-oxadiazinetrione ring.

As a modified product of the polyisocyanate, for example, the polyisocyanate or a derivative of the polyisocyanate and a low molecular weight polyol or a low molecular weight polyamine which will be described later, and the isocyanate group of the polyisocyanate is a hydroxyl group of a low molecular weight polyol or an amino group of a low molecular weight polyamine. The polyol modified body, polyamine modified body, etc. which are obtained by making it react by more equivalence ratio are mentioned. These polyisocyanates may be used alone or in combination of two or more.

(3) other ingredients

In addition to the said alkyd resin and polyisocyanate, the emulsion of this invention may contain the compound which has an active hydrogen atom (for example, hydroxyl group, a carboxyl group, an amino group, etc.) reactive with an isocyanate group as another component.

(Other polyols)

As the compound having a hydroxyl group, other polyol may be included in addition to the alkyd resin. Other polyols are not particularly limited, and various polyols used in the production of polyurethanes, for example, polyols exemplified in the above paragraphs of alkyd resins, polyester polyols (except the alkyd resins), and polyethers Polyols, polyetherester polyols, polyesteramide polyols, acrylic polyols, polycarbonate polyols, polyurethane polyols, polyhydroxyalkanes, polybutadiene polyols, modified castor oil polyols, and the like, and these polyols alone or It can be used in combination of 2 or more type.

As said polyester polyol, it can obtain by reaction of dicarboxylic acid and diol, for example. As dicarboxylic acid (or its anhydride), the dicarboxylic acid etc. which were illustrated by the term of the polycarboxylic acid in the said alkyd resin component are mentioned, for example. As a diol, the diol etc. which were illustrated by the term of the polyol in the said alkyd resin component are mentioned, for example. Furthermore, if necessary, polycarboxylic acids (trimellitic acid, pyromellitic anhydride, etc.) and polyhydroxy compounds (glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, etc.) may also be used. do. Polyol initiators such as triols (eg glycerin, 1,2,6-hexanetriol, 1,1,1-tris (hydroxymethyl) propane, etc.), tetraols (eg, Pentaerythritol, erythritol, methylglucoside, etc.), hexaols (e.g., sorbitol, dipentaerythritol, etc.), octaols (e.g., sucrose, etc.) or amine initiators, e.g., diamines ( For example, ethylenediamine, propylenediamine, hexamethylenediamine, hydrazine and the like, lactones using trifunctional or higher polyamines (for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc.) and the like are used. the can also be used polyester polyols obtained by ring-opening polymerization (ε- caprolactone, such as caprolactone, valerolactone, β- methyl -γ- C _4-10 lactone such as valerolactone, etc.).

As said polyether polyol, it is a single or copolymer of an oxirane compound (for example, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, etc.), ethylene glycol, propylene glycol, trimethylol. Low molecular weight polyols, such as propane, glycerin, and bisphenol A, and / or the polyether polyol obtained by superposing | polymerizing the said oxirane compound as an initiator as an initiator is mentioned.

As said polyether ester polyol, For example, the said dicarboxylic acid (aromatic dicarboxylic acid, alicyclic dicarboxylic acid, aliphatic dicarboxylic acid, etc.) or their dialkyl ester or its mixture, and the said poly The polyether ester polyol etc. which can be obtained by reaction of an ether polyol are mentioned.

As said polyesteramide polyol, in reaction of the said polyester polyol (reaction of dicarboxylic acid and diol, etc.), it is amino groups, such as diamine (for example, ethylenediamine, propylenediamine, hexamethylenediamine, etc.) as some reaction component. And polyesteramide polyols obtained by using an aliphatic diamine having a compound).

As said acryl polyol, the polymerizable monomer which has one or more hydroxyl groups in 1 molecule (for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate) Etc.) The acryl polyol etc. which are obtained by copolymerizing the (meth) acrylic-type monomer (for example, (meth) acrylic acid or its ester) which do not contain a hydroxyl group are mentioned.

Examples of the polycarbonate polyol include glycol (ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, Alkanediols such as 3-methyl-1,5-pentanediol, 1,9-nonanediol, 1,8-nonanediol, (poly) oxyalkylene glycols such as diethylene glycol and dipropylene glycol; 1,4- Cycloaliphatic diols such as cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenols such as bisphenol A, and aromatic diols such as alkylene oxide adducts of bisphenols; And polycarbonate polyols obtained by reacting two or more kinds of glycols) with carbonates (dimethyl carbonate, ethylene carbonate, diphenyl carbonate, and the like), phosgene, and the like.

As said polyurethane polyol, the polyol which has a urethane bond in 1 molecule is mentioned, for example. This polyol is, for example, a polyol having a molecular weight of 200 to 5,000 (polyether polyol, polyester polyol, polyether ester polyol, etc.) and an isocyanate group-containing compound having at least two isocyanate groups per molecule, for example, an isocyanate to a hydroxyl group. The polyurethane polyol etc. which were obtained by making the equivalence ratio (isocyanate group / hydroxyl group) of group react with less than 1 (preferably 0.9 or less, for example about 0.3-0.7) are mentioned.

As said polyhydroxyalkane, the liquid rubber etc. which are obtained by copolymerizing isoprene, butadiene, butadiene, acrylamide, etc. are mentioned, for example.

These other polyols may be used alone or in combination of two or more thereof. Among these other polyols, low molecular weight polyols such as alkanediols such as neopentyl glycol and 1,6-hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene poly C _2, such as glycol ether _{- 4} alkylene glycol, glycerin, trimethylolpropane, and polyol such as pentaerythritol, are preferred. The molecular weight of these low molecular weight polyols is a number average molecular weight 62-500, Preferably it is about 62-200.

If necessary, further, monools such as methanol, ethanol, propanols, butanols, 2-ethylhexanol, lauryl alcohol, stearyl alcohol, 2-mercaptoethanol, polyoxymethylenediol monomethyl ether and the like can be added. It can be used together.

The ratio of the other polyol is, for example, 0.1 to 300 parts by weight, preferably 1 to 200 parts by weight, more preferably 3 to 150 parts by weight, particularly 5 to parts by weight based on 100 parts by weight of the alkyd resin. 100 parts by weight).

(Compound Having Anionic Group)

In the polyurethane alkyd resin, the anionic group is not necessarily required, but by introducing an anionic group, the dispersion stability of the polyurethane alkyd resin can be improved. This anionic group is usually introduce | transduced by using the compound which has an active hydrogen atom reactive with anionic group and an isocyanate group.

The active hydrogen atom-containing compound having an anionic group is not particularly limited, and for example, contains an active hydrogen atom reactive with an anionic group and an isocyanate group such as a betaine-containing group such as a carboxyl group, sulfonyl group, phosphoric acid group or sulfobetaine. Group (for example, hydroxyl group, amino group, etc.).

Although the kind in particular of the active hydrogen atom containing compound which has such an anionic group is not restrict | limited, The compound which has at least 1 anionic group and 2 or more active hydrogen atoms is mentioned.

As the active hydrogen atom-containing compound having the carboxyl group, for example, 2,2-dimethylol acetic acid, 2,2-dimethylolactic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2 -dimethylolpropionic acid, 2,2-dimethyl-di-hydroxyl carboxylic acids such as all-valeric acid (dimethylolpropionic _2- C ₁₀ alkanoic acid or _{di-hydroxyl-2 C-10} alkanoic acid, etc.), e.g. And diamino carboxylic acids such as lysine and arginine.

As an active hydrogen atom containing compound which has the said sulfonyl group or sulfonic acid group, it is N, N-bis (2-hydroxyethyl) -2-aminoethane sulfonic acid, 1, 3- phenylenediamine-4, 6, for example. Disulfonic acid, diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,4-diamino-5-toluene sulfonic acid, and the like.

As an active hydrogen atom containing compound which has the said phosphate group, 2, 3- dihydroxypropyl phenyl phosphate etc. are mentioned, for example.

As an active hydrogen atom containing compound which has the said betaine structure containing group, it is obtained by reaction with tertiary amines, such as N-methyl diethanolamine, 1, 3- propane sultone, 1, 4- butane sultone, for example. Sulfobetaine group containing compound etc. are mentioned.

Moreover, the alkylene oxide modified body obtained by adding alkylene oxides, such as ethylene oxide and a propylene oxide, to the active hydrogen atom containing compound which has these anionic groups is also mentioned.

The active hydrogen atom containing compound which has these anionic groups can be used individually or in combination of 2 or more types. Among the compounds having anionic groups, active hydrogen atom-containing compounds having a carboxyl group are preferable.

The ratio of the compound which has an anionic group is 1-100 weight part, Preferably it is 3-50 weight part, More preferably, it is about 5-30 weight part with respect to 100 weight part of alkyd resin. In addition, the ratio of the compound having an anionic group and the polyisocyanate is, for example, 0.1 to 50 parts by weight of the compound having an anionic group, preferably 1 to 40 parts by weight, more preferably 3 to 100 parts by weight of the polyisocyanate. It is about 30 weight part.

(Compound Having Polymeric Group)

In order to improve a coating film physical property, a polyurethane alkyd resin may be made to react with the compound (polymerizable unsaturated compound) which has a polymeric group, and the characteristic by a polymerizable unsaturated compound and its polymer may be provided. When the compound which has an active hydrogen atom is used as a polymerizable unsaturated compound, the (meth) acryl component which has a polymeric group can be introduce | transduced into a polyurethane alkyd resin.

As a polymerizable unsaturated compound which has an active hydrogen atom, For example, a carboxyl group-containing compound [(meth) acrylic acid, maleic acid, itaconic acid, etc.], a hydroxyl group containing compound [2-hydroxyethyl (meth) acrylate, Alkanediol mono ((meth) acrylate), such as 2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate; Such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (poly) _oxy-2- C ₄ alkylene glycol mono (meth) acrylate; Trimethylolpropane mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, glycerol mono (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritoldi Polyol (meth) acrylates such as (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate; N-methylol (meth) acrylamide etc.], imino group containing compound [N-methylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, etc.], reaction of an epoxy compound and carboxylic acid Hydroxyl group-containing compound produced by a saturated or unsaturated carboxylic acid selected from an adduct of diglycidyl ether type epoxy resin with (meth) acrylic acid, glycidyl (meth) acrylate with monocarboxylic acid and dicarboxylic acid Adducts of acids; and the like. The unsaturated carboxylic acid also includes unsaturated fatty acids.

In these polymerizable unsaturated compounds, the compound which has 1-3 (for example, 1 or 2) hydroxyl groups in a molecule | numerator, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Roxypropyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, glycerol mono (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol mono (meth A) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable. In particular, a polymerizable unsaturated compound having one hydroxyl group in a molecule (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, trimethylolpropanedi (meth) acrylic) Latex, glycerol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritolpenta (meth) acrylate, etc.), a polymerizable unsaturated compound having two hydroxyl groups in a molecule (for example , Trimethylolpropane mono (meth) acrylate, glycerol mono (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and the like) are preferable. By using such a compound, a polyurethane alkyd resin becomes what has a (meth) acryl component which has a polymeric group in a molecule | numerator, and can also improve a coating film physical property.

The ratio of the compound which has a polymeric group is about 0-50 weight part with respect to 100 weight part of alkyd resins, for example.

(Low molecular weight polyamine)

In the polyurethane alkyd resin, a compound having an amino group, for example, a unit of a low molecular weight polyamine may be introduced. The low molecular weight polyamine is not particularly limited, and examples thereof include hydrazine, ethylenediamine, propylenediamine, hexamethylenediamine, 1,2-diaminoethane, 1,2-diaminopropane, and 1,3-diaminopentane. , Low molecular weight diamines such as 1,6-diaminohexane, diaminotoluene, bis- (4-aminophenyl) methane, bis- (4-amino-3-chlorophenyl) methane, and diethylenetriamine, tri Low molecular weight polyamine etc. which have three or more amino groups, such as ethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and 2,2'- diamino diethylamine, are mentioned. These low molecular weight polyamines can be used individually or in combination of 2 or more types. The molecular weight of these low molecular weight polyamines is 32-500 in number average molecular weight, Preferably it is about 62-200 in number average molecular weight.

[Preparation of Polyurethane Alkyd Resin]

In the preparation of a polyurethane alkyd resin (polyurethane prepolymer having an alkyd component), a reaction component (an alkyd resin, having a polyisocyanate and an active hydrogen atom, and optionally a polyol, a polymerizable unsaturated compound containing an active hydrogen atom), The active hydrogen atom-containing compound having an anionic group, a low molecular weight polyamine, hereinafter, may be referred to simply as a reaction component having an active hydrogen atom) in terms of active hydrogen atoms (hydroxyl groups and amino groups). As equivalent ratio (isocyanate group / active hydrogen atom) with respect to isocyanate group, it is 0.4-10, Preferably it is 0.6-5, More preferably, it is about 0.8-5 (for example, 1-3). Especially preferable said equivalent ratio (isocyanate group / active hydrogen atom) is more than 1 and 3 or less (for example, 1.01-2.7, Preferably it is 1.1-2.5, More preferably, about 1.2-2.3). By setting it as such a range, a polyurethane prepolymer can be chain-stretched after water dispersion using a free isocyanate group, and the molecular weight as a polyurethane alkyd resin component after water dispersion can be arbitrarily controlled according to the intended use. In particular, when a high molecular weight resin component is required, it is preferable because a uniform dispersion can be easily produced by chain elongation.

The preparation method of polyurethane alkyd resin is not specifically limited, For example, what is necessary is just to react according to a conventional method (bulk reaction method, solution reaction method, etc.). In the bulk reaction method, for example, the reaction component having a polyisocyanate and the active hydrogen atom in the absence of a solvent, in a nitrogen stream, at a reaction temperature of 40 to 85 ° C. for 1 to 24 hours, preferably 1 to 8 hours The reaction may be performed for about a time. The reaction is often carried out by adding a reaction component having the active hydrogen atom while stirring the polyisocyanate.

In the solution reaction method, for example, a reaction component having a polyisocyanate and an active hydrogen atom in the presence of an inert solvent (organic solvent and / or a polymerizable unsaturated compound having no active hydrogen atom) is reacted with a reaction temperature of 20 to What is necessary is just to react at about 90 degreeC (preferably 40-80 degreeC) for about 1 to 24 hours (preferably 1 to 8 hours). Moreover, the solution reaction method which is easier to adjust reactivity and a viscosity is preferable for preparation of the polyurethane prepolymer which has an alkyd resin component.

[menstruum]

The organic solvent is not particularly limited, and solvents inert to isocyanate groups, for example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, 4-methyl-2-pentanone, cyclohexanone, etc., esters (acetic acid) Ethyl, butyl acetate, isobutyl acetate, 1-methoxypropyl-2-acetate, 3-methoxybutyl acetate, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), alicyclic hydrocarbons (cyclohexane, etc.) , Aliphatic hydrocarbons (hexane, isooctane, etc.), ethers (dioxane, tetrahydrofuran, etc.), cellosolves or carbitols (ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate) , Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, di Tylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, di Propylene glycol dimethyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, 2,2,4-trimethyl-1,3-pentanediol diisobutylate, triethylene glycol bis 2-ethylhexa And the like, and a nitrogen-containing solvent (N-methylpyrrolidone, N-ethylpyrrolidone, N-methylcaprolactam, etc.) These solvents can be used alone or as mixed solvents of two or more thereof. Preferred organic solvents are low-boiling organic solvents that are easy to remove, such as ketones (acetone, methyl). Ylketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (dioxane, tetrahydrofuran, etc.), aromatic hydrocarbons (toluene, etc.) etc. are mentioned. Acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate and the like are often used.

As a solvent, you may use the polymerizable unsaturated compound (inert unsaturated compound) which does not have an active hydrogen atom. An inert unsaturated compound is especially effective when the (meth) acryl component which has a polymeric group is introduce | transduced in polyurethane alkyd resin.

The inert unsaturated compound is not particularly limited as long as it is a compound having an α, β-unsaturated bond that can be copolymerized with a (meth) acryl component having a polymerizable group. For example, styrene, vinyltoluene, divinylbenzene, α- Aromatic vinyls such as methyl styrene and aromatic vinylidene; Vinyl cyanide and vinylidene cyanide such as (meth) acrylonitrile; Conjugated dienes such as butadiene, isoprene and chloroprene; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl ( ₂₀ alkyl- _(meth) acrylate meth) acrylate, lauroyl (meth) acrylate, stearyl (meth) acrylate such as C _1; Cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate; Alkanediol di, such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, and nonanediol di (meth) acrylate (Meth) acrylate, oligoethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa ( Alkanes polyol poly (meth) acrylates, such as meth) acrylate; Unsaturated carboxylic allyl esters such as allyl (meth) acrylate, diallyl maleate, diallyl fumarate, and diallyl itaconate; Glycidyl (meth) acrylate; Urethane di (meth) acrylate; Polybutadiene di (meth) acrylate etc. are mentioned. These compounds can be used alone or in combination of two or more. Preferred compounds include acrylonitrile, vinyl aromatic (styrene, divinylbenzene, etc.), acrylonitrile, C _{1 - 10} alkyl (meth) acrylate (methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, ), Ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, allyl (meth) acrylate, and the like. Can be. When forming a hard film, as an inert compound, styrene, divinylbenzene, methyl methacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, trimethylol propane triacrylate, allyl methacrylate, etc. Often used.

The reaction may include, for example, commonly used urethanization catalysts such as amine catalysts (tertiary amines), tin catalysts (organic tin compounds, etc.) and lead-based catalysts, quinones, hydroquinones, and phenols. You may use radical polymerization inhibitors, such as these. In addition, you may remove unreacted components, such as polyisocyanate, from a reaction product using well-known removal means, such as distillation and extraction.

[corrector]

In addition, in preparing a polyurethane alkyd prepolymer having an anionic group, amines (e.g., trimethylamine, triethylamine, tri-n-propylamine) may be used in a suitable step (pre-reaction, after reaction, or a water dispersion process described later). , Tributylamine, diisopropylethylamine, triphenylamine, 2-dimethylaminoethanol, triethanolamine, dimethylpropanolamine, N-methylpiperidine, etc., inorganic bases (e.g., potassium hydroxide, sodium hydroxide, etc.) Neutralizers such as alkali metal hydroxides, ammonia and the like) may be added to neutralize the anionic group to form a salt. The amount of such neutralizer added is, for example, 0.6 to 1.2 equivalents, preferably 0.7 to 1.1 equivalents, more preferably about 0.8 to 1 equivalents, based on 1 equivalent of the anionic group.

[Chain extender]

And in order to obtain a polyurethane alkyd resin emulsion (A), a polyurethane alkyd prepolymer can be disperse | distributed in water with a solvent (inert unsaturated compound and / or organic solvent) as needed, and an aqueous dispersion can be obtained. Moreover, the polyurethane alkyd prepolymer which has an anionic group may prepare an aqueous dispersion using the said neutralizing agent. In addition, when a polyurethane alkyd prepolymer contains an isocyanate group, you may make it react with a chain extender (polyamine and / or water) in water. By this reaction, the polyurethane alkyd prepolymer having an isocyanate group at the terminal can form a polyurethane alkyd resin chain-stretched with a chain extender, and the polyurethane alkyd resin emulsion (A) in which the polyurethane alkyd resin is dispersed in water. Can be obtained.

The polyamine as a chain extender is not particularly limited as long as it is a compound having two or more amino groups, and examples thereof include alkylenediamine (ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexa). Methylenediamine), alicyclic diamine (1,4-cyclohexanediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (common name: isophoronediamine), 4,4'-dicyclohexylmethanediamine, 1,3-bis (aminomethyl) cyclohexane, norbornanediamine), aromaticdiamines (such as xylylenediamine), heterocyclic diamines (piperazine, 2,5-dimethylpiperazine, etc.), hydrazine, dicarboxylic acid di Polyamines such as hydrazide (such as adipic acid dihydrazide) and polyalkylene polyamine (diethylenetriamine, triethylenetetramine, etc.); For example, hydroxy-C _{2 - 10} alkyl hydrazine (hydroxyethyl hydrazine, etc.), hydroxy-C _{2 - 4} alkyl poly C _{2 - 4} alkylene polyamines (hydroxyethyl diethylene triamine, etc.), N- (amino C _{2 - 10} of the alkanediol (3-amino-amino alcohols such as propanediol, etc.) _{- 10} alkyl) hydroxy-C _{2- 10} alkyl amine (N- (2- aminoethyl) ethanolamine, etc.), amino-C ₂ Can be. These polyamines can be used alone or as a mixture of two or more thereof. When using the polyamine (the said amino alcohols) which have a hydroxyl group among these polyamines, active hydrogen atom can be introduce | transduced into a polyurethane alkyd resin. In addition, these polyamines may be added in a form in which part or all of them are masked, for example, ketamine, ketazine or amine salt.

The reaction method in water of the polyurethane prepolymer having the alkyd resin component and the terminal isocyanate group and the polyamine in water is not particularly limited, and a known dispersing method, for example, the polyurethane alkyd prepolymer may be used as a disperser (homodisper or homomixer). While stirring, the method of adding water and dispersing in water, the method of adding and dispersing the said polyurethane alkyd prepolymer in water, etc. can be employ | adopted. What is necessary is just to add a polyamine to the produced dispersion, and to carry out chain extension reaction of the polyurethane prepolymer which has an alkyd resin component and a terminal isocyanate group with polyamine.

The amount of water used to disperse the polyurethane alkyd prepolymer is not particularly limited as long as it can prepare an aqueous dispersion of the polyurethane alkyd prepolymer, and may be, for example, about 20 to 1000 parts by weight based on 100 parts by weight of the polyurethane alkyd prepolymer. do.

The amount of polyamine used is, for example, 0.2 to 1.5, preferably 0.5 to 1.3, and more preferably about 0.7 to 1.1 as an equivalent ratio (amino group / isocyanate group) of the amino group of the polyamine to the isocyanate group of the polyurethane alkyd prepolymer. . The polyamine is usually added dropwise while stirring the aqueous dispersion of the polyurethane alkyd prepolymer. It is preferable to perform dropping of polyamine at the temperature of 30 degrees C or less, and just after completion | finish of dripping, stirring may complete, for example, at normal temperature. By such a chain stretching reaction, the polyurethane alkyd prepolymer is chain stretched with polyamine and / or water, and an aqueous dispersion of the polyurethane alkyd resin having an active hydrogen atom can be obtained.

When the polyurethane alkyd prepolymer does not contain an isocyanate group, it is possible to obtain an aqueous dispersion (polyurethane alkyd emulsion) in which an active hydrogen atom-containing polyurethane alkyd resin is dispersed in water, without performing chain extension. have.

The concentration of anionic groups useful for obtaining a stable aqueous dispersion is a polyurethane alkyd resin (resin that neutralizes a polyurethane alkyd prepolymer containing a terminal isocyanate group, or a resin that neutralizes a polyurethane alkyd prepolymer containing a terminal hydroxyl group). In general, 0.1 to 1.15 mmol / g, preferably 0.2 to 0.95 mmol / g, more preferably about 0.3 to 0.8 mmol / g.

Moreover, if it is necessary for an emulsion, for example, when a polyurethane alkyd resin has a (meth) acryl component, a polymerizable unsaturated compound is added and a radical copolymerization of a polymerizable unsaturated compound and a polymerizable unsaturated bond in a polyurethane alkyd resin emulsion (A) is carried out. The polyurethane alkyd acrylic resin emulsion in which the polyurethane alkyd resin component and the acrylic component are chemically radically copolymerized can also be obtained.

As a polymerizable unsaturated compound, a diacetone acrylamide, an acrolein etc. are mentioned besides the polymerizable unsaturated compound which has the active hydrogen atom of the said illustration, the polymerizable unsaturated compound (inert unsaturated compound) which does not have the active hydrogen atom of the said example, etc. . Among these polymerizable unsaturated compounds, aromatic vinyl compounds having no active hydrogen atoms (styrene, divinylbenzene and the like), vinyl cyanide (acrylonitrile, etc.), C _{1 - 10} alkyl (meth) acrylate (methyl methacrylate Elate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), polyfunctional (meth) acrylate (ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, trimethylol propane tree (Meth) acrylate, pentaerythritol tetra (meth) acrylate), allyl (meth) acrylate, glycidyl (meth) acrylate, hydroxyl group-containing (meth) acrylate as a compound having an active hydrogen atom (2-hydroxyethyl (meth) acrylate of hydroxy-C _{2 -6} alkyl (meth) acrylate and the like), carboxyl group-containing compound ((meth) acrylic acid, etc.), diacetone acrylamide , Such as N- methylol (meth) acrylamide are preferred. Styrene, divinylbenzene, methyl methacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, trimethylolpropane tri (meth) acrylate, allyl methacrylate, glycidyl when forming a hard film Methacrylate, diacetone acrylamide, 2-hydroxyethyl (meth) acrylate, etc. are often used.

The amount of the polymerizable unsaturated compound to be used is not particularly limited. For example, the polyurethane alkyd resin / polymerizable unsaturated compound = 100/0 to 20/80, preferably 100/0 to 50/50, as a weight ratio in terms of solid content. More preferably, it may be about 100/0 to 60/40. The copolymerization method is not particularly limited, and the polyurethane alkyd resin can be reacted at a reaction temperature of 20 to 90 ° C. for about 1 to 8 hours by using a known polymerization method, for example, emulsion polymerization, suspension polymerization, or the like in an inert atmosphere. The component and the acrylic component are chemically copolymerized, and a polyurethane alkyd acrylic resin emulsion having an active hydrogen atom can be obtained.

The radical polymerization initiator is not particularly limited, and for example, benzoyl peroxide, o-methoxybenzoyl peroxide, o-chlorobenzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide Organic peroxides such as diisopropyl benzene hydroperoxide; 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2 Azo systems such as' -azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] and 2,2'-azobis [2- (2-imidazolin-2-yl) propane] Compound; Inorganic peroxides, such as hydrogen peroxide, sodium persulfate, potassium persulfate, and ammonium persulfate, etc. are mentioned. The organic or inorganic peroxide may be combined with a reducing agent to form a redox-based polymerization initiator. Examples of the reducing agent include L-ascorbic acid, L-sorbic acid, sodium metabisulfite, ferrous sulfate, rongalit and the like. These radical polymerization initiators can be used individually or in combination of 2 or more types. Among these radical polymerization initiators, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, Persulfates (sodium persulfate, potassium persulfate, ammonium persulfate, etc.) and the like are preferred. Moreover, cumene hydroperoxide, 2,2'- azobisisobutyronitrile, sodium persulfate, potassium persulfate, and ammonium persulfate are often used as a polymerization initiator.

Moreover, in order to adjust the molecular weight of a polymer, you may superpose | polymerize in presence of a molecular weight modifier. As a molecular weight modifier, mercaptans (n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, etc.), thioglycolic acid (thioglycolic acid, thioglycolic acid 2-ethylhexyl, for example) Etc.), thioalcohols (2-mercaptoethanol etc.) etc. can be illustrated. These molecular weight regulators can also be used individually or in combination of 2 or more types.

In the case where the polyurethane alkyd resin emulsion (A) is a polyurethane alkyd acrylic resin emulsion, the active hydrogen atom in the resin may be derived from a polyurethane alkyd resin component, a (meth) acrylic component, or the like, and the derived component is not particularly limited. For example, active hydrogen atoms, such as following (1)-(4), can be illustrated.

(1) Carboxyl group or hydroxyl group derived from polyurethane alkyd resin

(2) The hydroxyl group derived from polyamine etc. used for chain extension of a polyurethane alkyd resin

(3) hydroxyl group or carboxyl group derived from the (meth) acrylic component used for copolymerization or modification

(4) The hydroxyl group or carboxyl group derived from the other copolymerizable component used with a (meth) acryl component.

The urethane alkyd acrylic resin emulsion having an active hydrogen atom can be produced by introducing an active hydrogen atom into the resin using a component having an active hydrogen atom of the above (1) to (4). In addition, the component which has the active hydrogen atom of said (1)-(4) may be used individually, or may be used in combination of 2 or more type.

Moreover, in order to improve dispersion stability, the resin component of polyurethane alkyd acrylic resin emulsion may be comprised with an anionic copolymer. The anionic group of an anionic copolymer should just have at least one component among a urethane alkyd component and a (meth) acryl component. For example, a copolymer having a urethane alkyd component having an anionic group introduced therein and a (meth) acryl component having no anionic group, and having a urethane alkyd component having an anionic group introduced therein and an anionic group An anionic group can be introduce | transduced into the resin component of a polyurethane alkyd acrylic resin emulsion by copolymerization with a meth) acryl component ((meth) acrylic acid etc.). In a preferred embodiment, an anionic group is introduced into the urethane alkyd component by using a compound having an active hydrogen atom and an anionic group reactive with an isocyanate group.

In addition, when the emulsion produced by superposition | polymerization contains an organic solvent, you may remove an organic solvent by distillation etc. as needed.

Moreover, you may mix | blend surfactant with a polyurethane alkyd resin emulsion (A) in the range which does not impair water resistance in order to improve stability of a polyurethane alkyd resin emulsion as needed.

It does not specifically limit as surfactant, For example, anionic surfactant (For example, fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl Sulfuric acid ester salts), nonionic surfactants (e.g., polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers, polyoxyethylene derivatives, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxy) Ethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene alkylamines, alkylalkanolamides, etc.), cationic and amphoteric surfactants (e.g. alkylamine salts, quaternary ammonium salts, alkylbetaines, amine oxides) Water-soluble polymers or protective colloids (eg, gelatin, methylcellulose, hydroxyethylcellulose, Hydroxypropyl cellulose, carboxymethyl cellulose, polyethylene glycol, polyoxyethylene-polyoxypropylene block copolymer, polyacrylamide, polyacrylic acid, polyacrylic acid salt, sodium alginate, polyvinyl alcohol partial saponified product), and the like. . In the present invention, in addition to these polymer dispersants, inorganic substances such as tricalcium phosphate, titanium oxide, calcium carbonate and silicon dioxide can also be used as the surfactant. These surfactants may be used alone or in combination of two or more. In addition, in addition of surfactant, depending on the surfactant which has an ionic functional group, the stability of an aqueous dispersion may fall by interaction with the anionic group of a polyurethane alkyd resin. Therefore, a nonionic surfactant is often used.

For example, the surfactant may be added to the polyurethane alkyd prepolymer before dispersing in water, may be added to the aqueous dispersion of the polyurethane alkyd prepolymer, or the polyurethane alkyd resin emulsion or chain elongation chained with polyamine. It may be added to a polyurethane alkyd resin emulsion dispersed in water without being added, or may be added to a polyurethane alkyd acrylic resin emulsion produced by radical polymerization. In addition, you may add surfactant in batch or in several parts.

[Hardener (B)]

The polyurethane alkyd resin emulsion (A) having an active hydrogen atom may be used as an aqueous resin composition (adhesive or the like) or a coating composition (paint, printing ink, etc.), but in order to improve water resistance, moisture heat resistance and solvent resistance, It is preferable to use the polyurethane alkyd resin emulsion (A) and hardening | curing agent (B) which have an active hydrogen atom in combination. As a hardening | curing agent (B), various hardening agents which are reactive with the said active hydrogen atom, for example, isocyanate type hardener (polyisocyanate compound), epoxy type hardener (polyepoxy compound), amino resin type hardener (melamine compound, guar) Namin compound etc.), a dihydrazide type hardening | curing agent, a carbodiimide type hardening | curing agent, an oxazoline type hardening | curing agent, an aziridine type hardening | curing agent, etc. are mentioned. These hardeners can be used individually or in combination of 2 or more types. Although a hardening | curing agent may be a hydrophobic hardening | curing agent, a preferable hardening | curing agent is a hardening | curing agent which can be disperse | distributed to the said polyurethane alkyd resin emulsion (A).

As such a hardening | curing agent, polyisocyanate (isocyanate type hardening | curing agent) is preferable. As a polyisocyanate used for a hardening | curing agent, what kind of polyisocyanate may be sufficient as long as it can be disperse | distributed to a polyurethane alkyd resin emulsion (A), The polyisocyanate itself which can be disperse | distributed to a polyurethane alkyd resin emulsion (A) is necessary, The polyisocyanate which can be disperse | distributed to a polyurethane alkyd resin emulsion (A) may be sufficient by adding surfactant and a dispersing agent, and stirring (including the steel stirring using a homomixer etc.) and mixing. Among these polyisocyanates, polyisocyanate derivatives are preferable, it is more preferable to use polyisocyanate modified bodies, and it is particularly preferable to use dispersible polyisocyanates.

(Dispersible polyisocyanate)

The dispersible polyisocyanate can be obtained, for example, by reaction with a polyisocyanate and a surface active or dispersible component having a reactive hydrogen atom reactive with isocyanate groups (components having surface active or dispersing ability).

As said polyisocyanate, Aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic aliphatic polyisocyanate, aromatic isocyanate, polyisocyanate containing derivatives or modified bodies based on these polyisocyanates, derivatives or modified bodies thereof Etc. can be mentioned. These polyisocyanates can be used individually or in combination of 2 or more types.

As aliphatic polyisocyanate, the said aliphatic polyisocyanate etc. are mentioned, As a preferable polyisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, etc. are mentioned.

As alicyclic polyisocyanate, the said alicyclic polyisocyanate etc. are mentioned, As a preferable polyisocyanate, isophorone diisocyanate, 1, 3- or 1, 4-bis (isocyanate methyl) cyclohexane, norbornane diisocyanate Etc. can be mentioned.

As aromatic aliphatic polyisocyanate, the said aromatic aliphatic polyisocyanate etc. are mentioned, A preferable polyisocyanate is 1, 3- or 1, 4-bis (1-isocyanato-1-methylethyl) benzene, etc.

As aromatic polyisocyanate, the said aromatic polyisocyanate etc. are mentioned. Preferred polyisocyanates include 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate and the like.

These polyisocyanates can be used individually or in combination of 2 or more types.

Moreover, as a polyisocyanate derivative, For example, dimer, trimer (polyisocyanate containing isocyanurate group), biuret group containing polyisocyanate, allophanate group containing polyisocyanate, oxadiazine trione ring containing polyisocyanate And carbodiimide-modified polyisocyanates can also be used. In preparation of the polyisocyanate derivative, if necessary, a polyol or polyamine having a reactivity with the polyisocyanate may be used, and examples of the polyol and polyamine include, for example, glycols and triols, the polyester polyols, and polyether polyols. , Polyetherester polyol, polyesteramide polyol, acryl polyol, polycarbonate polyol, polyhydroxyalkane, polybutadienediol, polyurethane polyol, low molecular weight polyol, low molecular weight polyamine or mixtures thereof can be used. The polyisocyanate derivative may be an adduct type polyisocyanate or an isocyanate prepolymer in which the polyisocyanate is added to the polyol. These polyisocyanate derivatives may also be used alone or in combination of two or more thereof, and may be used in combination with the aforementioned polyisocyanate (aliphatic or alicyclic polyisocyanate or the like). Among these polyisocyanate derivatives, derivatives based on at least one member selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate and tolylene diisocyanate, in particular isocyanurate group-containing polyisocyanate and / or allophanate group A containing polyisocyanate etc. are preferable. In the polyisocyanate derivative, the isocyanate group content can be appropriately selected and is usually about 12 to 40% by weight, preferably 15 to 35% by weight, based on the entire polyisocyanate.

(Interactive or dispersible ingredients)

The surface active or dispersible component may be any component as long as it has an active hydrogen atom and has surface active ability or dispersibility. The surfactant or dispersible component may be an anionic surfactant, but is usually composed of at least one member selected from the group consisting of a compound having a nonionic surfactant and at least an ethylene oxide chain. Nonionic surfactant has reactive groups containing active hydrogen atoms, such as a hydroxyl group and a mercapto group, for example, and surfactant which has a hydroxyl group is preferable. The nonionic surfactant may be a polyol fatty acid ester such as glycerin fatty acid ester or sucrose fatty acid ester, but preferably has at least an ethylene oxide chain. That is, as the nonionic surfactant, polyoxyalkylene-based surfactants having at least oxyethylene units, in particular polyoxyethylene-based surfactants having hydroxyl groups, are particularly preferably used.

Polyoxyethylene in the alkyl-series surface active agent, the oxyalkylene units to include, for example, oxyethylene, oxypropylene, oxybutylene oxy-C _2, such as _{alkylene-containing 5} alkylene units, these oxyalkylene units are If includes at least oxyethylene units being, oxyethylene units and oxy-C _{3 -} or may be a random or block copolymer units of ₅ alkylene units. Content of the oxyethylene unit in a polyoxyalkylene unit is 70-100 mol% normally, Preferably it is about 80-100 mol%.

The nonionic surfactant may be any one as long as it has an active hydrogen atom. For example, polyoxyethylene alkyl ether (for example, polyoxyethylene monooctyl ether, polyoxyethylene monolauryl ether, polyoxyethylene mono decyl ether, polyoxyethylene mono cetyl ether, polyoxyethylene monostearyl ether, polyoxyethylene monooleyl ether, the polyoxyethylene C _{8 - 24} alkyl ether and the like), polyoxyethylene monoalkyl aryl ether (e. g., polyoxyethylene mono-octyl ether, polyoxyethylene mono nonyl phenyl ether, polyoxyethylene dodecyl mono ether, such as polyoxyethylene C _{8 - 12} alkyl, -C _6-12 aryl ether), polyoxyethylene polyoxypropylene Alkylene alkyl ether (for example, polyoxyethylene polyoxypropylene monooctyl ether, polyoxyethylene polyoxypropylene monolaura Polyoxyethylene poly, such as a reel ether, polyoxyethylene polyoxypropylene monodecyl ether, polyoxyethylene polyoxypropylene monocetyl ether, polyoxyethylene polyoxypropylene monostearyl ether, polyoxyethylene polyoxypropylene monostearyl ether, etc. polyoxypropylene alkyl ether, or C _{8- 24,} and their polyoxyethylene polyoxypropylene C _{8 - 24,} polyoxyethylene polyoxypropylene butylene C ₈ corresponding to the alkyl _{ether-24-alkyl} ether and the like), polyoxyethylene sorbitan higher fatty acid Esters (e.g., polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan distearate, polyoxyethylene sorbitan tristearate a mono-, di- or tri- C _{10 -24} fatty acid-polyoxyethylene sorbitan, such as Hotel, etc.), polyoxyethylene mono higher fatty acid esters (e.g., polyoxyethylene mono laurate esters, polyoxyethylene such as monostearate ester polyoxyethylene mono C _{10 -,} and the like ₂₄ fatty acid ester, etc.) have. These nonionic surfactants can be used individually or in combination of 2 or more types. Preferred non-ionic surfactants, polyoxyethylene _8- C ₂₄ alkyl ether, a polyoxyethylene C _8-is contained in the ether _{24 - 12} alkyl ether, polyoxyethylene polyoxypropylene C _3- C ₆ alkylene _8. In addition, in order to be able to stably disperse | distribute with respect to a polyurethane alkyd resin emulsion (A), the average content of the oxyethylene unit in 1 molecule of a nonionic surfactant is about 10-35 pieces normally, Preferably it is 12 It is about 30 pieces.

The compound having an ethylene oxide chain (particularly a polyethylene oxide chain) may be any compound having an active hydrogen atom. For example, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol and the like mono alkanol _- as a (C _{1 10} alkyl, lower alcohols such as alcohol) initiator, there can be mentioned in which the alkoxy polyalkylene glycol ethers by addition of an alkylene oxide containing at least ethylene oxide to ring-opening polymerization. In addition, in order to be able to stably disperse | distribute with respect to a polyurethane alkyd resin emulsion (A), the average molecular weight of the compound which has an active hydrogen atom and an ethylene oxide chain is about 100-4,000 normally, Preferably it is about 200-2,000 to be.

Compounds having ethylene oxide chains (particularly polyethylene oxide chains) include compounds in which alkoxypolyalkylene ether glycols and dialkanolamines are reacted with polyisocyanates, dialkanolamines and alkoxypolyoxyethylene glycol monoallyl ethers or alkoxypolyoxyethylene ( Michael adduct of meth) acrylate, etc. are also included.

Alkoxy polyalkylene ether glycols include, for example, methoxy polyethylene ether glycol, ethoxy polyethylene ether glycol, methoxy polybutylene ether glycol, ethoxy polybutylene ether glycol of C _{1 - 4} alkoxy poly C _{2 4} may be an alkylene glycol ether.

By Diallo kanol amine, diethanolamine, di-propanol amine, diisopropanolamine, di-di-hydroxy-C _2, such as ethanol, _aniline-6 may be mentioned alkylamines.

The reaction of polyisocyanate, alkoxypolyalkylene ether glycol and dialkanolamine is obtained by reacting polyisocyanate and alkoxypolyalkylene ether glycol at an equivalence ratio of isocyanate group / hydroxyl group of 3 to 30, preferably about 10 to 25. Thereafter, unreacted polyisocyanate is removed, and then dialkanolamine can be carried out at a ratio of 0.5 to 2, preferably 0.8 to 1.2, equivalent ratio of isocyanate group / amino group. Reaction of polyisocyanate and alkoxy polyalkylene ether glycol can be performed at about 40-100 degreeC for about 2 to 24 hours. It is preferable to perform reaction in nitrogen atmosphere, and you may use the inert organic solvent mentioned later. As removal of unreacted polyisocyanate, well-known methods, such as a distillation method and an extraction method, are used. As the distillation method, a continuous distillation method, a batch distillation method, a thin film distillation method, etc. are mentioned. Thin film distillation is preferably used. As the extraction method, liquid-liquid extraction such as continuous extraction or ash extraction is used, and as the extraction solvent, relatively low polar organic solvents such as hexane and acetic acid ester are used. It is preferable to perform reaction with a dialkanolamine in a nitrogen atmosphere at about room temperature to about 120 degreeC. In addition, you may also perform this reaction using an inert organic solvent similarly to the above.

The ratio of the polyisocyanate for the curing agent (B) and a nonionic compound having an active hydrogen atom (that is, including a nonionic surfactant having an active hydrogen atom and / or a compound having a polyethylene oxide chain) is polyisocyanate (poly 1 to 0.2 equivalents, preferably 0.012 to 0.15 equivalents, more preferably 0.012 to 0.1 equivalents of active hydrogen atoms of the nonionic compound, relative to 1 equivalent of the isocyanate group capable of reacting You can choose. When there are few ratios of a nonionic compound, the dispersibility with respect to a polyurethane alkyd resin emulsion (A) may fall, and when too much, hydrophilicity may become high too much and physical properties, such as water resistance, may fall.

Moreover, in order to improve the water resistance of a coating film, it is advantageous to make said polyisocyanate (preferably polyisocyanate derivative) react with a coupling agent. This coupling agent has functional groups, such as an active hydrogen atom reactive with the isocyanate group of polyisocyanate, for example, a mercapto group, an amino group, and a carboxyl group. The coupling agent has a crosslinking or a polymerizable group (such as a hydrolysis condensation group), and as the hydrolysis condensation group, for example, an alkoxy group (methoxy, ethoxy, propoxy, butoxy, t-butoxy group) C _{1 - 4} alkoxy group and the like). The coupling agent may have 1 to 3 such hydrolysis-condensable groups in 1 molecule. Such a coupling agent may be a titanium coupling agent or the like, but is typically a silane coupling agent.

A silane coupling agent is, for example, a mercapto group-containing silane coupling agent (β- mercaptoethyl tree on silane, γ- mercaptopropyl trimethoxy mercapto silane such as C _{2 - 4} alkyl, C _1- tree Amino such as ₄ alkoxysilanes), amino group-containing silane coupling agent (β-aminoethyltrimethoxysilane, β-aminoethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane C _{2 - 4} alkyl tree C _{1 - 4} alkoxy silanes, etc.), carboxyl group-containing silane coupling agent (β- carboxy ethyltrimethoxysilane, γ- carboxy trimethoxysilane, γ- carboxy in propyltriethoxysilane carboxy, such as silane C _{2 - 4} alkoxy silanes, and the like, and so on) _{- 4} alkyl, C ₁ tree. These silane coupling agents can be used individually or in combination of 2 or more types. Preferred coupling agents are mercapto group-containing silane coupling agents such as γ-mercaptopropyltrimethoxysilane and the like.

The proportion of the polyisocyanate to the coupling agent is in the range of 0.01 to 0.3 equivalents, preferably 0.02 to 0.25 equivalents, more preferably 0.05 to 0.2 equivalents, relative to 1 equivalent of the isocyanate group of the polyisocyanate. You can choose.

The polyisocyanate as the curing agent (B) is for example a compound having a nonionic surfactant and / or polyoxyethylene chain having an active hydrogen atom with the polyisocyanate (preferably a polyisocyanate derivative) and a coupling agent if necessary. It can obtain by making it react, stirring. Reaction temperature can be selected suitably, Usually, it is about 50-90 degreeC. The reaction time is also not particularly limited, and is, for example, 1 to 24 hours, preferably 1 to 8 hours. The reaction may be performed in the presence of a catalyst (amine catalyst, tin catalyst, and the like). In addition, although reaction may be performed in presence of an inert organic solvent (non-reactive organic solvent), in order to improve handleability, preventing reaction by the organic solvent of a 2-liquid curable aqueous resin composition, it is made to react in the absence of an organic solvent. It is preferable to produce a liquid polyisocyanate having fluidity at room temperature. Hereinafter, the case where polyisocyanate is used for a hardening | curing agent is described as hardening | curing agent (polyisocyanate).

As the inert organic solvent, for example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, 4-methyl-2-pentanone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, acetic acid) Isobutyl, 1-methoxypropyl-2-acetate, 3-methoxy butyl acetate and the like), aromatic hydrocarbons (benzene, toluene, xylene, etc.), alicyclic hydrocarbons (cyclohexane, aliphatic hydrocarbons (hexane, Isooctane, etc.), ethers (dioxane, tetrahydrofuran, etc.), cellosolves and carbitols (ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol dimethyl ether, ethylene Glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, die Tylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol dimethyl ether, triethylene glycol Butyl methyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, 2,2,4-trimethyl-1,3-pentanediol diisobutylate, triethylene glycol bis 2-ethylhexaate, etc.), nitrogen-containing solvent ( N-methylpyrrolidone, N-ethylpyrrolidone, N-methylcaprolactam, etc.) These solvent can be used individually or as a mixed solvent of 2 or more types.

In addition, the polyisocyanate derivative which has surfactant activity or dispersibility as a hardening | curing agent (polyisocyanate) (B) can be prepared using a well-known synthetic method, and the reaction order of each component can be selected according to the kind of reaction component, etc. . For example, a curing agent (polyisocyanate) (B), by reacting a polyisocyanate derivative (such as a trimer of a low molecular polyisocyanate) with a compound having a nonionic surfactant and / or a polyoxyethylene chain and, if necessary, a coupling agent, In particular, dispersible polyisocyanates can be obtained. In addition, when using the some reactive component which has the active hydrogen atom reactive with a polyisocyanate and an isocyanate group, you may use a some polyisocyanate, and each reaction component may be made to react in a suitable order. For example, a compound containing a terminal isocyanate group and a polyethylene oxide chain is produced by reaction of a polyisocyanate (low molecular polyisocyanate or polyisocyanate derivative) with a compound having a polyethylene oxide chain (alkoxypolyethylenealkylene ether glycol, etc.) After removal of the remaining polyisocyanate, a compound containing two hydroxyl groups and a polyethylene oxide chain is produced by the reaction of the produced compound with a dialkanolamine, and the compound and polyisocyanate (preferably poly In this way, the reactive component (a nonionic surfactant having an active hydrogen atom reactive with an isocyanate group and / or a compound having a polyoxyethylene chain) and optionally The fling agent) may be reacted with, for example, polyisocyanate in advance, or may be reacted in a step during the synthesis of the polyisocyanate derivative, and the reaction product may be reacted with the polyisocyanate derivative. After that, finally, trimerization, allophanation, biuretization reaction, or the like may be carried out, for example, a low molecular polyisocyanate, a diol having a polyoxyethylene chain (such as polyethylene glycol) and a trione are reacted to form a trimer. You may perform an allophanate reaction, etc. By these various reactions, the target hardening | curing agent (polyisocyanate) (B) can be obtained.

The average number of functional groups of the curing agent (polyisocyanate) (B) is 2 to 5, preferably 2.5 to 4, and the isocyanate group content is 3 to 50% by weight, preferably 5 to 30% by weight. If the average functional group number of a hardening | curing agent (polyisocyanate) (B) is less than 2, water resistance may fall, and if it exceeds 5, the polyurethane alkyd resin emulsion (A) which has an active hydrogen atom of a hardening | curing agent (polyisocyanate) (B) Dispersibility with respect to may fall. When the isocyanate group content is less than 3% by weight, the water resistance may be deteriorated due to the lack of crosslinking density. When the content of the isocyanate group is less than 50% by weight, the dispersibility in the polyurethane alkyd resin emulsion (A) having an active hydrogen atom It may fall.

In addition, in order to obtain polyisocyanate as a hardening | curing agent of desired isocyanate group content, reaction may be complete | finished when the predetermined | prescribed isocyanate group content became the reaction process. Preferred methods include polyisocyanates (preferably including polyisocyanate derivatives), nonionic surfactants having an active hydrogen atom, in a proportion at which the isocyanate group content in the resulting curing agent (polyisocyanate) (B) falls within the above range; And / or a compound having a polyethylene oxide chain and, if necessary, a coupling agent are mixed in advance, and the reaction is carried out until the reaction of each component is completed.

These curing agents (polyisocyanate) (B) may be used alone or in combination of two or more thereof. Among these curing agents (polyisocyanates) (B), preferred polyisocyanates include those produced by the reaction of polyisocyanates (preferably polyisocyanate derivatives) and nonionic surfactants having an active hydrogen atom reactive with isocyanate groups. Acidic polyisocyanates, polyisocyanates (preferably low molecular weight polyisocyanates or polyisocyanate derivatives) and compounds having a polyethylene oxide chain having an active hydrogen atom reactive with isocyanate groups (alkoxypolyethylenealkylene ether glycol) and dialkanolamines In the same manner as in the above to generate an active hydrogen atom-containing compound (eg, a terminal hydroxyl group compound) to form an active hydrogen atom-containing compound and a polyisocyanate (preferably Minutes, produced by the reaction of the isocyanate derivative), and the like acid polyisocyanate. More preferable hardener (polyisocyanate) (B) is polyoxyethylene modified polyisocyanate which is dispersible polyisocyanate.

The curing agent (polyisocyanate) (B) may contain a non-reactive coupling agent (particularly a silane coupling agent) with respect to the isocyanate group. As such a silane coupling agent, an epoxy group or glycidyl group containing silane coupling agent (for example, (gamma)-glycidoxy propylmethyl diethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, (beta)-( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc.), vinyl group-containing silane coupling agent (vinyl triethoxysilane, vinyltrimethoxysilane, β- (meth) allyloxyethyltrimethoxysilane, γ- (Meth) allyloxypropyl trimethoxysilane, etc.) etc. are mentioned.

In addition, when using polyisocyanate etc. as a hardening | curing agent (B), you may make it contain a non-reactive solvent with respect to an isocyanate group. As such a solvent, various inert organic solvents can be used. For example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, 4-methyl-2-pentanone, cyclohexanone, etc.), esters (Ethyl acetate, butyl acetate, isobutyl acetate, 1-methoxypropyl-2-acetate, 3-methoxybutyl acetate, etc.), aromatic hydrocarbons (benzene, toluene, xylene, etc.), alicyclic hydrocarbons (cyclohexane ), Aliphatic hydrocarbons (hexane, isooctane, etc.), ethers (dioxane, tetrahydrofuran, etc.), cellosolves or carbitols (ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl) Ether acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol Dimethyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, 2,2,4-trimethyl-1,3-pentanediol diisobutylate, triethylene glycol bis 2-ethylhexaate, etc. ), And nitrogen-containing solvents (N-methylpyrrolidone, N-ethylpyrrolidone, N-methylcaprolactam and the like). These solvents can be used alone or as mixed solvents of two or more thereof.

In the two-liquid curable aqueous resin composition of the present invention, the amount of the curing agent (B) to the polyurethane alkyd resin emulsion (A) is not particularly limited as long as the effect of the present invention is exerted, for example, in terms of solid content, 0.1 to 150 parts by weight of the curing agent (B), preferably 0.5 to 60 parts by weight, more preferably 1 to 40 parts by weight (for example, 2 to 35 parts by weight) with respect to 100 parts by weight of the urethane alkyd resin emulsion (A) Preferably it is 3-30 weight part).

The amount of the curing agent (B) used in the polyurethane alkyd resin emulsion (A) is, in terms of solid content, for example, a reactive group (for example, an isocyanate group in polyisocyanate) and a polyurethane alkyd resin emulsion ( As equivalent ratio (for example, isocyanate group / active hydrogen atom) of the active hydrogen atom in the polyurethane alkyd resin of A), it is 0.3-4, Preferably it is 0.4-3, More preferably, it is about 0.5-2. When the equivalent ratio of isocyanate group and active hydrogen atom exceeds this range, there is a possibility that excess isocyanate group reacts with water to generate carbon dioxide and significantly damage the appearance of the coating film. Moreover, if the equivalent ratio is less than this range, there is a lack of crosslinking density. And water resistance may remarkably fall with residual active hydrogen atoms in a coating film. In addition, the active hydrogen atom which occupies in the polyurethane alkyd resin in a polyurethane alkyd resin emulsion (A) is the hydroxyl group in the polyamine used at the time of chain extension of the polyurethane alkyd prepolymer which has a terminal isocyanate group, or a polyurethane alkyd prepolymer (isocyanate group) Sum of the carboxyl group in the active hydrogen atom-containing compound having an anionicity used in synthesizing the polyurethane alkyd prepolymer and the hydroxyl group and / or carboxyl group in the active hydrogen atom-containing unsaturated compound used in radical polymerization Indicates.

[Metal drier or desiccant (C)]

In the aqueous resin composition (two liquid curing type aqueous resin composition, etc.) of this invention, the metal drier (C) may be contained. As a metal dryer (C), the fatty acid metal salt which is a conventional metal dryer (drying agent for paints) can be used. Examples of such fatty acid metal salts include metal naphthenate salts (cobalt naphthenate, lead naphthenate, zirconium naphthenate, manganese naphthenate, polyvalent metal salts of naphthenic acid such as zinc naphthenate), and octylic acid metal salts (octyl cobalt acid). And polyvalent metal salts of octylic acid, such as manganese octylate, lead octylate, zirconium octylate, and zinc octylate). These metal dryers can be used individually or in combination of 2 or more types. In general, it is known that a combination of two or more of these fatty acid metal salts exhibits a high effect. For example, cobalt naphthenate and other naphthenate metal salts (for example, lead naphthenate, zirconium naphthenate and manganese naphthenate) And zinc naphthenate) are commonly used. In addition, in these fatty acid metal salts, the metal may form a complex with an amine. In particular, fatty acid metal salts containing other kinds of metals, or complexes of metals and amines can be prepared as lead-free dryers, and highly active dryers are also environmentally advantageous. The metal dryer of this amine complex is marketed by Dai Nippon Ink Chemical Co., Ltd. as a brand name "Dicnate 1000W" (cobalt amine complex dryer, cobalt content 3.6 weight%), etc., and a mix dryer is used by Yushibi Japan Ltd. is marketed as a brand name "ADDITOL VXW6206" (cobalt lithium zirconium compound salt, 5 weight% of cobalt content, 0.2 weight% of lithium content, 7.5 weight% of zirconium content), etc.

The proportion of the metal drier (C) is, for example, 0.01 parts by weight or more (eg, 0.01 to 30 parts by weight), preferably 0.05 to 20 parts by weight, and more preferably, based on 100 parts by weight of the polyurethane alkyd resin. Is about 0.1 to 10 parts by weight (particularly 0.1 to 5 parts by weight). In addition, the ratio of the metal drier (C) is 0.001 weight part or more (for example, 0.001-5 weight part), Preferably it is 0.01-1 weight part with respect to 100 weight part of polyurethane alkyd resin components in conversion to a metal component. Part, More preferably, it may be about 0.05 to 0.5 parts by weight. In the case where the alkyd resin component contains an unsaturated fatty acid component, when the ratio of the metal drier is in this range, the oxidative curing reaction is promoted and a high-performance coating film can be obtained in a short time.

In the aqueous resin composition of this invention, other resin (for example, acrylic resin emulsion, styrene resin emulsion, urethane resin emulsion, etc.), a curing catalyst, and various additives, for example, a plasticizer, a film | membrane as needed. Forming aids, film forming agents, cryoprotectants, antifoams, leveling agents, formalin catchers, fungicides, waterproofing agents, antiseptics, preservatives, gloss removers, flame retardants, thixotropic agents, tackifiers, thickeners, lubricants, antistatic agents, reaction retardants , Antioxidants, ultraviolet absorbers, hydrolysis inhibitors, weather stabilizers, heat stabilizers, fillers, salt pigments (dyes, inorganic pigments, organic pigments, extender pigments, etc.) may be appropriately added.

The two-component curable aqueous resin compositions of the present invention are useful as adhesives, coating agents (paints, printing inks, etc.), primers, and various substrates (metal, plastic or polymer materials, slate, concrete, mortar, etc., inorganic materials, paper, It can be used suitably for the surface coating of trees, etc.). In particular, the two-liquid curable aqueous coating of the present invention can be cured at room temperature and heat cured. For example, in a room temperature curing system, it can be used as a woodworking coating or an aqueous primer, and in a heat curing system, it can be used as an automotive coating. .

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail based on an Example, but this invention is not limited by these Examples. In addition, "part" and "%" in an Example and a comparative example represent a weight part and weight%.

[Preparation of alkyd resin (PES1)]

Into a five-necked flask equipped with a stirrer, a nitrogen inlet tube, a rectifying tower, and a thermometer, 3308.3 parts of a diene fatty acid (Keif Trading Co., Ltd., Heidiene), 821.2 parts of pentaerythritol, and 487.3 parts of isophthalic acid were added thereto. 0.2 part of mono n-butyltin oxide which is an esterification catalyst was added, performing nitrogen bubbling, the liquid mixture was heated up to 230 degreeC, and carboxyl group and hydroxyl group were made to react, extracting condensed water, stirring for 8 hours. It was confirmed that the reaction solution had reached a predetermined hydroxyl group content, and the temperature was lowered to 30 ° C to obtain an alkyd resin (PES1) having a hydroxyl value of 75.3.

[Preparation of alkyd resins (PES2, PES3, PES4, PES5)]

In the compounding formulation shown in Table 1, alkyd resins (PES2, PES3, PES4, PES5) were prepared by the same operation as alkyd resin (PES1).

[Preparation of active hydrogen atom-containing polyurethane alkyd resin emulsion (a1)]

174.2 parts of tolylene diisocyanate (manufactured by Mitsui Takeda Chemical, Cosmonate T-80), and methylethylketone 207.1 in a five-necked flask equipped with a stirrer, a luggage lot cooler, a nitrogen introduction tube, a silica gel drying tube, and a thermometer. 2 parts of an alkyd resin (PES1) with 75.3 alkyd resin (PES1), 38.1 parts of neopentyl glycol, and 32.6 parts of dimethylol butanoic acid were added, and the temperature was 70-80 degreeC. After stirring for 2 hours, it was confirmed that the reaction solution had reached the predetermined isocyanate content, and the reaction mixture solution containing the polyurethane alkyd prepolymer was cooled by adding 138.1 parts of methyl ethyl ketone (methyl ethyl ketone of the alkyd component-containing terminal isocyanate polyurethane prepolymer). Solution).

While stirring 863 parts of the obtained reaction mixture containing the polyurethane alkyd prepolymer using a homodisper, 117.5 parts of a 15% aqueous solution of 2-dimethylaminoethanol was added, and 1268.2 parts of deionized water was added again to give a light pale peach aqueous dispersion. Got. 192.3 parts of 10% aqueous solution of N- (2-aminoethyl) ethanolamine is dripped at this dispersion liquid at the temperature of 30 degrees C or less, chain extension reaction is performed, methyl ethyl ketone and water are removed at 50 degreeC under reduced pressure, and lead Active hydrogen atom-containing polyurethane alkyd resin emulsion which is 36.8% of solid content, viscosity (25 degreeC) 46mPa * s, pH 7.6, average particle diameter 84nm by adding 4.4 parts of free dryers (Yushibi Japan Co., Ltd. product, ADDITOL VXW6206) (a1) was obtained.

[Preparation of active hydrogen atom-containing polyurethane alkyd resin emulsion (a2)]

174.2 parts of tolylene diisocyanate (manufactured by Mitsui Takeda Chemical Co., Ltd., Cosmonate T-80), and methyl ethyl ketone, in a five-necked flask equipped with a stirrer, a luggage lot cooler, a nitrogen introduction tube, a silica gel drying tube, and a thermometer. 208.7 parts were added and stirred until completely homogeneous under a nitrogen atmosphere, and 276.9 parts of an alkyd resin (PES2) having a hydroxyl value of 74.2, 38.1 parts of neopentyl glycol and 32.6 parts of dimethylolbutanoic acid were added, and the temperature was 70-80. It stirred at 2 degreeC for 2 hours, it confirmed that the reaction liquid reached | attained the predetermined isocyanate content, and it cooled down adding 139.1 parts of methyl ethyl ketones, and it cooled and contained the reaction mixture liquid containing a polyurethane alkyd prepolymer (methylethyl of an alkyd component containing terminal isocyanate polyurethane prepolymer). Ketone solution).

To the reaction mixture containing the obtained polyurethane alkyd prepolymer, 3.7 parts of a cobalt naphthenate (cobalt content 6 wt%) solution, 5.6 parts of a zirconium naphthenate (6 wt% zirconium content) solution and 20 parts of triethylamine were added to make it uniform. Subsequently, 898.9 parts of the reaction mixture containing the polyurethane alkyd prepolymer was slowly added in small portions to 1377.1 parts of deionized water stirred using a homodisper to obtain a milky pale peach aqueous dispersion. 192.3 parts of 10% aqueous solution of N- (2-aminoethyl) ethanolamine was dripped at this dispersion liquid at the temperature of 30 degrees C or less, chain extending reaction was performed, and methyl ethyl ketone and water were removed at 50 degreeC under reduced pressure, solid content 36.7. %, A viscosity (25 degreeC), the active hydrogen atom containing polyurethane alkyd resin emulsion (a2) which is 37 mPa * s, pH 7.6, and an average particle diameter of 59 nm was obtained.

[Preparation of active hydrogen atom-containing polyurethane alkyd resin emulsion (a3, a4)]

In the formulations shown in Table 2, active hydrogen atom-containing polyurethane alkyd resin emulsions (a3, a4) were prepared by the same operation as that of active hydrogen atom-containing polyurethane alkyd resin emulsions (a2).

[Preparation of active hydrogen atom-containing polyurethane alkyd resin emulsion (a5)]

174.2 parts of tolylene diisocyanate (manufactured by Mitsui Takeda Chemical Co., Ltd., Cosmonate T-80) and methyl ethyl ketone 160.2 in a five-necked flask equipped with a stirrer, a luggage lot cooler, a nitrogen introduction tube, a silica gel drying tube, and a thermometer. 2 parts of an alkyd resin (PES3) with 85.8 alkyd resin (PES3), 36.4 parts of neopentyl glycol, and 33.7 parts of dimethylol butanoic acid were added, and the temperature was 70-80 degreeC. After stirring for 2 hours, it was confirmed that the reaction solution reached the predetermined isocyanate content, and the reaction mixture was lowered by adding 106.8 parts of methyl ethyl ketone to the reaction mixture containing the polyurethane alkyd prepolymer (methyl ethyl ketone of the alkyd component-containing terminal isocyanate polyurethane prepolymer). Solution).

762.9 parts of the reaction mixture solution containing the obtained polyurethane alkyd prepolymer was added while stirring using a homodisper, 121.6 parts of a 15% aqueous solution of 2-dimethylaminoethanol was added, and 1355.5 parts of deionized water was added again to give a milky pale peach aqueous dispersion. Got. 192.3 parts of 10% aqueous solution of N- (2-aminoethyl) ethanolamine was dripped at this dispersion liquid at the temperature of 30 degrees C or less, and chain extension reaction was performed and the active hydrogen atom containing polyurethane alkyd resin emulsion was obtained.

124.0 parts of styrene as an unsaturated compound and 2,2 'as a radical polymerization initiator were added to 2437.6 parts of an active hydrogen atom-containing polyurethane alkyd resin emulsion obtained in a flask equipped with a stirrer, a luggage cooler, a nitrogen inlet tube, and a thermometer. Solid content 37.7 was added by adding 7.9 parts of azobisisobutyronitrile to raise the temperature to 80 ° C, reacting for 4 hours, removing methyl ethyl ketone and water at 50 ° C under reduced pressure, and adding 5.3 parts of lead-free dryer (ADDITOL VXW6206). %, A viscosity (25 degreeC), the active hydrogen atom containing polyurethane alkyd resin emulsion (a5) which is 131 mPa * s, pH 8.0, and an average particle diameter of 74 nm was obtained.

[Preparation of Active Hydrogen Atom-Containing Polyurethane Alkyd Resin Emulsion (a6)]

174.2 parts of tolylene diisocyanate (manufactured by Mitsui Takeda Chemical Co., Ltd., Cosmonate T-80), and methyl ethyl ketone, in a five-necked flask equipped with a stirrer, a luggage lot cooler, a nitrogen introduction tube, a silica gel drying tube, and a thermometer. 202.9 parts were added and stirred until it became completely uniform under a nitrogen atmosphere, thereby adding 258.9 parts of an alkyd resin (PES2) having a hydroxyl value of 74.2, 8 parts of glycerol monomethacrylate, 35.6 parts of neopentyl glycol, and 30.4 parts of dimethylol butanoic acid. Then, the temperature was stirred at 70 to 80 ° C. for 2 hours, the reaction solution was confirmed to have reached a predetermined amount of isocyanate, and the reaction mixture solution containing polyurethane alkyd prepolymer was lowered to 30 ° C. while adding 135.2 parts of methyl ethyl ketone (alkyd). Methyl ethyl ketone solution of component containing terminal isocyanate polyurethane prepolymer) was obtained.

To 845.2 parts of the reaction mixture containing the obtained polyurethane alkyd prepolymer, 4.5 parts of a solution of cobalt naphthenate (cobalt content 6% by weight) and 6.7 parts of a solution of zirconium naphthenate (zirconium content 6% by weight) were added and stirred using a homodisper. 109.9 parts of 15% aqueous solution of 2-dimethylaminoethanol was added, followed by addition of 1694.7 parts of deionized water to obtain a milky pale peach aqueous dispersion. 192.3 parts of 10% aqueous solution of N- (2-aminoethyl) ethanolamine was dripped at this dispersion liquid at the temperature of 30 degrees C or less, and chain extension reaction was performed and the active hydrogen atom containing polyurethane alkyd resin emulsion was obtained.

120.4 parts of methyl methacrylate which is an unsaturated compound and ethylene glycol dimethacryl in 2853.3 parts of the obtained active hydrogen atom containing polyurethane alkyd resin emulsion in the flask provided with the stirrer, the zimmott cooler, the nitrogen inlet tube, and the thermometer Solid part 37.3 was added by adding 6.3 parts of a rate and 8 parts of 2,2'-azobisisobutyronitrile as a radical polymerization initiator, heating it to 80 degreeC, making it react for 4 hours, and removing methyl ethyl ketone and water at 50 degreeC under reduced pressure. %, A viscosity (25 degreeC) 100 mPa * s, pH 7.6, the active hydrogen atom containing polyurethane alkyd resin emulsion (a6) which is an average particle diameter of 82 nm was obtained.

[Preparation of active hydrogen atom-containing polyurethane alkyd resin emulsion (a7 to a9)]

In the formulation shown in Table 3, an active hydrogen atom-containing polyurethane alkyd resin emulsion (a7 to a9) was prepared by the same operation as that of the active hydrogen atom-containing polyurethane alkyd resin emulsion (a2).

[Preparation of an active hydrogen atom-containing polyurethane resin emulsion (a10)]

250.2 parts of 4,4'-diphenylmethane diisocyanate and 303.0 parts of methyl ethyl ketone were put into a 5-necked flask equipped with a stirrer, a gym cooler, a nitrogen introduction tube, a silica gel drying tube, and a thermometer, and under nitrogen atmosphere. It heated up at 40 degreeC and stirred until 4,4'- diphenylmethane diisocyanate completely dissolved. Then, it heated up to 50 degreeC, 26 parts of 2-hydroxyethyl methacrylates were added, and it stirred for 30 minutes, and made the isocyanate group and hydroxyl group react. After the reaction, 94.0 parts of polypropylene glycol (Mitsui Takeda Chemical Co., Ltd., Actocol P-22) having a molecular weight of 1000, 25.2 parts of dipropylene glycol, 20 parts of diethylene glycol and 39 parts of dimethylolbutanoic acid were added sequentially, Stirring for 4 hours while adjusting to 50-60 degreeC, it confirmed that the reaction liquid reached | attained the predetermined isocyanate content, it cooled down to 30 degreeC, and the reaction mixture liquid containing a polyurethane prepolymer (methyl ethyl ketone of terminal isocyanate polyurethane prepolymer) Solution).

156.4 parts of 2-dimethylaminoethanol 15% aqueous solution was added, stirring 757.4 parts of obtained reaction liquid containing polyurethane prepolymers using homodisper, 983.4 parts of deionized water was added again, and the milky blue-white aqueous dispersion was obtained. 138.9 parts of 10% aqueous solution of N- (2-aminoethyl) ethanolamine is dripped at this aqueous dispersion at the temperature of 30 degrees C or less, chain extending reaction is performed, and methyl ethyl ketone and water are removed at 50 degreeC under reduced pressure, The active hydrogen atom containing polyurethane resin emulsion (a10) of 34.9% of solid content, the viscosity (25 degreeC) 3400 mPa * s, pH 8.3, and an average particle diameter of 31 nm was obtained.

[Preparation of an active hydrogen atom-containing polyurethane acrylic resin emulsion (a11)]

250.2 parts of 4,4'-diphenylmethane diisocyanate and 116.1 parts of styrene as an unsaturated compound were thrown into the 5-neck flask equipped with the stirrer, the luggage lot cooler, the nitrogen introduction tube, the silica gel drying tube, and the thermometer. It heated up at 40 degreeC and stirred until 4,4'- diphenylmethane diisocyanate completely dissolved. Then, the liquid mixture was heated up to 50 degreeC, 128.6 parts of polypropylene glycol (Mitsui Takeda Chemical Co., Ltd. make, Actocol P-22), 27.3 parts of diethylene glycol, 12.4 parts of trimethylol propanes, and dimethylol butanoic acid 45.7 parts and 193.4 parts of methyl ethyl ketones are added sequentially for viscosity adjustment, stirring for 4 hours, adjusting the temperature to 50-60 degreeC, confirming that the reaction liquid reached | attained the predetermined isocyanate content, and temperature-falling to 30 degreeC The reaction mixture liquid (unsaturated monomer (styrene) -methyl ethyl ketone solution of terminal isocyanate polyurethane prepolymer) containing the polyurethane prepolymer was obtained.

17.4 parts of trimethylolpropane triacrylate as an unsaturated compound were added to 773.7 parts of reaction mixture liquids containing the obtained polyurethane prepolymer, 183.4 parts of 15% aqueous solutions of 2-dimethylaminoethanol were added while stirring using a homodisper, and again 1333 parts of ionized water were added to obtain a milky blue-white aqueous dispersion. 138.9 parts of 10% aqueous solution of N- (2-aminoethyl) ethanolamine was added dropwise to this aqueous dispersion to carry out a chain extension reaction to contain an unsaturated compound (styrene-trimethylolpropanetriacrylate). Polyurethane resin emulsion was obtained.

2, which is a radical polymerization initiator, while stirring in 2446.4 parts of a polyurethane resin emulsion containing an unsaturated compound (styrene-trimethylolpropanetriacrylate) obtained in a flask equipped with a stirrer, a jimrot cooler, a nitrogen introduction tube, and a thermometer. 3.8 parts of 2'-azobisisobutyronitrile were added, the temperature was raised to 80 ° C, the reaction was carried out for 2 hours, and methylethyl ketone and water were removed at 50 ° C under reduced pressure to obtain a solid content of 35.0% and a viscosity (25 ° C) of 42 mPa. S, pH 8.6, and the active hydrogen atom containing polyurethane acrylic resin emulsion (a11) which is an average particle diameter of 88 nm were obtained.

In addition, the component in Table 2 and Table 3 and its symbol are as follows.

[Polyisocyanate]

MDI: 4,4'-diphenylmethane diisocyanate

TDI: Tolylene diisocyanate (Mitsui Takeda Chemical Co., Ltd., Cosmonate T-80)

[Polyol]

PPG: Polypropylene glycol having a molecular weight of 1000 (Mitsui Takeda Chemical Co., Ltd., Actocol P-22)

PTG: Polytetramethylene ether glycol having molecular weight 2000 (manufactured by Hodogaya Chemical Industry Co., Ltd., PTG-2000SN)

[Low Molecular Weight Polyol]

DPG: Dipropylene Glycol

DEG: Diethylene Glycol

NPG: Neopentylglycol

TMP: trimethylolpropane.

[Anionic Group Containing Compound]

DMBA: Dimethylolbutanoic Acid

DMPA: Dimethylolpropionic acid

[Active hydrogen atom-containing unsaturated compound]

HEMA: 2-hydroxyethyl methacrylate

GLM: Glycerol Monomethacrylate (manufactured by Nippon Yushi Co., Ltd., Brenmer GLM).

[Organic Solvent]

MEK: methyl ethyl ketone

[Active hydrogen atom-free unsaturated compound (unsaturated organic solvent)]

SM: Styrene

MMA: Methyl methacrylate

TMP-A: Trimethylolpropanetriacrylate

EGMA: ethylene glycol dimethacrylate.

[corrector]

15% DMEtA: 15% aqueous 2-dimethylaminoethanol solution

TEA: Triethylamine

[Polyamine]

10% A-EA: 10% aqueous N- (2-aminoethyl) ethanolamine solution

[Radical polymerization initiator]

AIBN: 2,2'-azobisisobutyronitrile

[Metal dryer]

Mix Dryer: 5% by weight of cobalt content, 0.2% by weight of lithium content, 7.5% by weight of zirconium content (lead-free dryer (manufactured by Yushibi Japan Co., Ltd., ADDITOL VXW6206)

NapH Co: Naphthenate cobalt (cobalt content 6 wt%)

NapH Zr: zirconium naphthenate (6% by weight of zirconium)

NapH Mn: Manganese naphthenate (manganese content 6 weight%).

Example 1

[Preparation of 2-Liquid Curing Water-Based Coating (c1)]

To 178.4 parts of the active hydrogen atom-containing polyurethane alkyd resin emulsion (a1), 9.4 parts of N-methylpyrrolidone (NMP) is added as a film forming aid, and as the curing agent (B), a polyoxyethylene-modified hexamethylene diisocyanate trimer (Mitsui) Takeda Chemical Co., Ltd. product, Takenate WD-240) 12.2 parts was mixed, and the two-liquid curable aqueous coating material (c1) was prepared.

[Preparation of Coating Film for Evaluation]

The obtained two-liquid curable aqueous coating material (c1) was applied to a glass plate and a steel sheet using a 100 µm applicator. Moreover, after apply | coating the said aqueous coating material to a glass plate, it was made to dry-cure for one week at room temperature, and it was set as the coating film for evaluation. Moreover, after apply | coating the said aqueous coating material to a steel plate, it baked at 120 degreeC for 30 minutes, and used as the coating film for evaluation.

Further, the beech wood polished with sandpaper No. 240 was brush-coated, dried at room temperature until the next day, and the surface of the coating film was polished with No. 400 sandpaper and brush-coated again. Thereafter, the recoating was repeated twice to produce a total of four layers of coating film, and after final application, drying and curing were performed for 1 week at room temperature to obtain a coating film for evaluation.

Examples 2-9

In the compounding prescription shown in Table 4, two-liquid curable aqueous coatings (c2 to c9) were prepared by the same operation as in Example 1, and a coating film for evaluation was formed by the same operation as in Example 1.

Comparative Examples 1 to 4

In the compounding prescription shown in Table 3, two-liquid curable aqueous coating materials (c10 to c13) were prepared by the same operation as in Example 1, and a coating film for evaluation was formed by the same operation as in Example 1. In addition, since Comparative Examples 3 and 4 did not mix hardening | curing agent (B), it becomes the formulation prescription which does not contain a hardening | curing agent in Examples 3 and 4.

In addition, the component in Table 4 and its symbol are as follows.

[Film Formation Aids]

NMP: N-methylpyrrolidone

[Hardener (B)]

B1: Polyoxyethylene-modified hexamethylene diisocyanate trimer, Mitsui Takeda Chemical Co., Ltd. product, Takeate WD-240, Isocyanate group content 16.9 weight%

B2: Polyoxyethylene polyoxyalkylene modified hexamethylene diisocyanate trimer, Mitsui Takeda Chemical Co., Ltd. product, Takeate WD-248, Isocyanate group content 15.4 weight%.

[evaluation]

(1) Compatibility of Polyurethane Alkyd Resin Emulsion (A) and Curing Agent (B)

The polyurethane alkyd resin emulsion (A) and the curing agent (B) obtained in the preparation example of the active hydrogen atom-containing polyurethane alkyd resin emulsion (a1 to a11) were mixed in a proportion shown in Table 4 in a 300 ml sample bottle for about 1 minute. The compatibility at the time of evaluation was visually evaluated based on the following criteria.

(Double-circle): A sample bottle can be mixed gently by shaking gently.

(Circle): A sample bottle can be mixed completely by shaking strongly.

(Triangle | delta): A sample bottle can be shaken vigorously and mixed somehow (it causes phase separation as time passes).

X: Even if the sample bottle was shaken vigorously, mixing failed and phase separation was caused.

(2) Film Formability of Coating Film

The film formability of the coating film at the time of apply | coating the two-liquid curable aqueous coating material obtained by each Example and each comparative example to the glass plate was visually evaluated on the following references | standards.

(Double-circle): A crack does not generate | occur | produce in a coating film (The coating film is obtained without a problem.)

(Circle): A gap generate | occur | produces in a part of coating film.

(Triangle | delta): A gap arises in the whole coating film.

X: The film cannot be formed.

(3) coating film appearance

The coating film appearance at the time of apply | coating four layers of the 2-liquid curable aqueous coating material obtained by each Example and each comparative example to beech wood was visually evaluated based on the following references | standards.

◎: The whole coating is high gloss and has a sense of thickness

(Circle): Glossy whole coating film

(Triangle | delta): The whole coating film is a glossiness removal state or is cloudy.

X: The crack generate | occur | produces in the whole coating film.

(4) water resistance

When the two-liquid curable aqueous coatings obtained in each Example and each Comparative Example were applied to a glass plate, a steel sheet, and beech wood (four layers), water was dropped on the surface of the coating film, covered with water to prevent volatilization, and maintained for 24 hours. The following coating film state was visually evaluated based on the following criteria.

(Double-circle): No change is seen in the whole coating film.

○: The coating film partially swells (blister occurs)

(Triangle | delta): The whole coating film is swollen or whitened.

X: The whole coating film melts

××: water penetrates into the gap and cannot be evaluated.

(5) moisture heat resistance

A glass bottle in which boiling water is dropped on the surface of the coating film when the two-liquid curable water-based paints obtained in each example and each comparative example are applied to a glass plate, a steel plate and beech wood (four layers), and immediately boiled with water (bottom portion). A bottle having a diameter of about 5 cm in which a little space is formed) was placed thereon, covered with water vapor so as not to volatilize, and the coating film state after holding for 20 minutes was visually evaluated by the following criteria.

(Double-circle): No change is seen in the whole coating film.

○: The coating film is partially swollen

(Triangle | delta): The whole coating film is swollen or whitened.

X: The whole coating film melts

××: boiling water penetrates into the gap and cannot be evaluated.

(6) solvent resistance

The rubbing test of the coating film when the two-liquid curable water-based coating material obtained in each example and each comparative example was applied to a glass plate and a steel sheet was carried out with methyl ethyl ketone. When it performed, the number of times (one circuit for 1 round trip and an upper limit of 100 circuits) until peeling of a coating film was evaluated based on the following references | standards.

(Double-circle): It does not peel off even more than 100 times, and no change is seen in the whole coating film.

(Circle): Although it does not peel even more than 100 times, the whole coating film swells slightly

(Triangle | delta): The whole coating film comes off in 50 times or less.

X: The whole coating film is peeled off in 10 times or less.

(7) pencil hardness

Pencil hardness was measured based on JISK5600-5-4 about the coating film when the 2-liquid curable aqueous coating material obtained by each Example and each comparative example was apply | coated to a glass plate, a steel plate, and the beech wood (4 layers).

(8) Magic pollution

A black and red xylene-containing magic was drawn on the coating film formed by applying four layers of the two-liquid curable water-based paints obtained in each example and each comparative example to beech wood, held for 3 hours, and then wiped off with ethanol. The coating state was visually evaluated based on the following criteria.

◎: Black and red magic are completely wiped off

(Circle): Black and red magic are partially or only one color wiped off.

(Triangle | delta): Black and red magic are wiped off, but it melt | dissolves for every coating film.

X: Black and red magic penetrate a coating film, and it is not wiped off at all.

Table 5 shows the evaluation results of each example and each comparative example.

As can be seen from the results in Table 5, the paints of the examples are excellent in various characteristics. On the other hand, in the paint of a comparative example, water resistance, moisture heat resistance, solvent resistance, etc. cannot be improved. In addition, long time is required for the development of hardness.

Example 10

Polyurethane alkyd resin emulsion (AA) to which 88.2 parts of the above-mentioned active hydrogen atom-containing polyurethane alkyd resin emulsion (a4) was added 6.8 parts of N-methylpyrrolidone (NMP) as a film forming aid under the condition of 23 ° C. and 50% RH (A Polyoxyethylene polyoxyalkylene-modified hexamethylene diisocyanate trimer (made by Mitsui Takeda Chemical Co., Ltd., Takenate WD-248, isocyanate group content 15.4%) and tap water as a hardening | curing agent (B), and a polyurethane alkyd resin emulsion ( It was mixed by the ratio (weight ratio) of A) / hardening | curing agent (B) / tap water = 95/5/95, and the two-liquid hardening type aqueous primer was prepared. On the surface of the slate plate which previously treated the surface by air blow, the said two-liquid curable aqueous primer immediately after it was prepared on 23 degreeC and 50% RH conditions was apply | coated uniformly so that application amount might be 150 g / m <2>, and it was left to stand for 3 hours. . 2-component urethane resin immediately after mixing a main body and a hardening | curing agent in the ratio of 1: 1 (weight ratio) on this coating film surface (commercial coating material, Mitsui Takeda Chemical Co., Ltd. product, Main subject: Takenate F-135, Hardening agent: Takerak) PC-5300) was uniformly applied using a pharynx so that the coating amount was 2000 g / m 2, and incubated at 23 ° C. and 50 RH for 7 days to prepare a slate plate coated sample.

Example 11

To 88.2 parts of the active hydrogen atom-containing polyurethane alkyd resin emulsion (a4), 80% as a polyurethane alkyd resin emulsion (A) and a curing agent (B) added 6.8 parts of N-methylpyrrolidone (NMP) as a film forming aid. A solution of propylene glycol monomethyl ether acetate (PMA) containing the modified hexamethylene diisocyanate trimer (takeate WD-248) and tap water at a concentration was added to the polyurethane alkyd resin emulsion (A) / hardener (B) / tap water = 95 / A slate plate coated sample was produced in the same manner as in Example 10 except that the two-liquid curable aqueous primer mixed at a ratio (weight ratio) of 6.3 / 95 was used.

Example 12

80% concentration as a polyurethane alkyd resin emulsion (A) and a curing agent (B), in which 6.8 parts of N-methylpyrrolidone (NMP) was added to 88.2 parts of the active hydrogen atom-containing polyurethane alkyd resin emulsion (a4) as a film forming aid. The acetone solution and the tap water containing the modified hexamethylene diisocyanate trimer (Takenate WD-248) were added at a ratio (weight ratio) of polyurethane alkyd resin emulsion (A) / curing agent (B) / tap water = 95 / 6.3 / 95. A slate plate coated sample was prepared in the same manner as in Example 10 except that the mixed two-liquid curable aqueous primer was used.

Example 13

80% as the polyurethane alkyd resin emulsion (A) and the curing agent (B) to which 86.8 parts of the active hydrogen atom-containing polyurethane alkyd resin emulsion (a9) was added 8.2 parts of N-methylpyrrolidone (NMP) as a film forming aid. A solution of propylene glycol monomethyl ether acetate (PMA) containing the modified hexamethylene diisocyanate trimer (takeate WD-248) and tap water at a concentration was added to the polyurethane alkyd resin emulsion (A) / hardener (B) / tap water = 95 / A slate plate coated sample was prepared in the same manner as in Example 10 except that the two-liquid curable aqueous primer mixed at a ratio (weight ratio) of 6.3 / 95 was used.

Example 14

The modified hexa as a polyurethane alkyd resin emulsion (A) and a curing agent (B) having added 4.7 parts of N-methylpyrrolidone (NMP) as a film forming aid to 90.3 parts of the active hydrogen atom-containing polyurethane alkyd resin emulsion (a2). Methylene diisocyanate trimer (takeate WD-248) and tap water were mixed with a polyurethane alkyd resin emulsion (A) / curing agent (B) / tap water = 95/5/95 (weight ratio) using a two-liquid curable aqueous primer. A slate plate coated sample was prepared in the same manner as in Example 10 except for the above.

Comparative Example 5

A slate plate coated sample was prepared in the same manner as in Example 10 except that a TDI-based one-liquid moisture-curable solvent-based primer composition (Mitsui Takeda Chemical Co., Ltd. product, Takeate M-402p) was used instead of the two-liquid curable aqueous primer. It was.

Comparative Example 6

A slate plate coated sample was produced in the same manner as in Example 10 except that an MDI-based one-liquid moisture-curable solvent-based primer composition (Mitsui Takeda Chemical Co., Ltd. product, Hyphen AX-616) was used instead of the two-liquid curable aqueous primer. It was.

The slate plate coating samples for evaluation of these Examples 10-14 and Comparative Examples 5-6 were provided for the following evaluation tests.

[Evaluation test]

(1) Appearance change after domestic water

Tap water was filled into a plastic container with a lid, and the whole of the sample (slate plate on which the coating film was formed) was immersed in water while completely submerged in water, and left at 23 ° C. and 50% RH for 7 days. Then, the sample which remove | extracted from water and visually observed the surface state of a polyurethane coating film, and peeling and a swelling was not seen was made into the sample which the change of (circle), peeling, swelling, etc. was confirmed.

(2) State adhesiveness

The polyurethane coating film surface of the sample was cut out to 25 mm width, and the adhesive strength (N / mm) was measured by the 90 degree peel test.

(3) water resistance

Adhesive strength (N / mm) was measured by the method similar to state adhesiveness using the sample used for external appearance evaluation after water resistance.

(4) dry adhesiveness

The adhesive strength (N / mm) was measured by the same method as the state adhesiveness after leaving the sample used by the external appearance evaluation after water resistance for 1 day under the conditions of 23 degreeC and 50% RH.

Table 6 shows the test results of each example and each comparative example.

As can be seen from the results in Table 6, the aqueous primer of the example is obtained with a two-liquid curable aqueous primer at the same level as the solvent-based primer excellent in various inorganic material adherends, adhesion to the top coat, and durability.

Claims (14)

A two-liquid curable aqueous resin composition containing a polyurethane alkyd resin emulsion (A) having an active hydrogen atom in a molecule and a curing agent (B) that can be dispersed in the emulsion (A), wherein the curing agent (B) is a polyisocyanate and an isocyanate A two-liquid curable aqueous resin composition which is a dispersible polyisocyanate obtained by reaction with a surface active or dispersible component having an active hydrogen atom reactive with respect to the group. The method of claim 1, Polyurethane alkyd resin emulsion (A) A two-liquid curable aqueous resin composition which is an emulsion obtained by the reaction of an alkyd resin having a hydroxyl value of 30 to 250 and a polyisocyanate. The method of claim 1, A two-liquid curable aqueous resin composition in which the polyurethane alkyd resin emulsion (A) has an active hydrogen atom derived from a hydroxyl group. The method of claim 1, A two-liquid curable aqueous resin composition, further comprising a metal dryer (C), wherein the alkyd resin component of the polyurethane alkyd resin emulsion (A) contains an unsaturated fatty acid as a structural unit. The method of claim 1, A two-liquid curable aqueous resin composition in which the polyurethane alkyd resin emulsion (A) further contains a (meth) acrylic component having a polymerizable group. delete The method of claim 1, A two-liquid curable aqueous resin composition wherein the surfactant or dispersible component is at least one member selected from the group consisting of nonionic surfactants and compounds having at least ethylene oxide chains. The method of claim 1, A two-liquid curable aqueous resin composition in which the ratio of the curing agent (B) to the polyurethane alkyd resin emulsion (A) is 0.3 to 4 (equivalent ratio) as an isocyanate group / active hydrogen atom in terms of solid content. The method of claim 1, A two-liquid curable aqueous resin composition that can be cured at room temperature. A two-liquid curable aqueous coating containing a polyurethane alkyd resin emulsion (A) having an active hydrogen atom in a molecule and a curing agent (B) that can be dispersed in the emulsion (A), wherein the curing agent (B) is a polyisocyanate and isocyanate group. A two-liquid curable aqueous coating material, which is a dispersible polyisocyanate obtained by reaction with a surface active or dispersible component having an active hydrogen atom reactive toward. A two-liquid curable aqueous primer containing a polyurethane alkyd resin emulsion (A) having an active hydrogen atom in a molecule and a curing agent (B) that can be dispersed in the emulsion (A), wherein the curing agent (B) is a polyisocyanate and isocyanate group. A two-liquid curable aqueous primer which is a dispersible polyisocyanate obtained by reaction with a surface active or dispersible component having an active hydrogen atom reactive toward. The two-liquid curable aqueous resin composition according to claim 1, wherein the alkyd resin component of the polyurethane alkyd resin emulsion (A) contains a saturated fatty acid as a structural unit. The two-liquid curable aqueous resin composition according to claim 1, wherein the surfactant or dispersible component is a nonionic surfactant having an oxyethylene unit having an average content of 12 to 30 in one molecule. The group according to claim 1, wherein the surfactant or dispersible component is made of polyoxyethylene C8-24 alkyl ether, polyoxyethylene C8-12 alkylphenyl ether, and polyoxyethylene polyoxy C3-6 alkylene C8-24 ether. A two-liquid curable aqueous resin composition which is at least one member selected from.