JP4757067B2 - Two-component curable aqueous urethane alkyd resin composition and use thereof - Google Patents

Description

  The present invention comprises a polyurethane alkyd resin emulsion and a polyisocyanate curing agent dispersible in the emulsion, and is useful as an aqueous coating agent (aqueous paint such as wood paint and automobile paint) and an aqueous primer. The present invention relates to a curable aqueous resin composition (such as a coating composition) and its use.

  Polyurethane resins are widely used in applications such as various paints, adhesives, and various coating agents because they are excellent in adhesion to substrates, abrasion resistance, impact resistance, and mechanical strength. 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, organic solvents do not necessarily have a positive effect on the human body and the environment, and there is a risk of ignition. Therefore, in recent years, interest in the hygienic environment has increased, and instead of organic solvent-based polyurethane resin paints, development of water-based polyurethane resin paints composed of polyurethane resin aqueous dispersions in which polyurethane resins are dispersed in water has been rapidly advanced. Yes.

  On the other hand, alkyd resins have good gloss and water resistance on the coating surface, have a feeling of flesh and are inexpensive, and have been widely used for industrial and general purposes since ancient times. For example, in order to widely use in various paints, adhesives, and various coating agents, alkyd resin emulsions have been studied. In particular, in order to provide added value such as weather resistance and solvent resistance, a urethane alkyd resin emulsion in which a urethane resin is combined has been developed.

  For example, JP-A-6-299117 (Patent Document 1) discloses a resin (A) having a hydroxyl value of 30 to 250 obtained by reacting a drying oil or semi-drying oil and / or a fatty acid thereof as an essential component with oxy Disclosed is a coating composition for an aqueous synthetic resin blend paint comprising an aqueous resin obtained by reacting a carboxylic acid (B), another hydroxyl compound (C) and an organic isocyanate compound (D), a pigment and a desiccant. Has been. Specifically, in this document, alkyd resin obtained by transesterification of (semi) drying oil and pentaerythritol is used to urethanize, disperse in water, and then perform chain elongation. Such a composition can be cross-linked at room temperature, has good dryness of the coating film, has a good feeling of texture, and has good brush coatability, and has no ester bond adjacent to the carboxyl group, so it is resistant to hydrolysis. Also excellent. However, since a long time is required for the cross-linking reaction, a coating film having a high hardness cannot be obtained in a short time, and the degree of improvement in water resistance, moist heat resistance and solvent resistance is low.

  JP-A-6-329892 (Patent Document 2) discloses an alkyd resin (A) having a hydroxyl value 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 obtained by reacting and a curing agent. This document describes that a coating film having high hardness and various durability can be formed by curing an alkyd resin similar to Patent Document 1 with a curing agent such as an amino resin or blocked isocyanate. However, since this composition uses an amino resin or blocked isocyanate as a curing agent, baking is essential, and a coating film having high hardness cannot be obtained at room temperature.

In addition, when applying organic topcoat materials such as urethane-based coating materials to adherends of inorganic materials such as slate, concrete, mortar, etc., moisture-curing polyurethane resins, etc. to ensure stronger adhesion However, it is necessary to add a large amount of an organic solvent for the purpose of improving the impregnation property to the substrate and further the coating workability. Although a primer containing such a large amount of organic solvent is excellent in coating workability and coating film performance after curing, adverse effects on the health of workers due to volatilization of organic solvents during work, adverse effects on the environment, etc. This problem is pointed out, and the appearance of an aqueous primer composition is expected.
JP-A-6-299117 (claims, paragraph numbers [0011] [0047], examples) JP-A-6-329892 (Claims, paragraph numbers [0028] [0034], Examples)

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

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

  Still another object of the present invention is to use a two-component curing which is excellent in compatibility between the main agent and the curing agent, and also has a feeling of holding and coating workability in the formation of a coating film, even if a polyurethane alkyd resin emulsion is used as the main agent. It is providing a type | mold aqueous resin composition.

  Another object of the present invention is to provide a two-component curable aqueous resin composition in which the alkyd resin component in the urethane component can be adjusted to an arbitrary ratio and the coating film properties can be controlled.

  Still another object of the present invention is a two-part curable aqueous resin composition that is excellent in adhesion and durability to adherends of inorganic materials such as slate, concrete, and mortar, and also excellent in adhesion and durability with a top coating material. To provide things.

  Another object of the present invention is to provide a two-component curable aqueous resin composition (or paint) useful mainly as a paint for woodwork, a paint for automobiles, an aqueous primer, and the like.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have found that both a polyurethane resin and an alkyd resin can be obtained by combining a polyurethane alkyd resin emulsion having an active hydrogen atom in the molecule with a specific polyisocyanate as a curing agent. It has been found that a two-component curable aqueous resin composition can be obtained effectively in a short time, has excellent mechanical properties such as hardness and abrasion resistance, and has high water resistance, moist heat resistance and solvent resistance. The present invention has been completed.

  That is, the aqueous resin composition (two-part curable aqueous resin composition) of the present invention is a polyurethane alkyd resin emulsion (A) having an active hydrogen atom in the molecule and a polyisocyanate dispersible in the emulsion (A). And a configured curing agent (B). The polyurethane alkyd resin emulsion (A) may be an emulsion obtained by a reaction between an alkyd resin having a hydroxyl value of 30 to 250 and a polyisocyanate. The active hydrogen atom of the polyurethane alkyd resin emulsion (A) may be derived from, for example, a hydroxyl group. 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 constituent unit. The polyurethane alkyd resin emulsion (A) may further contain a (meth) acryl component having a polymerizable group. Further, the curing agent (B) may be a dispersible polyisocyanate obtained by reacting a polyisocyanate with a surface active or dispersible component having an active hydrogen atom reactive with an isocyanate group. In addition, the said surface active or dispersible component can be comprised with at least 1 type selected from the compound group which consists of a nonionic surfactant and the compound which has an ethylene oxide chain at least. Further, the ratio of the curing agent (B) to the polyurethane alkyd resin emulsion (A) may be about 0.3 to 4 (equivalent ratio) as an isocyanate group / active hydrogen atom in terms of solid content. This composition is usually curable at room temperature.

  The present invention includes a two-part curable aqueous solution comprising a polyurethane alkyd resin emulsion (A) having an active hydrogen atom in the molecule and a curing agent (B) composed of a polyisocyanate dispersible in the emulsion (A). Paint is also included.

  The present invention includes a two-part curable aqueous solution comprising a polyurethane alkyd resin emulsion (A) having an active hydrogen atom in the molecule and a curing agent (B) composed of a polyisocyanate dispersible in the emulsion (A). Primers are also included. This aqueous primer composition is excellent in adhesiveness and durability to adherends of inorganic materials such as slate, concrete and mortar. Furthermore, it is excellent in adhesion and durability with a top coat such as a waterproofing material, a flooring material, and a sealing material that exhibit an excellent adherend protecting effect after curing.

In this specification, “(meth) acrylic monomer” or “(meth) acrylic component” is not only a generic term for acrylic monomers and methacrylic monomers, but also polymerizable unsaturated. It may be used to include a polymerizable monomer having a bond (such as styrene or vinyltoluene).

  In the present invention, since the specific polyurethane alkyd resin emulsion and the curing agent composed of the specific polyisocyanate are combined, the characteristics of both the polyurethane resin and the alkyd resin can be effectively expressed in a short time. In addition to excellent mechanical properties such as hardness and wear resistance, water resistance, moist heat resistance and solvent resistance can also be improved. Furthermore, even if a polyurethane alkyd resin emulsion is used as the main agent, the compatibility between the main agent and the curing agent is excellent, and the feeling of holding in coating film formation and the coating workability are also excellent. Furthermore, the alkyd resin component in the urethane component can be adjusted to an arbitrary ratio, and the coating film characteristics can be controlled. Therefore, the two-component curable aqueous resin composition of the present invention is useful as an aqueous paint for woodwork paints, automotive paints, aqueous primers and the like.

  The two-part curable aqueous resin composition of the present invention comprises a polyurethane alkyd resin emulsion (A) having an active hydrogen atom in the molecule, and a curing agent (B) composed of a polyisocyanate dispersible in the emulsion (A). In addition to adhesion to the substrate, the coating film properties (particularly high hardness) and water resistance are also 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 the molecule, and is a compound having at least a polyisocyanate and an active hydrogen atom reactive with an isocyanate group ( It is obtained by reaction with an alkyd resin as a polyol component). In the present invention, the hydroxyl value of the alkyd resin is about 30 to 200, and the alkyd resin having such a hydroxyl value is used as the polyol component of the polyurethane alkyd resin emulsion. Furthermore, in addition to the alkyd resin, other components having an active hydrogen atom reactive with an isocyanate group may be used. The active hydrogen atom may be derived from at least one of the alkyd resin, the modified polyisocyanate having an active hydrogen atom, the chain extender, and other components.

(1) Alkyd resin The alkyd resin may be a polyester (oil-free alkyd resin) obtained by a condensation reaction of a polycarboxylic acid containing a long-chain aliphatic polycarboxylic acid and a polyol. Polyester (oil-modified alkyd resin) obtained in this way is preferable.

  Alkyd resins, also called oil-modified polyesters, are selected from polyesters, oils and fats and saturated or unsaturated higher fatty acids obtained by reaction of at least one oil component selected from oils and fats and saturated or unsaturated higher fatty acids with polyols. In addition, polyesters obtained by the reaction of at least one oil component, polyol and polycarboxylic acid are included. These reactions include not only esterification reactions but also transesterification reactions (for example, transesterification reactions of fats and oils (triglycerides, etc.) and polyols).

(Polyol)
Examples of the polyol include various polyols used in the production of polyester, such as aliphatic diol [alkanediol (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 C ₂ such as diethyl-1,3-propanediol, 3,3-dimethylolheptane, 2-ethyl-2-butyl-1,3-propanediol, 1,12-dodecanediol, 1,18-octadecanediol _-22 alkanediol), alkene diol (2-butene, - diol, 2,6-dimethyl-1-octene-3,8-diol, etc.), poly C _2-4 alkylene glycol (diethylene glycol, triethylene glycol, polyethylene glycol having an average molecular weight 150-4000, dipropylene glycol, average Polypropylene glycol having a molecular weight of about 150 to 4000, polytetramethylene ether glycol having an average molecular weight of about 150 to 4000, and the like], cycloalikane diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol s, hydrogenated bisphenol such as hydrogenated bisphenol a, also FUN C _2-4 alkylene oxide adduct of these etc.), benzene diols and aromatic diols (resorcinol, araliphatic such as xylylene glycol Ol, polyester diols such as bis-hydroxy ethylene terephthalate, bisphenol A, bisphenol S, bisphenol such as bisphenol F, or an C _2-4 alkylene oxide adduct thereof), trihydric or higher polyols [aliphatic polyols (glycerol, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3- (hydroxymethyl) pentane, 2,2 - bis (hydroxymethyl) -3-aliphatic C _3-24 triol, such as butanol, pentaerythritol, pentaerythritol such as dipentaerythritol etc.), sugar alcohols (D-sorbitol, xylitol, D- mannitol Etc.), etc.] can be exemplified. These polyols can be used alone or in combination of two or more. Of these, trihydric or higher polyols such as aliphatic polyols such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol are preferable.

(Oil component)
Oil components include fats and oils, saturated or unsaturated fatty acids. Examples of oils and fats include vegetable oil (cotton seed oil, sesame oil, castor oil, dehydrated castor oil, safflower oil (safflower oil), soybean oil, rice oil, corn oil, sesame oil, sunflower oil, rice sugar oil, assami oil, rapeseed oil, Peanut oil, palm oil, palm oil, kapok oil, tonsil oil, olive oil, tall oil, enamel oil, drill oil, etc., animal oil (beef tallow, pork fat, sheep fat, goat fat, horse fat, chicken fat, turkey) Fats, etc.), fish oil (herring oil, flatfish oil, cod oil, citrus oil, hariba oil, carp oil, trout oil, catfish oil, etc.), or hydrogenated oils thereof. These fats and oils can be used alone or in combination of two or more. Among these oils and fats, vegetable oils, especially dry oils such as linseed oil, linseed oil, persimmon oil, dehydrated castor oil, semi-dryness such as soybean oil, cottonseed oil, safflower oil, corn oil, sesame oil, rapeseed oil and rice bran oil Non-drying oils such as oil, palm oil and palm oil are preferred.

Examples of saturated fatty acids include linear or branched saturated C _8-24 fatty acids such as caprylic acid, capric acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, and behenic acid. Is mentioned. Examples of unsaturated fatty acids include linear or branched chains such as myristoleic acid, palmitoleic acid, petrothelic acid, oleic acid, vacenoic acid, linoleic acid, linolenic acid, eleostearic acid, gatrenic acid, arachidonic acid, and erucic acid. And unsaturated C _8-24 4 fatty acids. These fatty acids may have a substituent such as a hydroxyl group. Examples of the fatty acid having a hydroxyl group include ricinoleic acid, sabinic acid, and dioxystearic acid, which are the main components of castor oil. The fatty acid may be a fatty acid obtained by saponification or the like from the above fats and oils, for example, a high-diene fatty acid obtained from dehydrated castor oil, dehydrated castor oil, linseed oil, soybean oil, safflower oil, coconut oil or the like. Fatty acid (for example, dehydrated castor oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, safflower oil fatty acid, coconut oil fatty acid, etc.) may be used. These saturated or unsaturated fatty acids can be used alone or in combination of two or more. Of these fatty acids, fatty acids (such as oleic acid, linoleic acid, and linolenic acid) obtained from drying oils and semi-drying oils, and unsaturated fatty acids such as high diene fatty acids are preferred. Of these fatty acids, fatty acids (such as lauric acid, capric acid, caprylic acid, myristic acid, etc.) obtained from non-drying oils and fatty acids rich in saturated fatty acids such as coconut oil fatty acids suppress resin coloring. It is preferable from the point which can be performed.

  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 bond contained in these oil components reacts with oxygen in the air. Then, since an oxidative curing reaction is caused to cure, a more excellent coating film can be formed.

  Such an oxidative curing reaction usually reacts gradually using oxygen in the air, but in order to accelerate this reaction, a metal dryer or a desiccant (C) described later may be further added. Good. That is, by combining a polyurethane alkyd resin emulsion (A) having an alkyd resin component modified with an unsaturated fatty acid and a metal dryer (C), a coating film excellent in properties such as hardness can be formed in a short time. Can do.

(Polycarboxylic acid)
Examples of the polycarboxylic acid include various polycarboxylic acids used in the production of polyester, for example, aromatic dicarboxylic acid or its anhydride (terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, etc.), alicyclic dicarboxylic acid Or anhydrides thereof (tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, methyltetrahydrophthalic acid, anhydrous hetic acid, hymic anhydride, etc.), aliphatic dicarboxylic acids or anhydrides (succinic acid) C _4-20 alkane dicarboxylic acids such as succinic anhydride, adipic acid, azelaic acid, sebacic acid, etc., unsaturated dicarboxylic acids such as itaconic acid, itaconic anhydride, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, etc. ), Trimellitic acid, trimellitic anhydride, pyromellitic acid, anhydrous Romeritto acid, methyl cyclohexene tricarboxylic acid or mono- to tetra-alkyl esters of these carboxylic acids can be exemplified. These polycarboxylic acids can be used alone or in combination of two or more. Of these polycarboxylic acids, aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid are widely used.

  For the preparation of the alkyd resin, in addition to the fatty acid and polycarboxylic acid, for example, aromatic monocarboxylic acids such as benzoic acid and pt-butylbenzoic acid may be used as the carboxylic acid component.

  Such an alkyd resin can be produced by a conventional method, for example, a fatty acid method using a fatty acid as a raw material, or a monoglyceride method in which a transesterification reaction is performed using an oil or fat as a raw material. In the fatty acid method, for example, a fatty acid, a polyol, and a polycarboxylic acid may be charged, and the esterification reaction may be performed at about 220 to 250 ° C. for about 6 to 10 hours. In the esterification reaction, for example, a very small amount of an esterification catalyst such as mono n-butyltin oxide may be added. The ratio of the esterification catalyst is, for example, about 0.00001 to 0.1 parts by weight, and preferably about 0.0001 to 0.01 parts by weight with respect to 100 parts by weight of the oil component. In order to remove the condensed water in the esterification reaction, an inert solvent (such as an aromatic hydrocarbon such as toluene or xylene) azeotropic with water may be used.

  In the monoglyceride method, for example, a transesterification reaction is performed for 2 to 3 hours at about 230 to 250 ° C. in the presence of an alkali catalyst while stirring oils and polyols, and then charged with a polyol and, if necessary, a polycarboxylic acid. The esterification reaction may be performed at about 220 to 250 ° C. In the transesterification reaction, for example, a basic catalyst such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium acetate or lithium acetate may be added in a very small amount.

  Regarding the ratio of each component in the alkyd resin, the ratio (weight ratio) of the oil component to the total amount of the polyol component and the polycarboxylic acid is the former / the latter = 10/1 to 1/5, preferably 5/1 to 1. / 3, more preferably 4/1 to 1/1 (particularly 3/1 to 1.5 / 1).

  The proportion of the polyol component is, for example, about 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) with respect to 100 parts by weight of the oil component. .

  The proportion of the polycarboxylic acid is, for example, about 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) with respect to 100 parts by weight of the oil component. is there.

  The alkyd resin may have a hydroxyl group and / or a carboxyl group, but usually has at least a hydroxyl group for use as a polyol component. The alkyd resin may have a hydroxyl group at the branched chain or at both ends. Usually, it has a hydroxyl group at least at both ends.

  The hydroxyl value (KOHmg / g) of the alkyd resin is, for example, about 30 to 250, preferably about 40 to 230, and more preferably about 50 to 220 (particularly 60 to 200).

(2) Polyisocyanate Polyisocyanate is not particularly limited as long as it has two or more isocyanate groups in the molecule, and polyisocyanate usually used in the production of polyurethane, for example, aliphatic polyisocyanate, alicyclic polyisocyanate. Examples thereof include low molecular weight polyisocyanates such as isocyanate, araliphatic polyisocyanate, and aromatic polyisocyanate, prepolymers, isocyanurate bodies, trione bodies, and derivatives and modified bodies of these polyisocyanates.

  “Polyisocyanate” is a general term for compounds having a plurality of isocyanate groups in the molecule, and low molecular polyisocyanates such as diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and derivatives obtained from these polyisocyanates, Includes modified products, prepolymers and the like. “Polyisocyanate derivative” is a general term for compounds obtained from low-molecular polyisocyanates, and includes modified products, prepolymers, and the like. The “polyisocyanate modified product” means a reaction product obtained by modifying a low molecular polyisocyanate or a prepolymer.

Examples of the aliphatic polyisocyanate include diisocyanates (for example, trimethylene diisocyanate, 1,2-propylene diisocyanate, tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, hexamethylene. Diisocyanates, pentamethylene diisocyanates, C _2-16 alkane diisocyanates such as 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate), polyisocyanates (for example, Lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatome Ruokutan, 1,3,6-tri-diisocyanatohexane, 2,5,7-like C _6-20 alkanes triisocyanates such as trimethyl-1,8-diisocyanato-5-isocyanatomethyl octane) and the like.

Examples of the alicyclic polyisocyanates include diisocyanates (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-cyclohexanediisocyanate, 1,3- or 1,4-bis (isocyanato) Methyl) cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, norbornane diisocyanate, etc.), polyisocyanate (for example, 1,3,5-triisocyanatooxy) Rhohexane, 1,3,5-trimethylisocyanatocyclohexane, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo [2.2.1] heptane, 2- (3-isocyanate Natopropyl) -2,6-di (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-Isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2.2.1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- 3-Isocyanatopropyl) -bicyclo [2.2.1] -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo [2.2. 1] triisocyanate such as heptane).

  Examples of the araliphatic polyisocyanate include diisocyanates (for example, 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω, ω′-diisocyanato-1,4-diethylbenzene, 1,3- or 1,4. -Bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or a mixture thereof, polyisocyanate (for example, triisocyanate such as 1,3,5-triisocyanatomethylbenzene) ).

  Examples of the aromatic polyisocyanate include diisocyanates (for example, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 2,4′- or 4,4′-diphenylmethane diisocyanate). Or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof, 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate, etc.), polyisocyanate (for example, triphenylmethane-4,4 Triisocyanates such as', 4 ''-triisocyanate, 1,3,5-triisocyanate benzene, 2,4,6-triisocyanate toluene, for example, 4,4'-diphenylmethane 2,2 ', such as tetra-isocyanates such as 5,5'-tetra-isocyanate) and the like.

  Examples of the polyisocyanate derivative include 2,4,6-, which can be obtained by reacting the polyisocyanate with a dimer, trimer (isocyanurate ring-containing polyisocyanate), biuret, allophanate, carbon dioxide and the above polyisocyanate monomer. Examples thereof include polyisocyanates having an oxadiazine trione ring, carbodiimides, uretdiones, polymethylene polyphenyl polyisocyanates (crude MDI, polymeric MDI), and crude TDI.

  Furthermore, as the modified polyisocyanate, for example, the polyisocyanate or a polyisocyanate derivative and a low molecular weight polyol or a low molecular weight polyamine described later, the isocyanate group of the polyisocyanate is a hydroxyl group or a low molecular weight of a low molecular weight polyol. Examples include polyol-modified products, polyamine-modified products, and the like obtained by reacting at an equivalent ratio in excess of the amino group of polyamine. These polyisocyanates may be used alone or in combination of two or more.

(3) Other components In the emulsion of the present invention, in addition to the alkyd resin and polyisocyanate, as other components, active hydrogen atoms reactive with isocyanate groups (for example, hydroxyl group, carboxyl group, amino group) Etc.) may be included.

(Other polyols)
As the compound having a hydroxyl group, in addition to the alkyd resin, other polyols may be contained. Other polyols are not particularly limited, and various polyols used in the production of polyurethane, for example, polyols exemplified in the above-mentioned alkyd resin, polyester polyols (excluding the alkyd resins), polyether polyols, poly polyetherester polyols, polyesteramide polyols, acrylic polyols, polycarbonate polyols, Po Li urethane polyol, polyhydroxy alkane, polybutadiene polyols, etc. can be exemplified modified castor oil polyol, these polyol may be used singly or in combination.

As said polyester polyol, it can obtain by reaction of dicarboxylic acid and diol, for example. Examples of the dicarboxylic acid (or its anhydride) include the dicarboxylic acids exemplified in the section of polycarboxylic acid in the alkyd resin component. Examples of the diol include diols exemplified in the section of polyol in the alkyd resin component. If necessary, polycarboxylic acids (such as trimellitic acid and pyromellitic anhydride) and polyhydroxy compounds (such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, and dipentaerythritol) may be used. In addition, polyol initiators such as triols (eg glycerin, 1,2,6-hexanetriol, 1,1,1-tris (hydroxymethyl) propane), tetraols (eg pentaerythritol, erythritol, methyl glucoside) Etc.), hexaols (eg, sorbitol, dipentaerythritol, etc.), octaols (eg, sucrose), and amine initiators, eg, diamines (eg, ethylenediamine, propylenediamine, hexamethylenediamine, hydrazine, etc.), A triamine or higher polyamine (for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc.) is used to make lactones (caprolactone such as ε-caprolactone, valerolactone, β-methyl-γ-ba C _4-10 polyester polyols obtained by a lactone, etc.) ring-opening polymerization, such as Rorakuton can also be used.

  Examples of the polyether polyol include oxirane compounds (for example, ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, etc.) or copolymers, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, bisphenol A and other low molecular weights. Examples thereof include polyether polyols obtained by polymerizing the oxirane compound using a polyol and / or a low molecular weight polyamine described later as an initiator.

  Examples of the polyether ester polyol include a reaction between the dicarboxylic acid (aromatic dicarboxylic acid, alicyclic dicarboxylic acid, aliphatic dicarboxylic acid, etc.) or a dialkyl ester thereof or a mixture thereof and the polyether polyol. Examples include polyether ester polyols obtained.

As the polyester amide polyol, an aliphatic group having an amino group such as ethylene diamine, propylene diamine, hexamethylene diamine or the like as a reaction component in the reaction of the polyester polyol (reaction of dicarboxylic acid and diol). And amide polyols obtained by using diamines).

  As the acrylic polyol, a polymerizable monomer having one or more hydroxyl groups in one molecule (for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, etc.), Examples thereof include acrylic polyols obtained by copolymerizing a (meth) acrylic monomer not containing a hydroxyl group (for example, (meth) acrylic acid or an ester thereof).

  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, 3- Alkanediols such as methyl-1,5-pentanediol, 1,9-nonanediol and 1,8-nonanediol; (poly) oxyalkylene glycols such as diethylene glycol and dipropylene glycol; 1,4-cyclohexanediol, 1, 1 type selected from the group consisting of alicyclic diols such as 4-cyclohexanedimethanol and hydrogenated bisphenol A; bisphenols such as bisphenol A, and aromatic diols such as alkylene oxide adducts of bisphenols or Species more glycols) and carbonate (dimethyl carbonate, ethylene carbonate, diphenyl carbonate), and polycarbonate polyols obtained by reacting phosgene and the like.

  As said polyurethane polyol, the polyol which has a urethane bond in 1 molecule is mentioned, for example. This polyol includes, 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. And an equivalent ratio of isocyanate groups to (isocyanate groups / hydroxyl groups) of less than 1 (preferably 0.9 or less, for example, about 0.3 to 0.7).

  Examples of the polyhydroxyalkane include isoprene, butadiene, or liquid rubber obtained by copolymerizing butadiene and acrylamide.

These other polyols may be used alone or in combination of two or more. 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 ether glycol, etc. Polyols such as poly C _2-4 alkylene glycol, glycerin, trimethylol propane and pentaerythritol are preferred. The molecular weight of these low molecular weight polyols is about number average molecular weight 62-500, preferably about number average molecular weight 62-200.

  If necessary, monools such as methanol, ethanol, propanols, butanols, 2-ethylhexanol, lauryl alcohol, stearyl alcohol, 2-mercaptoethanol, polyoxymethylenediol monomethyl ether can be used in combination. it can.

  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 100 parts by weight) with respect to 100 parts by weight of the alkyd resin. Part) grade.

(Compound having an anionic group)
In the polyurethane alkyd resin, an anionic group is not always necessary, but the dispersion stability of the polyurethane alkyd resin can be improved by introducing the anionic group. This anionic group is usually introduced by using a compound having an anionic group and an active hydrogen atom reactive with an isocyanate group.

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

  The type of the active hydrogen atom-containing compound having such an anionic group is not particularly limited, and examples thereof include compounds having at least one anionic group and two or more active hydrogen atoms.

Examples of the active hydrogen atom-containing compound having a carboxyl group include 2,2-dimethylolacetic acid, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2- Dihydroxyl carboxylic acids such as dimethylolbutyric acid and 2,2-dimethylolvaleric acid (such as dimethylol C _2-10 alkanecarboxylic acid or dihydroxyl C _2-10 alkanecarboxylic acid), for example, diaminocarboxylic acids such as lysine and arginine Can be mentioned.

  Examples of the active hydrogen atom-containing compound having a sulfonyl group or a sulfonic acid group include N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, 1,3-phenylenediamine-4,6-disulfone. Examples include acid, diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, and 2,4-diamino-5-toluenesulfonic acid.

  Examples of the active hydrogen atom-containing compound having a phosphoric acid group include 2,3-dihydroxypropylphenyl phosphate.

  Examples of the active hydrogen atom-containing compound having a betaine structure-containing group include a sulfobetaine group-containing compound obtained by a reaction of a tertiary amine such as N-methyldiethanolamine with 1,3-propane sultone, 1,4-butane sultone, etc. Etc.

  Furthermore, 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 can also be mentioned.

  These active hydrogen atom-containing compounds having an anionic group can be used alone or in combination of two or more. Of these compounds having an anionic group, active hydrogen atom-containing compounds having a carboxyl group are preferred.

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

(Compound having a polymerizable group)
The polyurethane alkyd resin may be reacted with a compound having a polymerizable group (polymerizable unsaturated compound) from the viewpoint of improving the physical properties of the coating film, thereby imparting characteristics due to the polymerizable unsaturated compound and the polymer. When a compound having an active hydrogen atom is used as the polymerizable unsaturated compound, a (meth) acryl component having a polymerizable group can be introduced into the polyurethane alkyd resin.

Examples of the polymerizable unsaturated compound having an active hydrogen atom include a carboxyl group-containing compound [(meth) acrylic acid, maleic acid, itaconic acid, etc.], a hydroxyl group-containing compound [2-hydroxyethyl (meth) acrylate, 2- Alkanediol mono ((meth) acrylate) such as hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate; (poly) oxy C ₂ such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate _-4 alkylene glycol mono (meth) acrylate; trimethylolpropane mono (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerol mono (meth) acrylate, glycerol di (meth) acrylate Polyols (meth) acrylates such as pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate N-methylol (meth) acrylamide, etc.], imino group-containing compounds [N-methylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, etc.], hydroxyl produced from the reaction of an epoxy compound and a carboxylic acid Group-containing compound [adduct of diglycidyl ether type epoxy resin and (meth) acrylic acid, saturated or unsaturated carbon selected from glycidyl (meth) acrylate, monocarboxylic acid and dicarboxylic acid] Adducts of phosphate, etc.] and the like. The unsaturated carboxylic acid also includes an unsaturated fatty acid.

  Among these polymerizable unsaturated compounds, compounds having 1 to 3 (for example, 1 or 2) hydroxyl groups in the molecule, such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) Acrylate, trimethylolpropane mono (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerol mono (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, Pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferred. In particular, polymerizable unsaturated compounds having one hydroxyl group in the molecule (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerol di ( (Meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc.), polymerizable unsaturated compounds having two hydroxyl groups in the molecule (for example, trimethylolpropane mono (meth) acrylate), Glycerol mono (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol tetra (meth) acrylate, etc.) are preferred. By using such a compound, the polyurethane alkyd resin has a (meth) acrylic component having a polymerizable group in the molecule, and the physical properties of the coating film can be improved.

  The ratio of the compound having a polymerizable group is, for example, about 0 to 50 parts by weight with respect to 100 parts by weight of the alkyd resin.

(Low molecular weight polyamine)
A compound having an amino group, for example, a low molecular weight polyamine unit may be introduced into the polyurethane alkyd resin. The low molecular weight polyamine is not particularly limited. For example, hydrazine, ethylenediamine, propylenediamine, hexamethylenediamine, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopentane, 1,6-diamino Low molecular weight diamines such as hexane, diaminotoluene, bis- (4-aminophenyl) methane, bis- (4-amino-3-chlorophenyl) methane, and diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, And low molecular weight polyamines having 3 or more amino groups such as 2,2′-diaminodiethylamine. These low molecular weight polyamines can be used alone or in combination of two or more. The molecular weight of these low molecular weight polyamines is a number average molecular weight of 32 to 500, preferably about 62 to 200.

[Preparation of polyurethane alkyd resin]
In the preparation of polyurethane alkyd resin (polyurethane prepolymer having alkyd component), reaction component having polyisocyanate and active hydrogen atom (alkyd resin, and if necessary, other polyol, polymerizable unsaturated compound containing active hydrogen atom) , Active hydrogen atom-containing compound having an anionic group, low molecular weight polyamine, hereinafter, these components may be simply referred to as reaction components having an active hydrogen atom), the ratio of active hydrogen atoms (hydroxyl group and amino group) The equivalent ratio of isocyanate groups to (isocyanate groups / active hydrogen atoms) is 0.4 to 10, preferably 0.6 to 5, and more preferably 0.8 to 5 (for example, 1 to 3). The particularly preferred equivalent ratio (isocyanate group / active hydrogen atom) exceeds 1 and is 3 or less (for example, 1.01 to 2.7, preferably 1.1 to 2.5, more preferably 1.2 to 2.3). Degree). By setting it as such a range, a polyurethane prepolymer can be chain-extended after water dispersion using a free isocyanate group, and the molecular weight as a polyurethane alkyd resin component after water dispersion depends on its intended use. Can be controlled arbitrarily. 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 method for preparing the polyurethane alkyd resin is not particularly limited, and for example, it may be reacted by a conventional method (such as a bulk reaction method or a solution reaction method). In the bulk reaction method, for example, in the absence of a solvent, in a nitrogen stream, the polyisocyanate and the reaction component having an active hydrogen atom are reacted at a reaction temperature of 40 to 85 ° C. for 1 to 24 hours, preferably 1 to 8 hours. What is necessary is just to make it react. In many cases, the reaction is usually carried out by adding the reaction component having an active hydrogen atom while stirring the polyisocyanate.

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

[solvent]
The organic solvent is not particularly limited, and is an inert solvent with respect to an isocyanate group, 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, etc.), 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, 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- Rimechiru 1,3-pentanediol diisobutyrate, and triethylene glycol bis 2-ethylhexanoate benzoate), nitrogen-containing solvent (N- methylpyrrolidone, N- ethylpyrrolidone, such as N- methyl caprolactam) and the like. These solvents can be used alone or as a mixed solvent of two or more. Preferred organic solvents are low-boiling organic solvents that can be easily removed, such as ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (dioxane, tetrahydrofuran, etc.), aromatic Group hydrocarbons (toluene and the like). As the organic solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate and the like are often used.

  As the solvent, a polymerizable unsaturated compound having no active hydrogen atom (inert unsaturated compound) may be used. The inert unsaturated compound is particularly effective when a (meth) acrylic component having a polymerizable group is introduced into the 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, vinyl toluene, divinyl Aromatic vinyl and aromatic vinylidene such as benzene and α-methylstyrene; vinyl cyanide and vinylidene cyanide such as (meth) acrylonitrile; conjugated dienes such as butadiene, isoprene and chloroprene; methyl (meth) acrylate and ethyl (meth) C such as acrylate, propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, lauroyl (meth) acrylate, stearyl (meth) acrylate, etc. _1-20 alkyl - Meth) acrylate; cycloalkyl (meth) acrylate such as cyclohexyl (meth) acrylate; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) Acrylates, alkanediol di (meth) acrylates such as nonanediol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) Alkane polyols such as acrylate, dipentaerythritol hexa (meth) acrylate, poly (meth) acrylate; allyl (meth) acrylate, diallyl male And unsaturated carboxylic acid allyl esters such as acrylate, diallyl fumarate and diallyl itaconate; glycidyl (meth) acrylate; urethane di (meth) acrylate; polybutadiene di (meth) acrylate and the like. These compounds can be used alone or in combination of two or more. Preferred compounds include aromatic vinyl (styrene, divinylbenzene, etc.), acrylonitrile, C _1-10 alkyl (meth) acrylate (methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), ethylene glycol di (meth) Examples include acrylate, butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and allyl (meth) acrylate. When forming a hard film, styrene, divinylbenzene, methyl methacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, trimethylolpropane triacrylate, allyl methacrylate, and the like are often used as the inactive compound.

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

[Neutralizer]
Furthermore, in the preparation of the polyurethane alkyd prepolymer having an anionic group, amines (for example, trimethylamine, triethylamine, tri-n-propylamine, at a suitable stage (before the reaction, after the reaction or an aqueous dispersion process described later), Tributylamine, diisopropylethylamine, triphenylamine, 2-dimethylaminoethanol, triethanolamine, dimethylpropanolamine, N-methylpiperidine, etc.), inorganic bases (for example, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide) A neutralizing agent such as ammonia may be added to neutralize the anionic group to form a salt. The addition amount of such a neutralizing agent is, for example, 0.6 to 1.2 equivalents, preferably 0.7 to 1.1 equivalents, more preferably 0.8 to 1 to 1 equivalent of anionic group. It is about equivalent.

[Chain extender]
In order to obtain the polyurethane alkyd resin emulsion (A), the polyurethane alkyd prepolymer can be dispersed in water together with a solvent (an inert unsaturated compound and / or an organic solvent) as necessary to obtain an aqueous dispersion. . In addition, the polyurethane alkyd prepolymer having an anionic group may be prepared as an aqueous dispersion using the neutralizing agent. Further, when the polyurethane alkyd prepolymer contains an isocyanate group, it may be reacted with a chain extender (polyamine and / or water) in water. By this reaction, it is possible to form a polyurethane alkyd resin in which a polyurethane alkyd prepolymer having an isocyanate group at the terminal is chain-extended with a chain extender and to obtain a polyurethane alkyd resin emulsion (A) in which the polyurethane alkyd resin is dispersed in water. Can do.

The polyamine as the chain extender is not particularly limited as long as it is a compound having two or more amino groups. For example, alkylenediamine (ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6 -Hexamethylenediamine), alicyclic diamine (1,4-cyclohexanediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (common name: isophoronediamine), 4,4'-dicyclohexylmethanediamine, 1 , 3-bis (aminomethyl) cyclohexane, norbornanediamine), aromatic diamine (such as xylylenediamine), heterocyclic diamine (such as piperazine, 2,5-dimethylpiperazine), hydrazine, dicarboxylic acid dihydrazide (such as adipic acid dihydrazide) ), Polyalkylene polyami Polyamines such as diethylenetriamine and triethylenetetramine; for example, hydroxy C _2-10 alkyl hydrazine (hydroxyethyl hydrazine, etc.), hydroxy C _2-4 alkyl poly C _2-4 alkylene polyamine (hydroxyethyl diethylene triamine, etc.), Amino alcohols such as N- (amino C _2-10 alkyl) hydroxy C _2-10 alkylamine (N- (2-aminoethyl) ethanolamine etc.), amino C _2-10 alkanediol (3-aminopropanediol etc.) Kind. These polyamines can be used alone or as a mixture of two or more. Among these polyamines, when a polyamine having a hydroxyl group (the aforementioned amino alcohol) is used, an active hydrogen atom can be introduced into the polyurethane alkyd resin. In addition, these polyamines may be added in a partially or completely masked form such as ketimine, ketazine or amine salt.

The reaction method of the polyurethane prepolymer having an alkyd resin component, a terminal isocyanate group and a polyamine in water is not particularly limited. A known dispersion method, for example, the polyurethane alkyd prepolymer is dispersed in a disperser (a homodisper or a homomixer). with stirring using a) a method of dispersing in water with the addition of water, with the addition of pre Kipo Li urethane alkyd prepolymer in water, and a method of dispersion can be employed. A polyamine is added to the produced dispersion, and a polyurethane prepolymer having an alkyd resin component and a terminal isocyanate group may be subjected to a chain extension reaction with the polyamine.

  The amount of water used to disperse the polyurethane alkyd prepolymer is not particularly limited as long as an aqueous dispersion of the polyurethane alkyd prepolymer can be prepared. For example, 20 to 1000 weights with respect to 100 parts by weight of the polyurethane alkyd prepolymer. It may be about a part.

  Moreover, the usage-amount of a polyamine is 0.2-1.5 as an equivalent ratio (amino group / isocyanate group) of the amino group of polyamine with respect to the isocyanate group of a polyurethane alkyd prepolymer, for example, Preferably it is 0.5-1. 3, more preferably about 0.7 to 1.1. The polyamine is usually added dropwise while stirring an aqueous dispersion of a polyurethane alkyd prepolymer. The polyamine is preferably added dropwise at a temperature of 30 ° C. or lower. After completion of the addition, for example, the reaction may be completed at room temperature with further stirring. By such a chain extension reaction, an aqueous dispersion of a polyurethane alkyd resin in which the polyurethane alkyd prepolymer is chain-extended with polyamine and / or water and has active hydrogen atoms can be obtained.

  In addition, when the polyurethane alkyd prepolymer does not contain an isocyanate group, an aqueous dispersion in which the active hydrogen atom-containing polyurethane alkyd resin is dispersed in water by dispersing in water without performing chain extension (polyurethane alkyd emulsion). Can be obtained.

  Useful concentrations of anionic groups for obtaining stable aqueous dispersions are polyurethane alkyd resins (polyurethane alkyds containing terminal isocyanate groups, neutralized polyurethane alkyd prepolymers, or polyurethane alkyds containing terminal hydroxyl groups). In the resin obtained by neutralizing the prepolymer), usually 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. It is.

  Furthermore, when the polyurethane alkyd resin has a (meth) acrylic component, a polymerizable unsaturated compound is added to the emulsion if necessary, and the polymerizable unsaturated compound and the polymerizable property in the polyurethane alkyd resin emulsion (A) are added. It is also possible to obtain a polyurethane alkyd acrylic resin emulsion in which a polyurethane alkyd resin component and an acrylic component are chemically radically copolymerized by radical copolymerization with an unsaturated bond.

Examples of the polymerizable unsaturated compound include a polymerizable unsaturated compound having an active hydrogen atom as exemplified above, a polymerizable unsaturated compound having no active hydrogen atom as exemplified above (an inert unsaturated compound), and diacetone. Examples include acrylamide and acrolein. Among these polymerizable unsaturated compounds, compounds having no active hydrogen atom include aromatic vinyl (styrene, divinylbenzene, etc.), vinyl cyanide (acrylonitrile, etc.), C _1-10 alkyl (meth) acrylate ( Methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), polyfunctional (meth) acrylate (ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol) Tetra (meth) acrylate), allyl (meth) acrylate, glycidyl (meth) acrylate, hydroxyl group-containing (meth) acrylate (2-hydroxyethyl) as a compound having an active hydrogen atom Meth) hydroxyalkyl C _2-6 alkyl (meth) acrylates such as acrylate), a carboxyl group-containing compound ((meth) acrylic acid), diacetone acrylamide, etc. N- methylol (meth) acrylamide is preferable. When forming a hard film, styrene, divinylbenzene, methyl methacrylate, ethylene glycol dimethacrylate, butylene glycol diacrylate, trimethylolpropane tri (meth) acrylate, allyl methacrylate, glycidyl methacrylate, diacetone acrylamide, 2-hydroxyethyl (meth) ) Acrylate is often used.

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

  The radical polymerization initiator is not particularly limited. For example, benzoyl peroxide, o-methoxybenzoyl peroxide, o-chlorobenzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene. Organic peroxides such as hydroperoxide; 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis (2-amidinopropane) di Azo such as hydrochloride, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2′-azobis [2- (2-imidazolin-2-yl) propane] Compounds: hydrogen peroxide, sodium persulfate, potassium persulfate Arm, and the like inorganic peroxides such as ammonium persulfate. The organic or inorganic peroxide may be combined with a reducing agent to form a redox polymerization initiator. Examples of the reducing agent include L-ascorbic acid, L-sorbic acid, sodium metabisulfite, ferrous sulfate, Rongalite and the like. These radical polymerization initiators can be used alone or in combination of two or more. Among these radical polymerization initiators, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, Sulfates (sodium persulfate, potassium persulfate, ammonium persulfate, etc.) are preferred. In addition, cumene hydroperoxide, 2,2'-azobisisobutyronitrile, sodium persulfate, potassium persulfate, and ammonium persulfate are often used as the polymerization initiator.

  In addition, in order to adjust the molecular weight of a polymer, you may superpose | polymerize in presence of a molecular weight regulator. Examples of the molecular weight regulator include mercaptans (n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, etc.), thioglycolic acids (thioglycolic acid, 2-ethylhexyl thioglycolate), thioalcohols (2 -Mercaptoethanol etc.) etc. can be illustrated. These molecular weight regulators can also be used alone or in combination of two or more.

When 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 is particularly limited to the component derived therefrom. However, for example, active hydrogen atoms such as the following (1) to (4) can be exemplified.
(1) Carboxyl group or hydroxyl group derived from polyurethane alkyd resin (2) Hydroxyl group derived from polyamine used for chain elongation of polyurethane alkyd resin (3) Hydroxyl derived from (meth) acrylic component used for copolymerization or modification Group or carboxyl group (4) hydroxyl group or carboxyl group derived from other copolymerizable component used with (meth) acrylic component.

  The urethane alkyd acrylic resin emulsion having active hydrogen atoms can be produced by introducing active hydrogen atoms into the resin using the components (1) to (4) having active hydrogen atoms. Moreover, the component which has the active hydrogen atom of said (1)-(4) may be used independently, and may be used in combination of 2 or more types.

Further, the resin component of the polyurethane alkyd acrylic resin emulsion may be composed of an anionic copolymer in order to enhance dispersion stability. The anionic group of the anionic copolymer may have at least one of the urethane alkyd component and the (meth) acrylic component. For example, a copolymer of a urethane alkyd component having an anionic group introduced by a compound having an anionic group as exemplified above and a (meth) acrylic component having no anionic group, a urethane alkyd component having an anionic group introduced An anionic group can be introduced into the resin component of the polyurethane alkyd acrylic resin emulsion by copolymerization of (meth) acrylic component (such as (meth) acrylic acid) having an anionic group. In a preferred embodiment, an anionic group is introduced into the urethane alkyd component using a compound having an active hydrogen atom reactive with an isocyanate group and an anionic group.

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

  Furthermore, in the polyurethane alkyd resin emulsion (A), if necessary, a surfactant may be blended within a range not impairing water resistance in order to improve the stability of the polyurethane alkyd resin emulsion.

  The surfactant is not particularly limited, and examples thereof include anionic surfactants (for example, fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl sulfates). Ester salts), nonionic surfactants (for example, polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ether, polyoxyethylene derivatives, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin) Fatty acid esters, polyoxyethylene alkylamines, alkylalkanolamides, etc.), cationic and zwitterionic surfactants (eg, alkylamine salts, quaternary ammonia) Um salt, alkylbetaine, amine oxide, etc.), water-soluble polymer or protective colloid (eg gelatin, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, polyethylene glycol, polyoxyethylene-polyoxypropylene block copolymer, polyacrylamide) , Polyacrylic acid, polyacrylate, sodium alginate, partially saponified polyvinyl alcohol, etc.). Furthermore, in the present invention, in addition to these polymer dispersants, for example, inorganic substances such as tricalcium phosphate, titanium oxide, calcium carbonate, and silicon dioxide can be used as the surfactant. These surfactants may be used alone or in combination of two or more. In addition, depending on the surfactant having an ionic functional group in the addition of the surfactant, the stability of the aqueous dispersion may decrease due to the interaction with the anionic group of the polyurethane alkyd resin. Therefore, nonionic surfactants are often used.

  The surfactant may be added to, for example, the polyurethane alkyd prepolymer before being dispersed in water, may be added to the aqueous dispersion of the polyurethane alkyd prepolymer, or the polyurethane alkyd resin emulsion chain-extended with polyamine, or It may be added to a polyurethane alkyd resin emulsion dispersed in water without chain extension, or may be added to a polyurethane alkyd acrylic resin emulsion produced by radical polymerization. Further, the surfactant may be added all at once or divided into a plurality of times.

[Curing agent (B)]
The polyurethane alkyd resin emulsion (A) having an active hydrogen atom can be used as an aqueous resin composition (adhesive, etc.) or a coating composition (paint, printing ink, etc.). In order to improve the solvent resistance, it is preferable to use a combination of the polyurethane alkyd resin emulsion (A) having an active hydrogen atom as the main agent and the curing agent (B). As the curing agent (B), various curing agents having reactivity with the active hydrogen atom, for example, an isocyanate curing agent (polyisocyanate compound), an epoxy curing agent (polyepoxy compound), and an amino resin curing. Agents (melamine compounds, guanamine compounds, etc.), dihydrazide curing agents, carbodiimide curing agents, oxazoline curing agents, aziridine curing agents and the like. These hardening | curing agents can be used individually or in combination of 2 or more types. The curing agent may be a hydrophobic curing agent, but a preferable curing agent is a curing agent dispersible in the polyurethane alkyd resin emulsion (A).

  As such a curing agent, polyisocyanate (isocyanate-based curing agent) is preferable. The polyisocyanate used for the curing agent may be any polyisocyanate as long as it can be dispersed in the polyurethane alkyd resin emulsion (A), and the polyisocyanate itself dispersible in the polyurethane alkyd resin emulsion (A). Even if it is a polyisocyanate that can be dispersed in the polyurethane alkyd resin emulsion (A) by adding a surfactant or a dispersing agent if necessary and stirring (including strong stirring using a homomixer) and mixing. Good. Of these polyisocyanates, polyisocyanate derivatives are preferred, polyisocyanate-modified products are more preferred, and dispersible polyisocyanates are particularly preferred.

(Dispersible polyisocyanate)
The dispersible polyisocyanate can be obtained, for example, by reacting a polyisocyanate with a surface active or dispersible component (component having surface active ability or dispersibility) having an active hydrogen atom reactive with an isocyanate group. .

Examples of the polyisocyanate, usually aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates, aromatic polyisocyanates, these polyisocyanates based and the derivatives and modifications thereof, the derivatives and modifications thereof Examples thereof include polyisocyanates. These polyisocyanates can be used alone or in combination of two or more.

  Examples of the aliphatic polyisocyanate include the aliphatic polyisocyanates, and preferred polyisocyanates include tetramethylene diisocyanate, pentamethylene diisocyanate, and hexamethylene diisocyanate.

  Examples of the alicyclic polyisocyanate include the alicyclic polyisocyanate, and preferred polyisocyanates include isophorone diisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, norbornane diisocyanate, and the like. .

  Examples of the araliphatic polyisocyanate include the araliphatic polyisocyanate, and the preferred polyisocyanate is 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene.

  Examples of the aromatic polyisocyanate include the aromatic polyisocyanates. Preferred polyisocyanates include 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate and the like.

  These polyisocyanates can be used alone or in combination of two or more.

Furthermore, as polyisocyanate derivatives, for example, dimer, trimer (isocyanurate group-containing polyisocyanate), biuret group-containing polyisocyanate, allophanate group-containing polyisocyanate, oxadiazinetrione ring-containing polyisocyanate, carbodiimide-modified polyisocyanate, etc. are also used. it can. In the preparation of the polyisocyanate derivative, if necessary, a polyol or polyamine having reactivity with the polyisocyanate may be used. Examples of the polyol and polyamine include glycols and triols, the polyester polyol, and the polyether polyol. , Polyether ester polyols, polyester amide polyols, acrylic polyols, polycarbonate polyols, polyhydroxyalkanes, polybutadiene diols, polyurethane polyols, low molecular weight polyols, low molecular weight polyamines or mixtures thereof. Such a polyisocyanate derivative may be an adduct type polyisocyanate or an isocyanate prepolymer obtained by adding the polyisocyanate to a polyol. These polyisocyanate derivatives can be used alone or in combination of two or more thereof, and may be used in combination with the polyisocyanate (such as aliphatic or alicyclic polyisocyanate). Among these polyisocyanate derivatives, derivatives based on at least one selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, and tolylene diisocyanate, particularly isocyanurate group-containing polyisocyanate and / or allophanate group-containing polyisocyanate, etc. 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 whole polyisocyanate.

(Surfactant or dispersible component)
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 surface active or dispersible component may be an anionic surfactant, but is usually composed of at least one selected from the group consisting of a nonionic surfactant and a compound having at least an ethylene oxide chain. The nonionic surfactant has, for example, a reactive group containing an active hydrogen atom such as a hydroxyl group or a mercapto group, and a surfactant having 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, a polyoxyalkylene surfactant having at least an oxyethylene unit, particularly a polyoxyethylene surfactant having a hydroxyl group, is particularly preferably used.

In the polyoxyalkylene surfactant, the oxyalkylene unit includes, for example, oxyC _2-5 alkylene units such as oxyethylene, oxypropylene, and oxybutylene, and these oxyalkylene units include at least oxyethylene units. It may be a random or block copolymer unit of an oxyethylene unit and an oxy C _3-5 alkylene unit. The content of oxyethylene units in the polyoxyalkylene units is usually about 70 to 100 mol%, preferably about 80 to 100 mol%.

Any nonionic surfactant may be used as long as it has an active hydrogen atom. For example, polyoxyethylene alkyl ether (for example, polyoxyethylene monooctyl ether, polyoxyethylene monolauryl ether, polyoxyethylene monoester) Decyl ether, polyoxyethylene monocetyl ether, polyoxyethylene monostearyl ether, polyoxyethylene _C8-24 alkyl ether such as polyoxyethylene _monooleyl ether), polyoxyethylene monoalkylaryl ether (eg, polyoxyethylene mono octyl phenyl ether, polyoxyethylene monononylphenyl ether, polyoxyethylene C _8-12 alkyl -C _6-12 arylene, such as polyoxyethylene mono decyl ether Ethers), polyoxyethylene polyoxyalkylene alkyl ethers (eg, polyoxyethylene polyoxypropylene monooctyl ether, polyoxyethylene polyoxypropylene monolauryl ether, polyoxyethylene polyoxypropylene monodecyl ether, polyoxyethylene polyoxy Polyoxyethylene polyoxypropylene C _8-24 alkyl ethers such as propylene monocetyl ether, polyoxyethylene polyoxypropylene monostearyl ether, polyoxyethylene polyoxypropylene _monooleyl ether, and these polyoxyethylene polyoxypropylene C _{8 -24} polyoxyethylene polyoxybutylene C _8-24 alkyl ether corresponding to the alkyl ether), polyoxyethylene Sorbitan higher fatty acid esters (for example, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan distearate, polyoxyethylene sorbitan tristearate, etc. Ethylene sorbitan mono-, di- or tri-C _10-24 fatty acid esters), polyoxyethylene mono-higher fatty acid esters (for example, polyoxyethylene mono C _10- such as polyoxyethylene monolaurate, polyoxyethylene monostearate) ₂₄ fatty acid esters). These nonionic surfactants can be used alone or in combination of two or more. Preferred nonionic surfactants include polyoxyethylene C _8-24 alkyl ether, polyoxyethylene C _8-12 alkyl phenyl ether, polyoxyethylene polyoxy C _3-6 alkylene C _8-24 ether. In order to enable stable dispersion in the polyurethane alkyd resin emulsion (A), the average content of oxyethylene units in one molecule of the nonionic surfactant is usually about 10 to 35. The number is preferably about 12 to 30.

As the compound having an ethylene oxide chain (especially a polyethylene oxide chain), any compound having an active hydrogen atom may be used. For example, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, etc. Examples include alkoxy polyalkylene ether glycols in which alkylene oxide containing at least ethylene oxide is added by ring-opening polymerization using monoalkanol (lower alcohol such as C _1-10 alkyl alcohol) as an initiator. In order to make the polyurethane alkyd resin emulsion (A) dispersible stably, the average molecular weight of the compound having an active hydrogen atom and an ethylene oxide chain is usually about 100 to 4,000, preferably 200 to 2. About 1,000.

  Further, compounds having an ethylene oxide chain (especially a polyethylene oxide chain) include compounds obtained by reacting an alkoxy polyalkylene ether glycol and a dialkanol amine with polyisocyanate, dialkanol amine and alkoxy polyoxyethylene glycol monoallyl ether or alkoxy. Also included are Michael adducts with polyoxyethylene (meth) acrylate.

Examples of the alkoxy polyalkylene ether glycol include C _1-4 alkoxy poly C _2-4 alkylene ether glycol such as methoxy polyethylene ether glycol, ethoxy polyethylene ether glycol, methoxy polybutylene ether glycol, and ethoxy polybutylene ether glycol.

Examples of dialkanolamines include dihydroxy C _2-6 alkylamines such as diethanolamine, dipropanolamine, diisopropanolamine, and diethanolaniline.

  The reaction of polyisocyanate, alkoxy polyalkylene ether glycol and dialkanolamine is carried out by reacting polyisocyanate and alkoxy polyalkylene ether glycol in an isocyanate group / hydroxyl group equivalent ratio of 3 to 30, preferably about 10 to 25. Thereafter, unreacted polyisocyanate is removed, and then dialkanolamine can be carried out at an isocyanate group / amino group equivalent ratio of 0.5 to 2, preferably about 0.8 to 1.2. The reaction between the polyisocyanate and the alkoxy polyalkylene ether glycol can be carried out at about 40 to 100 ° C. for about 2 to 24 hours. The reaction is desirably performed in a nitrogen atmosphere, and an inert organic solvent described later may be used. For removing the unreacted polyisocyanate, a known method such as a distillation method or an extraction method is used. Examples of the distillation method include a continuous distillation method, a batch distillation method, and a thin film distillation method. A thin film distillation method is preferably used. As the extraction method, liquid-liquid extraction such as continuous extraction and batch extraction is used, and as the extraction solvent, a relatively low-polar organic solvent such as hexane or acetate is used. The reaction with the dialkanolamine is preferably performed at room temperature to about 120 ° C. in a nitrogen atmosphere. This reaction may also be performed using an inert organic solvent as described above.

  The ratio between the polyisocyanate for the curing agent (B) and the 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 The active hydrogen atom of the nonionic compound is 0.01 to 0.2 equivalent, preferably 0.012 to 0.15 equivalent, more preferably 1 equivalent of isocyanate group (including polyisocyanate derivative) with which the isocyanate can react. It can select from the range of about 0.015-0.1 equivalent. When the ratio of the nonionic compound is small, the dispersibility in the polyurethane alkyd resin emulsion (A) may be lowered. When the proportion is too large, the hydrophilicity becomes too high and physical properties such as water resistance may be lowered.

Furthermore, in order to increase the water resistance of the coating film, it is advantageous to react the polyisocyanate (preferably a polyisocyanate derivative) with a coupling agent. This coupling agent has an active hydrogen atom reactive to the isocyanate group of the polyisocyanate, for example, a functional group such as a mercapto group, an amino group, or a carboxyl group. The coupling agent has a crosslinkable or polymerizable group (such as a hydrolytic condensable group), and examples of the hydrolytic condensable group include an alkoxy group (methoxy, ethoxy, propoxy, butoxy, t-butoxy group, and the like). C _1-4 alkoxy group). The coupling agent may have about 1 to 3 of such hydrolytic condensable groups in one molecule. Such a coupling agent may be a titanium coupling agent or the like, but is typically a silane coupling agent.

Examples of the silane coupling agent include mercapto group-containing silane coupling agents (mercapto C _2-4 alkyltri C _1-4 alkoxysilane such as β-mercaptoethyltriethoxysilane and γ-mercaptopropyltrimethoxysilane), Amino group-containing silane coupling agents (amino C _2-4 alkyltri C ₁ such as β-aminoethyltrimethoxysilane, β-aminoethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane) _-4 alkoxysilane, etc.), carboxyl group-containing silane coupling agents (carboxy C _2-4 alkyltri C ₁ -such as β-carboxyethyltrimethoxysilane, γ-carboxypropyltrimethoxysilane, γ-carboxypropyltriethoxysilane) ₄ alkoxy silane ), And the like. These silane coupling agents can be used alone or in combination of two or more. A preferred coupling agent is a mercapto group-containing silane coupling agent such as γ-mercaptopropyltrimethoxysilane.

  The ratio of the polyisocyanate to the coupling agent is 0.01 to 0.3 equivalents, preferably 0.02 to 0.25 equivalents, of the active hydrogen atom of the coupling agent with respect to 1 equivalent of the isocyanate group of the polyisocyanate. More preferably, it can select from the range of about 0.05-0.2 equivalent.

  The polyisocyanate as the curing agent (B) includes, for example, the polyisocyanate (preferably a polyisocyanate derivative), a nonionic surfactant having an active hydrogen atom and / or a compound having a polyoxyethylene chain, and a cup if necessary. It can be obtained by reacting with a ring agent while stirring. The reaction temperature can be appropriately selected and is usually about 50 to 90 ° C. The reaction time is not particularly limited, and is, for example, about 1 to 24 hours, preferably about 1 to 8 hours. The reaction may be performed in the presence of a catalyst (such as an amine catalyst or a tin catalyst). In addition, the reaction may be performed in the presence of an inert organic solvent (non-reactive organic solvent), but in order to improve handling while preventing contamination of the two-part curable aqueous resin composition with the organic solvent. Is preferably reacted in the absence of an organic solvent to produce a liquid polyisocyanate having fluidity at room temperature. Hereinafter, the case where polyisocyanate is used as the curing agent is referred to as a curing agent (polyisocyanate).

  Examples of the inert organic solvent include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, 4-methyl-2-pentanone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, isobutyl acetate, 1-methoxy). Propyl-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 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, 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-pentanedio Such as rudiisobutyrate, triethylene glycol bis-2-ethylhexaate), nitrogen-containing solvents (N-methylpyrrolidone, N-ethylpyrrolidone, N-methylcaprolactam, etc.) These solvents may be used alone or in combination It can be used as the above mixed solvent.

  Moreover, the polyisocyanate derivative having the surface active ability or the dispersibility as the curing agent (polyisocyanate) (B) can be prepared by using a known synthesis method, and the reaction order of each component depends on the kind of the reaction component. You can choose according to your needs. For example, a curing agent (polyisocyanate) (by reacting a polyisocyanate derivative (such as a trimer of low molecular weight polyisocyanate) with a nonionic surfactant and / or a compound having a polyoxyethylene chain and, if necessary, a coupling agent. B), in particular dispersible polyisocyanates can be obtained. Moreover, when using polyisocyanate and a plurality of reaction components having an active hydrogen atom reactive with an isocyanate group, a plurality of polyisocyanates may be used, and each reaction component may be reacted in an appropriate order. Good. For example, a compound containing a terminal isocyanate group and a polyethylene oxide chain is produced by a reaction between a polyisocyanate (low molecular weight polyisocyanate or a polyisocyanate derivative) and a compound having a polyethylene oxide chain (such as alkoxy polyethylene alkylene ether glycol), After removing the remaining polyisocyanate if necessary, a compound containing two hydroxyl groups and a polyethylene oxide chain is produced by a reaction between the produced compound and dialkanolamine, and this compound and polyisocyanate (preferably trimer, etc.) May be reacted with a polyisocyanate derivative). In this way, the reactive component (nonionic surfactant having an active hydrogen atom reactive with an isocyanate group and / or compound having a polyoxyethylene chain and, if necessary, a coupling agent) is, for example, a polyisocyanate in advance. Or may be reacted in the middle of the synthesis of the polyisocyanate derivative. Further, the reaction product may be reacted with a polyisocyanate derivative. Furthermore, after reacting a polyisocyanate and a reactive component, final trimerization, allophanation, biuretization, and the like may be performed. For example, a low molecular weight polyisocyanate, a diol (polyethylene glycol or the like) having a polyoxyethylene chain and a trione form may be reacted to perform trimerization, allophanation reaction, or the like. The target curing agent (polyisocyanate) (B) can be obtained by such various reactions.

  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 about 3 to 50% by weight, preferably about 5 to 30% by weight. It is. When the average functional group number of the curing agent (polyisocyanate) (B) is less than 2, the water resistance may be inferior, and when it exceeds 5, the polyurethane alkyd having an active hydrogen atom of the curing agent (polyisocyanate) (B) Dispersibility in the resin emulsion (A) may be reduced. Further, if the isocyanate group content is less than 3% by weight, the water resistance may be inferior due to insufficient crosslinking density, and if it exceeds 50% by weight, it is dispersed in the polyurethane alkyd resin emulsion (A) having active hydrogen atoms. May decrease.

  In order to obtain a polyisocyanate as a curing agent having a desired isocyanate group content, the reaction may be terminated when the predetermined isocyanate group content is reached in the reaction process. A preferred method has a polyisocyanate (preferably including a polyisocyanate derivative) and an active hydrogen atom in such a ratio that the isocyanate group content in the resulting curing agent (polyisocyanate) (B) falls within the above range. A nonionic surfactant 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 (polyisocyanates) (B) may be used alone or in combination of two or more. Among these curing agents (polyisocyanates) (B), preferred polyisocyanates include polyisocyanates (preferably polyisocyanate derivatives), nonionic surfactants having active hydrogen atoms reactive with isocyanate groups, and Dispersible polyisocyanate produced by the reaction of the above, polyisocyanate (preferably low molecular weight polyisocyanate or polyisocyanate derivative), and a compound having a polyethylene oxide chain having an active hydrogen atom reactive with an isocyanate group (alkoxy polyethylene alkylene) Ether glycol) and dialkanolamine are reacted in the same manner as above to produce an active hydrogen atom-containing compound (for example, a terminal hydroxyl group compound). Over DOO (preferably polyisocyanate derivatives, such as trimers) such as dispersible polyisocyanate produced by reaction of the like. A more preferable curing agent (polyisocyanate) (B) is polyoxyethylene-modified polyisocyanate which is a dispersible polyisocyanate.

  The curing agent (polyisocyanate) (B) can contain a coupling agent (in particular, a silane coupling agent) that is non-reactive with respect to the isocyanate group. Examples of such silane coupling agents include epoxy group or glycidyl group-containing silane coupling agents (for example, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane), vinyl group-containing silane coupling agents (vinyltriethoxysilane, vinyltrimethoxysilane, β- (meth) allyloxyethyltrimethoxysilane, γ- (meth) allyloxy Propyltrimethoxysilane, etc.).

  Furthermore, when using polyisocyanate etc. as a hardening | curing agent (B), it is also possible to 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, etc.), 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, 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 diisobutyrate, triethylene glycol bis 2-ethylhexaate, etc.), nitrogen-containing solvents (N-methylpyrrolidone, N-ethylpyrrolidone, N-methylcaprolactam, etc.). It can be used alone or as a mixed solvent of two or more.

  In the two-component curable aqueous resin composition of the present invention, the amount of the curing agent (B) used for the polyurethane alkyd resin emulsion (A) is not particularly limited as long as the effect of the present invention is achieved. And 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 parts by weight) with respect to 100 parts by weight of the polyurethane alkyd resin emulsion (A). ˜35 parts by weight, preferably 3 to 30 parts by weight).

  The amount of the curing agent (B) used for the polyurethane alkyd resin emulsion (A) is, for example, in terms of solid content, for example, a reactive group in the curing agent (B) (for example, an isocyanate group in polyisocyanate) and a polyurethane alkyd resin. The equivalent ratio of active hydrogen atoms in the polyurethane alkyd resin of the emulsion (A) (for example, isocyanate group / active hydrogen atom) is 0.3 to 4, preferably 0.4 to 3, more preferably 0.5 to 2. Degree. If the equivalent ratio of isocyanate groups and active hydrogen atoms exceeds this range, excess isocyanate groups may react with water to generate carbon dioxide, which may significantly impair the appearance of the coating film. However, if it is less than this range, water resistance may be remarkably inferior due to insufficient crosslinking density and residual active hydrogen atoms in the coating film. The active hydrogen atom in the polyurethane alkyd resin in the polyurethane alkyd resin emulsion (A) is the hydroxyl group in the polyamine used at the time of chain extension of the polyurethane alkyd prepolymer having a terminal isocyanate group, or the polyurethane alkyd prepolymer ( Hydroxyl group in the non-isocyanate group), carboxyl group in the active hydrogen atom-containing compound having an anionic property used in the synthesis of the polyurethane alkyd prepolymer, and hydroxyl in the active hydrogen atom-containing unsaturated compound used in the radical polymerization. The total with a group and / or a carboxyl group is shown.

[Metal dryer or desiccant (C)]
The metal dryer (C) may be contained in the aqueous resin composition (such as a two-component curable aqueous resin composition) of the present invention. As the metal dryer (C), a fatty acid metal salt which is a conventional metal dryer (drying agent for paint) can be used. Examples of such fatty acid metal salts include naphthenic acid metal salts (eg, polyvalent metal salts of naphthenic acid such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, manganese naphthenate, and zinc naphthenate), and metal octylates. Salts (such as cobalt octylate, manganese octylate, lead octylate, zirconium octylate, and polyvalent metal salts of octylate such as zinc octylate). These metal dryers can be used alone or in combination of two or more. In general, it is known that a combination of two or more of these fatty acid metal salts produces a high effect. For example, cobalt naphthenate and other naphthenic acid metal salts (for example, lead naphthenate, zirconium naphthenate, naphthene) Combined use with manganese acid, zinc naphthenate, etc.) is widely used. Furthermore, in these fatty acid metal salts, the metal may form a complex with an amine. In particular, fatty acid metal salts containing different metals and composites of metals and amines can be highly active as lead-free dryers, and are environmentally advantageous. As such a metal dryer, an amine complex metal dryer is commercially available from Dainippon Ink and Chemicals Co., Ltd. under the trade name “Dicnate 1000W” (cobalt / amine complex dryer, cobalt content 3.6% by weight). , Mix Dryer is a product name “ADDITOL VXW6206” (Cobalt / lithium / zirconium composite salt, cobalt content 5% by weight, lithium content 0.2% by weight, zirconium content 7. 5% by weight) and the like.

  The proportion of the metal dryer (C) is, for example, 0.01 parts by weight or more (for example, 0.01 to 30 parts by weight), preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the polyurethane alkyd resin. Preferably it is about 0.1-10 weight part (especially 0.1-5 weight part). Further, the ratio of the metal dryer (C) is 0.001 part by weight or more (for example, 0.001 to 5 parts by weight), preferably 0 with respect to 100 parts by weight of the polyurethane alkyd resin component in terms of the metal component. It may be about 0.01 to 1 part by weight, more preferably about 0.05 to 0.5 part by weight. When the alkyd resin component contains an unsaturated fatty acid component, if the ratio of the metal dryer is in such a range, the oxidation-curing reaction is promoted, and a high-performance coating film can be obtained in a short time.

  In the aqueous resin composition of the present invention, if necessary, other resins (for example, acrylic resin emulsion, styrene resin emulsion, urethane resin emulsion, etc.), curing catalysts and various additives such as plasticizer, Film forming aid, film forming agent, antifreezing agent, antifoaming agent, leveling agent, formalin catcher agent, antifungal agent, rust inhibitor, antibacterial agent, antiseptic, matting agent, flame retardant, thixotropic agent, Tackifiers, thickeners, lubricants, antistatic agents, reaction retarders, antioxidants, UV absorbers, hydrolysis inhibitors, weathering stabilizers, heat stabilizers, fillers, dyes and pigments (dyes, inorganic pigments, organic Pigments, extender pigments, etc.) may be added as appropriate.

  The two-component curable aqueous resin composition of the present invention is useful as an adhesive, a coating agent (paint, printing ink, etc.) and a primer, and various substrates (metal, plastic or polymer material, slate, concrete, mortar) Inorganic materials such as paper, wood, etc.) can be suitably used. In particular, the two-component curable water-based paint of the present invention can be cured at room temperature and heat-cured. For example, it can be used as a woodwork paint or water-based primer in a room-temperature curable system, and as a car paint in a heat-cured system.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the examples and comparative examples, “parts” and “%” indicate parts by weight and% by weight.

[Preparation of Alkyd Resin (PES1)]
In a five-necked flask equipped with a stirrer, a nitrogen inlet tube, a rectifying column, and a thermometer, 3318.3 parts of a high-diene fatty acid (manufactured by KEI Trading Co., Ltd., Heidiene), 821.2 parts of pentaerythritol, and 487 .3 parts is added, 0.2 part of mono-n-butyltin oxide as an esterification catalyst is added while performing nitrogen bubbling, and the mixture is heated to 230 ° C., and condensed water is added while stirring for 8 hours. While removing, the carboxyl group and the hydroxyl group were reacted. After confirming that the reaction solution reached the predetermined hydroxyl group content, the temperature was lowered to 30 ° C. to obtain an alkyd resin (PES1) having a hydroxyl value of 75.3.

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

[Preparation of active hydrogen atom-containing polyurethane alkyd resin emulsion (a1)]
To a five-necked flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, a silica gel drying tube, and a thermometer, 174.2 parts of tolylene diisocyanate (Cosmonate T-80 manufactured by Mitsui Takeda Chemical Co., Ltd.), And 207.1 parts of methyl ethyl ketone were added and stirred under nitrogen atmosphere until completely uniform, 272.9 parts of an alkyd resin (PES1) having a hydroxyl value of 75.3, 38.1 parts of neopentyl glycol and dimethylolbutane. 32.6 parts of acid was added, the temperature was stirred at 70 to 80 ° C. for 2 hours, and it was confirmed that the reaction solution had reached a predetermined isocyanate content. The temperature was lowered while 138.1 parts of methyl ethyl ketone was added, and polyurethane alkyd Reaction mixture containing prepolymer (methyl of terminal isocyanate polyurethane prepolymer containing alkyd component) An ethyl ketone solution) was obtained.

  While stirring 863 parts of the resulting 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 further added. This was added to obtain a milky pink aqueous dispersion. To this dispersion, 192.3 parts of a 10% aqueous solution of N- (2-aminoethyl) ethanolamine was added dropwise at a temperature of 30 ° C. or lower to carry out a chain extension reaction, and methyl ethyl ketone and water were added at 50 ° C. under reduced pressure. By removing and adding 4.4 parts of a lead-free dryer (manufactured by UCB Japan Co., Ltd., ADDITOL VXW6206), solid content 36.8%, viscosity (25 ° C.) 46 mPa · s, pH 7.6, average An active hydrogen atom-containing polyurethane alkyd resin emulsion (a1) having a particle diameter of 84 nm was obtained.

[Preparation of active hydrogen atom-containing polyurethane alkyd resin emulsion (a2)]
To a five-necked flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, a silica gel drying tube, and a thermometer, 174.2 parts of tolylene diisocyanate (Cosmonate T-80 manufactured by Mitsui Takeda Chemical Co., Ltd.), And 208.7 parts of methyl ethyl ketone were added and stirred under a nitrogen atmosphere until it was completely uniform, and 276.9 parts of an alkyd resin (PES2) having a hydroxyl value of 74.2, 38.1 parts of neopentyl glycol and dimethylolbutane. 32.6 parts of acid was added, the temperature was stirred at 70 to 80 ° C. for 2 hours, and it was confirmed that the reaction solution had reached a predetermined isocyanate content. The temperature was lowered while adding 139.1 parts of methyl ethyl ketone, and polyurethane alkyd Reaction mixture containing prepolymer (methyl of terminal isocyanate polyurethane prepolymer containing alkyd component) An ethyl ketone solution) was obtained.

  To the reaction mixture containing the resulting polyurethane alkyd prepolymer, 3.7 parts of a cobalt naphthenate (cobalt content 6 wt%) solution, 5.6 parts of a zirconium naphthenate (zirconium content 6 wt%) solution, and triethylamine 20 Parts were added and made uniform. Subsequently, 898.9 parts of the reaction mixture containing the above-mentioned polyurethane alkyd prepolymer was slowly added little by little to 1377.1 parts of deionized water stirred with a homodisper. An aqueous dispersion was obtained. To this dispersion, 192.3 parts of a 10% aqueous solution of N- (2-aminoethyl) ethanolamine was added dropwise at a temperature of 30 ° C. or lower to carry out a chain extension reaction, and methyl ethyl ketone and water were added at 50 ° C. under reduced pressure. By removal, an active hydrogen atom-containing polyurethane alkyd resin emulsion (a2) having a solid content of 36.7%, a viscosity (25 ° C.) of 37 mPa · s, a pH of 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 formulation shown in Table 2, an active hydrogen atom-containing polyurethane alkyd resin emulsion (a3, a4) was prepared by the same operation as the active hydrogen atom-containing polyurethane alkyd resin emulsion (a2).

[Preparation of active hydrogen atom-containing polyurethane alkyd resin emulsion (a5)]
In a five-necked flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, a silica gel drying tube, and a thermometer, 174.2 parts of tolylene diisocyanate (Mitsui Takeda Chemical Co., Ltd. Cosmonate T-80) and 160.2 parts of methyl ethyl ketone was added and stirred under a nitrogen atmosphere until completely uniform, 251.6 parts of an alkyd resin (PES3) having a hydroxyl value of 85.8, 36.4 parts of neopentyl glycol, and dimethylolbutanoic acid. 33.7 parts were added, the temperature was stirred at 70 to 80 ° C. for 2 hours, it was confirmed that the reaction solution had reached a predetermined isocyanate content, and the temperature was lowered while 106.8 parts of methyl ethyl ketone was added. Reaction mixture containing polymer (methyl ether of terminal isocyanate polyurethane prepolymer containing alkyd component) Tilketone solution) was obtained.

  While stirring 762.9 parts of the resulting liquid mixture containing the polyurethane alkyd prepolymer using a homodisper, 121.6 parts of a 15% aqueous solution of 2-dimethylaminoethanol was added, and 1355.5 deionized water. Part was added to obtain a milky pink aqueous dispersion. To this dispersion, 192.3 parts of a 10% aqueous solution of N- (2-aminoethyl) ethanolamine was dropped at a temperature of 30 ° C. or lower to carry out a chain elongation reaction, and an active hydrogen atom-containing polyurethane alkyd resin emulsion was obtained. Obtained.

  In a flask equipped with a stirrer, a Dimroth cooler, a nitrogen introduction tube, and a thermometer, 2437.6 parts of the obtained active hydrogen atom-containing polyurethane alkyd resin emulsion was stirred and styrene 124.0 which is an unsaturated compound. Part, 7.9 parts of 2,2′-azobisisobutyronitrile as a radical polymerization initiator was added, heated to 80 ° C., reacted for 4 hours, and methyl ethyl ketone and water were removed at 50 ° C. under reduced pressure. By adding 5.3 parts of a lead-free dryer (ADDITOL VXW6206), an active hydrogen atom-containing polyurethane alkyd resin emulsion having a solid content of 37.7%, a viscosity (25 ° C.) of 131 mPa · s, a pH of 8.0, and an average particle size of 74 nm (A5) was obtained.

[Preparation of active hydrogen atom-containing polyurethane alkyd resin emulsion (a6)]
To a five-necked flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, a silica gel drying tube, and a thermometer, 174.2 parts of tolylene diisocyanate (Cosmonate T-80 manufactured by Mitsui Takeda Chemical Co., Ltd.), And 202.9 parts of methyl ethyl ketone were added and stirred under a nitrogen atmosphere until completely uniform, 258.9 parts of an alkyd resin (PES2) having a hydroxyl value of 74.2, 8 parts of glycerol monomethacrylate, 35. 6 parts and 30.4 parts of dimethylol butanoic acid were added, the temperature was stirred at 70-80 ° C. for 2 hours, and it was confirmed that the reaction solution had reached a predetermined isocyanate content, and 135.2 parts of methyl ethyl ketone was added. While cooling to 30 ° C, reaction mixture containing polyurethane alkyd prepolymer (end containing alkyd component) Methyl ethyl ketone solution of isocyanate polyurethane prepolymer) was obtained.

  To 845.2 parts of the reaction mixture containing the obtained polyurethane alkyd prepolymer, 4.5 parts of a cobalt naphthenate (cobalt content 6 wt%) solution and a zirconium naphthenate (zirconium content 6 wt%) solution 6.7 While stirring with a homodisper, add 109.9 parts of a 15% aqueous solution of 2-dimethylaminoethanol, add 1694.7 parts of deionized water, and add a milky pink aqueous dispersion. Obtained. To this dispersion, 192.3 parts of a 10% aqueous solution of N- (2-aminoethyl) ethanolamine was dropped at a temperature of 30 ° C. or lower to carry out a chain elongation reaction, and an active hydrogen atom-containing polyurethane alkyd resin emulsion was obtained. Obtained.

  In a flask equipped with a stirrer, a Dimroth cooler, a nitrogen introducing tube, and a thermometer, 2853.3 parts of the obtained active hydrogen atom-containing polyurethane alkyd resin emulsion were stirred with methyl methacrylate 120. 4 parts, 6.3 parts of ethylene glycol dimethacrylate, and 8 parts of 2,2′-azobisisobutyronitrile as a radical polymerization initiator were added, the temperature was raised to 80 ° C., the reaction was performed for 4 hours, and 50 ° C. under reduced pressure. Then, methyl ethyl ketone and water were removed to obtain an active hydrogen atom-containing polyurethane alkyd resin emulsion (a6) having a solid content of 37.3%, a viscosity (25 ° C.) of 100 mPa · s, a pH of 7.6, and an average particle diameter of 82 nm.

[Preparation of active hydrogen atom-containing polyurethane alkyd resin emulsion (a7 to a9)]
In the formulation shown in Table 3, active hydrogen atom-containing polyurethane alkyd resin emulsions (a7 to a9) were prepared in the same manner as in the active hydrogen atom-containing polyurethane alkyd resin emulsion (a2).

[Preparation of active hydrogen atom-containing polyurethane resin emulsion (a10)]
To a five-necked flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, a silica gel drying tube, and a thermometer, 250.2 parts of 4,4′-diphenylmethane diisocyanate and 303.0 parts of methyl ethyl ketone were added, and nitrogen was added. Under an atmosphere, the temperature was raised to 40 ° C., and the mixture was stirred until 4,4′-diphenylmethane diisocyanate was completely dissolved. Thereafter, the temperature was raised to 50 ° C., 26 parts of 2-hydroxyethyl methacrylate was added, and the mixture was stirred for 30 minutes to react an isocyanate group and a hydroxyl group. After the reaction, 94.0 parts of polypropylene glycol having a molecular weight of 1000 (Accor P-22, manufactured by Mitsui Takeda Chemical Co., Ltd.), 25.2 parts of dipropylene glycol, 20 parts of diethylene glycol, and 39 parts of dimethylolbutanoic acid were sequentially added. The mixture was stirred for 4 hours while adjusting the temperature to 50 to 60 ° C., and it was confirmed that the reaction solution had reached a predetermined isocyanate content, the temperature was lowered to 30 ° C., and the reaction mixture containing the polyurethane prepolymer (terminal isocyanate polyurethane) (Methyl ethyl ketone solution of prepolymer) was obtained.

  While stirring 757.4 parts of the resulting polyurethane prepolymer containing a homopolymer, 156.4 parts of a 15% aqueous solution of 2-dimethylaminoethanol was added, and 983.4 parts of deionized water was further added. Was added to obtain a milky blue aqueous dispersion. To this aqueous dispersion, 138.9 parts of a 10% aqueous solution of N- (2-aminoethyl) ethanolamine was added dropwise at a temperature of 30 ° C. or lower to carry out a chain extension reaction, and methyl ethyl ketone and water at 50 ° C. under reduced pressure. The active hydrogen atom-containing polyurethane resin emulsion (a10) having a solid content of 34.9%, a viscosity (25 ° C.) of 3400 mPa · s, a pH of 8.3, and an average particle diameter of 31 nm was obtained.

[Preparation of active hydrogen atom-containing polyurethane acrylic resin emulsion (a11)]
In a five-necked flask equipped with a stirrer, Dimroth cooler, nitrogen inlet tube, silica gel drying tube, and thermometer, 250.2 parts of 4,4′-diphenylmethane diisocyanate and 116.1 parts of styrene as an unsaturated compound were added. The mixture was charged, heated to 40 ° C. under a nitrogen atmosphere, and stirred until 4,4′-diphenylmethane diisocyanate was completely dissolved. Thereafter, the temperature of the mixed solution was raised to 50 ° C., and 128.6 parts of polypropylene glycol having a molecular weight of 1000 (manufactured by Mitsui Takeda Chemical Co., Ltd., Actol P-22), 27.3 parts of diethylene glycol, and 12.4 parts of trimethylolpropane. Then, 45.7 parts of dimethylol butanoic acid and 193.4 parts of methyl ethyl ketone were added in order to adjust the viscosity, and the mixture was stirred for 4 hours while adjusting the temperature to 50-60 ° C. After confirming that the temperature reached 30 ° C., a reaction mixture containing a polyurethane prepolymer (an unsaturated monomer (styrene) -methyl ethyl ketone solution of a terminal isocyanate polyurethane prepolymer) was obtained.

  17.7 parts of trimethylolpropane triacrylate, which is an unsaturated compound, was added to 773.7 parts of the reaction mixture liquid containing the polyurethane prepolymer, and the mixture was stirred with a homodisper while stirring 15 of 2-dimethylaminoethanol. 183.4 parts of a% aqueous solution was added, and 1333 parts of deionized water was further added to obtain a milky-white aqueous dispersion. To this aqueous dispersion, 138.9 parts of a 10% aqueous solution of N- (2-aminoethyl) ethanolamine was added dropwise at a temperature of 30 ° C. or lower to carry out chain elongation reaction, and an unsaturated compound (styrene-trimethylol). A polyurethane resin emulsion containing propane triacrylate) was obtained.

  In a flask equipped with a stirrer, a Dimroth cooler, a nitrogen inlet tube, and a thermometer, the polyurethane resin emulsion 2446.4 parts containing the obtained unsaturated compound (styrene-trimethylolpropane triacrylate) was stirred. By adding 3.8 parts of 2,2′-azobisisobutyronitrile as a radical polymerization initiator, raising the temperature to 80 ° C., reacting for 2 hours, and removing methyl ethyl ketone and water at 50 ° C. under reduced pressure. An active hydrogen atom-containing polyurethane acrylic resin emulsion (a11) having a solid content of 35.0%, a viscosity (25 ° C.) of 42 mPa · s, a pH of 8.6, and an average particle size of 88 nm was obtained.

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

[Polyisocyanate]
MDI: 4,4′-diphenylmethane diisocyanate TDI: tolylene diisocyanate (manufactured by Mitsui Takeda Chemical Co., Ltd., Cosmonate T-80)
[Polyol]
PPG: Polypropylene glycol having a molecular weight of 1000 (manufactured by Mitsui Takeda Chemical Co., Ltd. Actol P-22)
PTG: Polytetramethylene ether glycol having a molecular weight of 2000 (manufactured by Hodogaya Chemical Co., Ltd., PTG-2000SN)
[Low molecular weight polyol]
DPG: Dipropylene glycol DEG: Diethylene glycol NPG: Neopentyl glycol TMP: Trimethylolpropane.

[Anionic group-containing compound]
DMBA: dimethylolbutanoic acid DMPA: dimethylolpropionic acid [unsaturated compound containing active hydrogen atoms]
HEMA: 2-hydroxyethyl methacrylate GLM: Glycerol monomethacrylate (manufactured by NOF Corporation, BLEMMER GLM).

[Organic solvent]
MEK: methyl ethyl ketone [active hydrogen atom-free unsaturated compound (unsaturated organic solvent)]
SM: Styrene MMA: Methyl methacrylate TMP-A: Trimethylolpropane triacrylate EGMA: Ethylene glycol dimethacrylate.

[Neutralizer]
15% DMEtA: 15% 2-dimethylaminoethanol aqueous solution TEA: triethylamine [polyamine]
10% A-EA: 10% N- (2-aminoethyl) ethanolamine aqueous solution [Radical polymerization initiator]
AIBN: 2,2′-azobisisobutyronitrile [metal dryer]
Mixed dryer: Lead-free dryer with cobalt content of 5% by weight, lithium content of 0.2% by weight and zirconium content of 7.5% by weight (manufactured by UCB Japan Co., Ltd., ADDITOL VXW6206)
NaPhCo: Cobalt naphthenate (cobalt content 6% by weight)
NaPhZr: zirconium naphthenate (zirconium content 6% by weight)
NaPhMn: Manganese naphthenate (manganese content 6% by weight).

Example 1
[Preparation of two-component curable water-based paint (c1)]
9.4 parts of N-methylpyrrolidone (NMP) is added as a film forming aid to 178.4 parts of the active hydrogen atom-containing polyurethane alkyd resin emulsion (a1), and polyoxyethylene-modified hexamethylene diisocyanate trimer is used as a curing agent (B). A two-component curable aqueous coating material (c1) was prepared by mixing 12.2 parts (Mitsui Takeda Chemicals, Takenate WD-240).

[Preparation of coating film for evaluation]
The obtained two-component curable aqueous paint (c1) was applied to a glass plate and a steel plate using a 100 μm applicator. In addition, after apply | coating the said water-based coating material to a glass plate, it was made to dry-cure for 1 week at room temperature, and was set as the coating film for evaluation. Moreover, after apply | coating the said aqueous coating material to a steel plate, it baked for 30 minutes at 120 degreeC, and was set as the coating film for evaluation.

  Also, beech wood whose base was polished with No. 240 sandpaper was brush-coated, dried and cured at room temperature until the next day, the surface of the coating film was polished with No. 400 sandpaper, and brush-coated again. . Thereafter, repeated coating was repeated twice to prepare a total of 4 coating films. After the final coating, the coating film was dried and cured at room temperature for 1 week to obtain a coating film for evaluation.

Examples 2-9
In the formulation shown in Table 4, two-component curable water-based paints (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 1-4
In the formulation shown in Table 3, two-component curable water-based paints (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 the comparative examples 3 and 4 are not mixing the hardening | curing agent (B), it becomes a mixing | blending prescription which does not contain a hardening | curing agent in Example 3 and 4. FIG.

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

[Filming aid]
NMP: N-methylpyrrolidone [curing agent (B)]
B1: Polyoxyethylene-modified hexamethylene diisocyanate trimer, manufactured by Mitsui Takeda Chemical Co., Ltd., Takenate WD-240, isocyanate group content 16.9% by weight
B2: Polyoxyethylene polyoxyalkylene modified hexamethylene diisocyanate trimer, manufactured by Mitsui Takeda Chemical Co., Ltd., Takenate WD-248, isocyanate group content 15.4% by weight.

[Evaluation]
(1) Compatibility of polyurethane alkyd resin emulsion (A) and curing agent (B) Polyurethane alkyd resin emulsion (A) obtained in the preparation example of active hydrogen atom-containing polyurethane alkyd resin emulsion (a1 to a11) and curing agent When (B) was mixed in a 300 ml sample bottle for about 1 minute at a ratio shown in Table 4, the compatibility was visually evaluated according to the following criteria.

◎: Shake the sample bottle lightly to mix thoroughly ○: Shake the sample bottle vigorously to mix completely △: Shake the sample bottle vigorously to mix (phase separation occurs over time)
×: Phase separation occurs without mixing even if the sample bottle is shaken strongly.

(2) Film-forming property of coating film The film-forming property of the coating film when the two-component curable aqueous paint obtained in each Example and each Comparative Example was applied to a glass plate was visually evaluated according to the following criteria. did.

A: Cracks do not occur in the coating film (the coating film can be obtained without problems)
○: A crack occurs in a part of the coating film. Δ: A crack occurs in the entire coating film.

(3) Coating Film Appearance The coating film appearance when four layers of the two-component curable aqueous paint obtained in each Example and each Comparative Example were applied to beech wood was visually evaluated according to the following criteria.

◎: The entire coating film is highly glossy and has a feeling of fleshiness ○: The entire coating film is glossy △: The entire coating film is matte or cloudy ×: The entire coating film is cracked appear.

(4) Water resistance The two-component curable water-based paint obtained in each Example and each Comparative Example was dropped on the surface of the coating film when applied to a glass plate, a steel plate, and beech wood (four layers). The state of the coating film after being covered so as not to evaporate and maintained for 24 hours was visually evaluated according to the following criteria.

A: No change is observed in the entire coating film B: The coating film partially swells (blisters are generated)
Δ: The entire coating film swells or whitens. X: The entire coating film dissolves. XX: Water penetrates into the crack and cannot be evaluated.

(5) Moisture and heat resistance Boiling water is dripped immediately on the coating film surface when the two-component curable aqueous paint obtained in each Example and each Comparative Example is applied to a glass plate, a steel plate and beech wood (four layers). A glass bottle containing boiling water (a bottle with a diameter of about 5 cm with a small space at the bottom) is placed on it, covered so that water vapor does not volatilize, and the state of the coating film is maintained visually for 20 minutes. The evaluation was based on the following criteria.

◎: No change is observed in the entire coating film ○: The coating film is partially swollen △: The entire coating film is swollen or whitened ×: The entire coating film is dissolved XX: Boiling water is infiltrated into cracks I can't.

(6) Solvent resistance When the two-part curable aqueous paint obtained in each Example and each Comparative Example is applied to a glass plate and a steel plate, the coating film is rubbed with methyl ethyl ketone (gauze is attached to the tip of the chopsticks) When the coating film was rubbed after being immersed in methyl ethyl ketone, the number of times until the coating film was peeled off (one reciprocation and one upper limit was 100) was evaluated according to the following criteria.

A: No peeling even after 100 times, and no change is observed in the entire coating film. ○: No peeling even after 100 times or more, but the whole coating film is slightly swollen. Δ: The entire coating film is peeled after 50 times or less. The entire coating is peeled off after the first time.

(7) Pencil hardness About JIS K5600-5-4 about a coating film when apply | coating the two-component curable aqueous coating material obtained by each Example and each comparative example to a glass plate, a steel plate, and beech wood (4 layers). The pencil hardness was measured in conformity.

(8) Magic stain resistance A line is drawn with magic containing black and red xylene on a coating film formed by applying four layers of the two-component curable aqueous paint obtained in each Example and each Comparative Example to beech wood. After holding for 3 hours, it was wiped off with ethanol and the state of the coated film was visually evaluated according to the following criteria.

◎: Black and red magic can be completely wiped off ○: Black and red magic can be partially or only wiped off △: Black and red magic can be wiped off, but the entire coating film dissolves ×: Black , Red magic soaks into the coating and cannot be wiped off.

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

  As is clear from the results in Table 5, the paints of the examples are excellent in various properties. On the other hand, the paint of the comparative example cannot improve water resistance, moist heat resistance, solvent resistance and the like. Moreover, it takes a long time to develop the hardness.

Example 10
Polyurethane alkyd obtained by adding 6.8 parts of N-methylpyrrolidone (NMP) as a film forming aid to 88.2 parts of the active hydrogen atom-containing polyurethane alkyd resin emulsion (a4) under the conditions of 23 ° C. and 50% RH. Resin emulsion (A) and curing agent (B), polyoxyethylene polyoxyalkylene modified hexamethylene diisocyanate trimer (Mitsui Takeda Chemical Co., Ltd., Takenate WD-248, isocyanate group content 15.4%), Tap water was mixed with polyurethane alkyd resin emulsion (A) / curing agent (B) / tap water = 95/5/95 (weight ratio) to prepare a two-component curable aqueous primer. The surface of a slate plate whose surface has been previously treated with air blow is uniformly applied at 23 ° C. and 50% RH so that the application amount of the two-part curable aqueous primer immediately after preparation is 150 g / m ² with a brush. And applied for 3 hours. Two-component urethane resin (floor coating material, manufactured by Mitsui Takeda Chemical Co., Ltd., main agent: Takenate) immediately after mixing the main agent and curing agent on the surface of the coating film at a ratio of 1: 1 (weight ratio). F-135, curing agent: Takelac PC-5300) was applied uniformly using a trowel so that the coating amount was 2000 g / m ^2, and cured for 7 days at 23 ° C. and 50 RH to produce a slate plate coating sample. did.

Example 11
A polyurethane alkyd resin emulsion (A) obtained by adding 6.8 parts of N-methylpyrrolidone (NMP) as a film forming aid to 88.2 parts of the active hydrogen atom-containing polyurethane alkyd resin emulsion (a4), and a curing agent (B ), A propylene glycol monomethyl ether acetate (PMA) solution containing the modified hexamethylene diisocyanate trimer (Takenate WD-248) at a concentration of 80% and tap water, and a polyurethane alkyd resin emulsion (A) / curing agent (B ) / Tap water = A slate plate-coated sample was prepared in the same manner as in Example 10 except that a two-component curable aqueous primer mixed at a ratio (weight ratio) of 95 / 6.3 / 95 was used.

Example 12
A polyurethane alkyd resin emulsion (A) obtained by adding 6.8 parts of N-methylpyrrolidone (NMP) as a film forming aid to 88.2 parts of the active hydrogen atom-containing polyurethane alkyd resin emulsion (a4), and a curing agent (B ), An acetone solution containing the modified hexamethylene diisocyanate trimer (Takenate WD-248) at a concentration of 80% and tap water, polyurethane alkyd resin emulsion (A) / curing agent (B) / tap water = 95 / A sample coated with a slate plate was produced in the same manner as in Example 10 except that a two-component curable aqueous primer mixed at a ratio (weight ratio) of 6.3 / 95 was used.

Example 13
A polyurethane alkyd resin emulsion (A) obtained by adding 8.2 parts of N-methylpyrrolidone (NMP) as a film forming aid to 86.8 parts of the active hydrogen atom-containing polyurethane alkyd resin emulsion (a9), and a curing agent (B ), A propylene glycol monomethyl ether acetate (PMA) solution containing the modified hexamethylene diisocyanate trimer (Takenate WD-248) at a concentration of 80% and tap water, and a polyurethane alkyd resin emulsion (A) / curing agent (B ) / Tap water = A slate plate-coated sample was prepared in the same manner as in Example 10 except that a two-component curable aqueous primer mixed at a ratio (weight ratio) of 95 / 6.3 / 95 was used.

Example 14
A polyurethane alkyd resin emulsion (A) obtained by adding 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), and a curing agent (B ), The modified hexamethylene diisocyanate trimer (Takenate WD-248) and tap water, polyurethane alkyd resin emulsion (A) / curing agent (B) / tap water = 95/5/95 (weight ratio) A slate plate-coated sample was prepared in the same manner as in Example 10 except that the two-component curable aqueous primer mixed in (1) was used.

Comparative Example 5
In the same manner as in Example 10, except that a TDI-based one-component moisture-curable solvent-based primer composition (Takenate M-402p, manufactured by Mitsui Takeda Chemical Co., Ltd.) was used instead of the two-component curable aqueous primer. A slate plate coating sample was prepared.

Comparative Example 6
The same method as in Example 10 except that instead of the two-component curable aqueous primer, an MDI-based one-component moisture curable solvent-based primer composition (Mitsui Takeda Chemical Co., Ltd., Hyprene AX-616) was used. A slate plate coating sample was prepared.

  The evaluation slate plate coating samples of Examples 10 to 14 and Comparative Examples 5 to 6 were subjected to the following evaluation tests.

[Evaluation test]
(1) Appearance change after water resistance A plastic container with a lid is filled with tap water, and the entire sample (slate plate on which the coating film is formed) is completely immersed in water. , Left at 50% RH for 7 days. Thereafter, the sample was taken out from water, and the surface state of the polyurethane coating film was visually observed. A sample in which no peeling or swelling was observed was designated as X, and a sample in which changes such as peeling or swelling were recognized was designated as X.

(2) Normal adhesiveness A cut was made with a width of 25 mm on the surface of the sample polyurethane coating, and the adhesive strength (N / mm) was measured by a 90-degree peel test.

(3) Water-resistant adhesiveness The adhesive strength (N / mm) was measured by the same method as normal adhesiveness using the sample used in the appearance evaluation after water-resistant.

(4) Dry adhesion The sample used in the appearance evaluation after water resistance was allowed to stand for 1 day under conditions of 23 ° C. and 50% RH, and then the adhesion strength (N / mm) was measured by the same method as that for normal adhesion.

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

  As is apparent from the results in Table 6, the aqueous primer of the example provides a two-component curable aqueous primer similar to a solvent-based primer excellent in adhesion to various inorganic material adherends and topcoat materials and durability. .

Claims (9)

A polyurethane alkyd resin emulsion (A) having an active hydrogen atom in the molecule, a curing agent (B) composed of polyisocyanate dispersible in the emulsion (A), and a lead-free metal composed of a fatty acid composite metal salt A two-component curable aqueous resin composition comprising a dryer (C) ,
The polyurethane alkyd resin emulsion (A) is an emulsion obtained by a reaction between an alkyd resin and an aromatic polyisocyanate, and
The curing agent (B) is _{composed of} polyisocyanate, polyoxyethylene C _8-24 alkyl ether, polyoxyethylene C _8-12 alkyl phenyl ether and polyoxyethylene polyoxy C _3-6 alkylene C _8-24 alkyl ether. Two-part curable aqueous resin, which is a dispersible polyisocyanate obtained by reaction with a nonionic surfactant that is at least one selected from the group consisting of and having an average addition mole number of oxyethylene units of 12 to 30 moles Composition . The two-component curable aqueous resin composition according to claim 1, wherein the polyurethane alkyd resin emulsion (A) is an emulsion obtained by a reaction between an alkyd resin having a hydroxyl value of 30 to 250 and an aromatic polyisocyanate.   The two-component curable aqueous resin composition according to claim 1, wherein the polyurethane alkyd resin emulsion (A) has an active hydrogen atom derived from a hydroxyl group. Alkyd resin component of Po Li urethane alkyd resin emulsion (A) is, two-component curable aqueous resin composition of claim 1 comprising an unsaturated fatty acid as a constituent unit.   The two-component curable aqueous resin composition according to claim 1, wherein the polyurethane alkyd resin emulsion (A) further comprises a (meth) acrylic component having a polymerizable group.   The two-part curable aqueous resin according to claim 1, wherein 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. Composition.   The two-part curable aqueous resin composition according to claim 1, which is curable at room temperature. A polyurethane alkyd resin emulsion (A) having an active hydrogen atom in the molecule, a curing agent (B) composed of polyisocyanate dispersible in the emulsion (A), and a lead-free metal composed of a fatty acid composite metal salt A two-component curable water-based paint comprising a dryer (C) ,
The polyurethane alkyd resin emulsion (A) is an emulsion obtained by a reaction between an alkyd resin and an aromatic polyisocyanate, and
The curing agent (B) is _{composed of} polyisocyanate, polyoxyethylene C _8-24 alkyl ether, polyoxyethylene C _8-12 alkyl phenyl ether and polyoxyethylene polyoxy C _3-6 alkylene C _8-24 alkyl ether. Two-component curable water-based paint which is a dispersible polyisocyanate obtained by a reaction with a nonionic surfactant which is at least one selected from the group consisting of and having an average addition mole number of oxyethylene units of 12 to 30 moles . A polyurethane alkyd resin emulsion (A) having an active hydrogen atom in the molecule, a curing agent (B) composed of polyisocyanate dispersible in the emulsion (A), and a lead-free metal composed of a fatty acid composite metal salt A two-component curable aqueous primer containing a dryer (C) ,
The polyurethane alkyd resin emulsion (A) is an emulsion obtained by a reaction between an alkyd resin and an aromatic polyisocyanate, and
The curing agent (B) is _{composed of} polyisocyanate, polyoxyethylene C _8-24 alkyl ether, polyoxyethylene C _8-12 alkyl phenyl ether and polyoxyethylene polyoxy C _3-6 alkylene C _8-24 alkyl ether. Two-part curable aqueous primer which is a dispersible polyisocyanate obtained by reaction with a nonionic surfactant which is at least one selected from the group consisting of and having an average addition mole number of oxyethylene units of 12 to 30 moles .