Aqueous coating composition

Distemper constituent

0001The present invention relates to a distemper constituent.

0002In recent years, converting into distemper from a solvent system paint is socially called for from a viewpoint of environmental protection. As such distemper, the two-component distemper constituent containing an epoxy resin and polyamine compound is mentioned, for example (patent documents 1). Such a distemper constituent shows hardenability sufficient at the temperature more than normal temperature, and can form a normal coat. However, since it is inferior to hardenability under low temperature (for example, around 5 ), when using it with a low-temperature background (for example, outdoors of winter), there is a problem of being hard to demonstrate original sufficient coat performance.

<p num="0003"><patcit num="1"><text>JP,11-166153,A</text></patcit></p>

<p num="0004">There is a place which is made in order that the present invention may solve the above-mentioned conventional subject, and is made into the object in providing the distemper constituent which is excellent in cold cure nature.</p>

<p num="0005">Water solubility or polyamine resin (A) of water distributed type in which the distemper constituent of the present invention has one or more primary amine machines and/or the 2nd amine machines in a molecule, Amine this quantity of the polyamine resin (A) is 100-3000 including a compound (B) which has one or more acrylyl groups (meta) in a molecule. Viscosity at 25 of the compound (B) is 3000 or less mPa-s.</p><p num="0006">In a desirable embodiment, the above-mentioned distemper constituent is a two-component distemper constituent, base resin paint liquid contains the above-mentioned polyamine resin (A), and a hardening agent contains the above-mentioned compound (B).</p><p num="0007">In a desirable embodiment, the above-mentioned polyamine resin (A) is acrylic polyamine resin or epoxy system polyamine resin.</p><p num="0008">In a desirable embodiment, the molecular weights of the above-mentioned compound (B) are 150 or more and 2000 or less.</p><p num="0009">In a desirable embodiment, the above-mentioned compound (B) is a water-soluble compound, and the above-mentioned polyamine resin (A) is water distributed resin.</p><p num="0010">In a desirable embodiment, the above-mentioned compound (B) is a self-emulsifiability compound.</p><p num="0011">The above-mentioned compound (B) is emulsified or distributed by the above-mentioned polyamine resin (A) in the desirable embodiment.</p><p num="0012">In a desirable embodiment, the above-mentioned compound (B) is a mixture of a water-soluble compound and a non-water solubility compound.</p><p num="0013">In a desirable embodiment, the above-mentioned compound (B) is an emulsification thing.</p><p num="0014">In a desirable embodiment, the above-mentioned hardening agent further contains an emulsifier.</p>

<p num="0015">The distemper constituent of the present invention shows the outstanding cold cure nature by including the water solubility or polyamine resin (A) of water distributed type which has one or more primary amine machines and/or the 2nd amine machines in a molecule, and the compound (B) which has one or more acrylyl groups (meta) in a molecule. That is, since these will show high reactivity mutually and a reaction will progress under low temperature if the above-mentioned polyamine resin (A) and the above-mentioned compound (B) are used, the distemper constituent which is excellent in the hardenability under low temperature can be obtained. Since the above-mentioned polyamine resin (A) may have the structure which crosslinked with the above-mentioned compound (B), the output obtained by the reaction of the above-mentioned polyamine resin (A) and the above-mentioned compound (B) can obtain the distemper constituent excellent in the coat performance.</p>

0016A. The outline of a distemper constituent<br />Water solubility or polyamine resin (A) of water distributed type in which the distemper constituent of the present invention has one or more primary amine machines and/or the 2nd amine machines in a molecule, In a molecule, including the compound (B) which has one or more acrylyl groups (meta), it can harden by the reaction of polyamine resin (A) and a compound (B), and can obtain a coat.

0017A distemper constituent of the present invention is a two-component distemper constituent consisting of base resin paint liquid and a hardening agent preferably. The base resin paint liquid concerned contains the above-mentioned polyamine resin (A), and the hardening agent concerned contains the above-mentioned compound (B). Since the combination both indicate high reactivity to be mutually about polyamine resin (A) and a compound (B) by using the above-mentioned polyamine resin (A) and the above-mentioned compound (B) as a two-component distemper constituent can be chosen, The distemper constituent which is excellent in cold cure nature can be obtained.

0018Content as solid content of the above-mentioned polyamine resin (A) is 5 to 95 % of the weight preferably to the total amount of solid content of a distemper constituent. It is 10 to 90 % of the weight preferably.

0019Content of the above-mentioned compound (B) is 2 to 40 % of the weight preferably to the total amount of solid content of a distemper constituent. It is 5 to 30 % of the weight preferably.

0020The ratio (amine machine: acrylyl group) of the number of the amine machine which the above-mentioned polyamine resin (A) has to the number of the acrylyl group which the above-mentioned compound (B) has (meta), Preferably it is 1:0.5 to 1:1.5, still more preferably is 1:0.75 to 1:1.25, and, especially preferably is 1:0.9 to 1:1.1. In this specification, it is with "the number of an amine machine", When it has a primary amine machine in a molecule (it contains also when it has a primary amine machine and the 2nd amine machine), the number (that is, the number of the 2nd amine machine does not contain) of a primary amine machine is meant, and when polyamine resin (A) has only the 2nd amine machine in a molecule, it means the number of the 2nd amine machine.

0021The distemper constituent of the present invention may blend paints, a solvent, an additive agent, etc. if needed. As paints, they are titanium oxide, yellow iron oxide, red oxide of iron, and carbon black, for example, Color pigments, such as copper phthalocyanine blue, copper phthalocyanine green, azo red, cinchona bark Cridon red, and Benz imidazolone yellow; constitution paints, such as calcium carbonate, barium sulfate, kaolin, clay, and talc, are mentioned. As a solvent, they are ethylene glycol, propylene glycol, and ethylene glycol monobutyl ether, Propylene glycol monobutyl ether, diethylene glycol, The Zypro pyrene glycol, diethylene glycol monobutyl ether, Glycol system solvents, such as dipropyleneglycol monobutyl ether and diethylene glycol dibutyl ether; xylene, The aromatic solvent of Solvesso 100, Solvesso 150, and Solvesso 200 grade; hydrocarbon system solvent [, such as mineral spirit, ];2, 2, 4-Tori Methyl- 1, 3-pentanediol Monoiso butyrate (CS-12), Esters solvents, such as 2, 2, 4-Tori Methyl- 1, 3-pentanediol Diiso butyrate (CS-16), Diethyl adipate, and diisobutyl horse mackerel Pate, are mentioned. As an additive agent, a dispersing agent, a viscous adjustment agent, a curing catalyst, a surface adjustment agent, an antifoaming agent, a plasticizer, a film formation auxiliary agent, an ultraviolet ray absorbent, an antioxidant, etc. are mentioned.

0022B. Polyamine resin (A)<br />The polyamine resin (A) used for the distemper constituent of the present invention has one or more primary amine machines and/or the 2nd amine machines, and if it is resin of water solubility or water distributed type, arbitrary suitable resin may be adopted. As such resin, fatty series polyamine resin, aromatic series polyamine resin, and alicycle fellows polyamine resin are mentioned, for example.

0023Quantity of an amine machine which polyamine resin (A) has is 100-3000 as an amine this quantity. Preferably it is 500-2000 and is 800-1500 especially preferably. If the amine this quantity of polyamine resin (A) is such a range, polyamine resin (A) has water solubility or water-dispersion, and can obtain the coat which is excellent in cold cure nature. The amine this amount of above is shown by the molecular weight of the resin solid content per primary amine basis when polyamine resin (A) has primary amine, and when polyamine resin (A) does not have a primary amine machine, it is shown by the molecular weight of the resin solid content per one of the 2nd amine machine. The amine this quantity of polyamine resin (A) can be calculated from materials loadings.

0024Arbitrary suitable molecular weights can be used for the molecular weight (number average) of the above-mentioned polyamine resin (A) according to desired coat physical properties. Preferably, in the standard polystyrene conversion using a gel permeation chromatography (GPC), it is 500-20000 and is 1000-3000 still more preferably. Since the above-mentioned compound (B) can be easily mixed with polyamine resin (A) if the molecular weight of polyamine resin (A) is such a range, it can be made to react efficiently. If the molecular weight of polyamine resin (A) is such a range, the coat which is excellent in anti-corrosiveness, water resistance, and adhesion can be obtained.

0025Arbitrary suitable glass transition temperature can be used for the glass transition temperature of the above-mentioned polyamine resin (A) according to desired coat physical properties. Preferably -50-100 is 0-50 still more preferably.

0026What was water-ized can be used for the above-mentioned polyamine resin (A) by neutralizing an amine machine from acid. According to the state (water solubility - water dispersing element) of the polyamine resin (A) considered as a request, the kind and neutralization rate of arbitrary suitable acid can be used for the kind and neutralization rate (neutralization rate to the amine machine of polyamine resin before water-izing) of acid. As the above-mentioned acid, acetic acid, formic acid, lactic acid, phosphoric acid, etc. are mentioned, for example. A neutralization rate (neutralization rate to the amine machine of polyamine resin before water-izing) is 10 to 70% preferably, and, still more preferably is 15 to 50%.

0027The above-mentioned polyamine resin (A) is the acrylic polyamine resin which carried out amine denaturation of epoxy system polyamine resin or the acrylic resin which carried out amine denaturation of the epoxy resin preferably, and, especially preferably is epoxy system polyamine resin. It is because the distemper constituent which is more excellent in anti-corrosiveness can be obtained if it is epoxy system polyamine resin. Namely, the thing for which epoxy system polyamine resin and the above-mentioned compound (B) as polyamine resin (A) are used, The conventional epoxy resin paint constituent which consists of epoxy resin-polyamine compound, and the distemper constituent which can form the coat which demonstrates the anti-corrosiveness which excelled more than equivalent under low temperature can be obtained.

0028The above-mentioned epoxy system polyamine resin and acrylic polyamine resin may be obtained by arbitrary suitable modification methods. As the above-mentioned modification method, the method of adding primary amine machine content polyamine to an epoxy resin or an acrylic resin and the method of adding the ketimine-ized amine machine content compound to an epoxy resin or an acrylic resin are mentioned, for example. Thus, the obtained polyamine resin (A) has one or more primary amine machines and/or the 2nd amine machines, and the 2nd class hydroxyl groups in the molecule. The above-mentioned polyamine resin may be resin produced by making the compound which has functional groups, such as an epoxy group, an acid anhydride machine, an acid halogen group, and an isocyanate group, react to some of primary amine machines of the polyamine resin (A) concerned, 2nd amine machines, and/or hydroxyl groups. The physical properties of the coat obtained can be adjusted by making the polyamine resin to which such a functional group was made to react contain as some polyamine resin to be used.

0029About how to add the above-mentioned primary amine machine content polyamine to an epoxy resin or an acrylic resin, Namely, the reaction group of the primary amine machine of the above-mentioned primary amine machine content polyamine, an epoxy resin, or an acrylic resin (For example, epoxy group) It is the method of making the above-mentioned epoxy system polyamine resin or the above-mentioned acrylic polyamine resin which makes it reacting, makes the 2nd amine machine forming, and has the 2nd amine machine as a result generating.

0030About how to add the amine machine content compound ketimine-ized [ above ] to an epoxy resin or an acrylic resin, Namely, the thing for which a ketimine machine is hydrolyzed after making the amine machine content compound, epoxy resin, or acrylic resin ketimine-ized [ above ] react, It is the method of making the above-mentioned epoxy system polyamine resin or the above-mentioned acrylic polyamine resin which makes a primary amine machine forming and has a primary amine machine as a result generating. When making the amine machine content compound, epoxy resin, or acrylic resin ketimine-ized [ above ] react, secondary amine, such as Diethanol amine, methylethanol amine, and Diethyl amine, may be made to coexist.

0031The suitable thing which has the above-mentioned arbitrary epoxy resin may be used. Preferably it is a bisphenol A type epoxy resin or a screw phenol F type epoxy resin, and, especially preferably is a bisphenol A type epoxy resin.

0032The epoxy equivalent of the above-mentioned epoxy resin can be determined according to desired coat physical properties. desirable -- 180-2000 -- still more preferably it is 400-1500. If the epoxy equivalent of an epoxy resin is such a range, the coat which is excellent in water resistance, anti-corrosiveness, and adhesion can be obtained.

0033The above-mentioned epoxy resin carries out chain extension using the reaction of the active hydrogen content compound and epoxy group which can react to an epoxy group, and it can make a molecular weight able to increase or it can denature it. As the above-mentioned active hydrogen content compound, the compound of two functionality, such as dimer acid, Gia Min, and polyether polyol, is mentioned, for example.

0034Before carrying out amine denaturation according to a use, by making fatty acid add and reducing the number of epoxy groups, the above-mentioned epoxy resin may reduce the part which carries out amine denaturation, may reduce reactivity, and it may use it.

0035The suitable thing which has the above-mentioned arbitrary acrylic resin may be used. It is an acrylic resin produced by copolymerizing the monomer constituent containing the radical pile affinity monomer which has an epoxy group and/or a glycidyl group preferably. As the radical pile affinity monomer which has the above-mentioned epoxy group and/or a glycidyl group, For example, glycidyl acrylate, glycidyl methacrylate, methyl glycidyl acrylate, methyl glycidyl methacrylate, 3, 4-epoxycyclohexyl methylacrylate, 3, and 4-epoxycyclohexyl methylmethacrylate etc. are mentioned.

0036As the above-mentioned primary amine machine content polyamine, diethylene triamine, dipropylenetriamine, Djibouti Wren Tori Amin, Triethylene tetramine, etc. are mentioned, for example. These may be used independently, and may be combined and used.

0037The amine machine content compound ketimine-ized [ above ] can be obtained by the ability to make a primary amine machine content compound and ketone able to react. As the above-mentioned primary amine machine content compound, it is diethylene triamine, for example, Primary amine machine content polyamine, such as dipropylenetriamine, Djibouti Wren Tori Amin, and Triethylene tetramine; aminoethylethanolamine, methylamino propylamine, ethylamino ethyl amine, etc. are mentioned. These may be used independently, and may be combined and used. As the above-mentioned ketone, methyl ethyl ketone, acetone, methyl isobutyl ketone, etc. are mentioned, for example.

0038C. Compound (B)<br />The compound (B) used for the distemper constituent of the present invention has one or more acrylyl groups (meta) in a molecule.

0039Molecular weights of the above-mentioned compound (B) are 150 or more and 2000 or less preferably. It is 250 or more and 1300 or less especially preferably 200 or more and 1700 or less preferably. If the molecular weight of a compound (B) is such a range, it can mix polyamine resin (A) and a compound (B) easily, without using a special mixed device, and can obtain the paint constituent excellent in dispersibility. As a result, a compound (B) can make it able to react to polyamine resin (A) mutually efficiently, and it can obtain the distemper constituent which is excellent in hardenability. The molecular weight of the above-mentioned compound (B) is computable from a chemical formula.

0040The number of acrylyl groups which the above-mentioned compound (B) has (meta) is one or more. Preferably, it is 2-4. The number of the acrylyl groups which a compound (B) has (meta) may be determined according to desired coat physical properties.

0041Viscosity at 25 of the above-mentioned compound (B) is 3000 or less mPa-s. Preferably it is 50 or more mPa-s and 3000 mPa-s or less, and still more preferably is 50 or more mPa-s and 2200 mPa-s or less, and, especially preferably they are 50 or more mPa-s and 1100 mPa-s or less. If the viscosity of a compound (B) is such a range, polyamine resin (A) and a compound (B) can be mixed easily, without using a special mixed device, and the paint constituent excellent in dispersibility can be obtained. As a result, polyamine resin (A) and a compound (B) can be made to be able to react mutually efficiently, and the distemper constituent which is excellent in hardenability can be obtained.

0042As the above-mentioned compound (B), it is a polymerization unsaturated monocarboxylic acid ester compound of polyhydric alcohol, for example. (For example, ethylene glycol diacrylate, ethylene glycol dimethacrylate) Triethylene glycol diacrylate, triethylene glycol dimethacrylate, Tetraethylene glycol diacrylate, tetra-ethylene glycol dimethacrylate, 1, 3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, Trimethylolpropane triacrylate, trimethylolpropane tri-methacrylate, 1, 4-butanediol diacrylate, 1, 4-butanediol Dimeta acrylate, Neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, Penta erythritol diacrylate, pentaerythritol dimethacrylate, a Penta erythritol Triacli rate, pentaerythritoltrimetaacrylate, Penta erythritol tetraacrylate, pentaerythritol tetramethacrylate, Glycerol diacrylate, glycerol dimethacrylate, glycerol Acroxidge methacrylate, 1, 1, and 1-tris hydroxymethyl ethane diacrylate, 1 and 1, and 1-tris hydroxymethyl Ethanedi methacrylate, 1, 1, and 1-tris hydroxymethyl Etantori acrylate, 1 and 1, and 1-tris hydroxymethyl ethane trimetaacrylate, 1, 1, and 1-tris hydroxymethyl propane diacrylate, 1 and 1, and 1-tris hydroxymethyl Propandi methacrylate etc., The addition of an epoxy group content ethylenic unsaturated monomer and a carboxyl group content ethylenic unsaturated machine monomer (For example, the reaction thing of glycidyl acrylate, glycidyl methacrylate, and acrylic acid, methacrylic acid, crotonic acid and maleic acid), etc. and the polymerization unsaturated monocarboxylic acid amide compounds (for example, ethylene diamine diacrylate etc.) of Many value amine are mentioned. These may be used independently, and may be combined and used.

0043It is as above-mentioned that there is [ the above-mentioned compound (B) ] mixable necessity (both can react) easily with the above-mentioned polyamine resin (A). Preferably, polyamine resin (A) and a compound (B) are easily used for mixable within the limits (both can react) in the uneven state. Preferably a compound (B) and polyamine resin (A) are used with a mutually different phase state. Since advance of the rapid reaction of polyamine resin (A) and a compound (B) can be controlled and reactivity can be moderately adjusted, if it is in such a state, For example, when using the distemper constituent of the present invention as a two-component paint, the distemper constituent which is excellent in handling nature can be obtained. When a compound (B) is a water-soluble compound, and polyamine resin (A) is water distributed resin as a desirable example of such a state and a compound (B) is self-emulsifiability, the case where a compound (B) may be emulsified or distributed by polyamine resin (A) is mentioned. The above-mentioned compound (B) can make that judgment which is any of "non-water solubility", "water solubility", or "self-emulsifiability" by viewing the state after adding 5 g of compounds (B) to 100 g of water, agitating this (for example, for 3 minutes) and settling under room temperature (for example, after 5 minutes). There are not "non-water solubility" and precipitation, after settlement, if precipitation has arisen, if transparent, there will not be "water solubility" and precipitation, and if there is muddiness, it can be judged as "self-emulsifiability."

0044When having denatured by polyethylene oxide, by increasing the number of ethylene oxide addition Mol, the above-mentioned compound (B) can improve hydrophilicity and can use it as the compound of water solubility or self-emulsifiability, for example.

0045As the above-mentioned water-soluble compound (B), it is ethoxy Turn bisphenol A diacrylate (EO30mol), for example, Ethoxy Turn trimethylolpropane triacrylate (EO20mol), Ethoxy Turn trimethylolpropane triacrylate (EO30mol), Ethoxy Penta erythritol tetraacrylate (EO35mol), ethoxy Turn glyceryl triacrylate (EO20mol), ethoxy Turn bisphenol A dimethacrylate (EO30mol), etc. are mentioned. These may be used independently, and may be combined and used. In this specification, the notation of "EO30mol" means having 30 ethylene oxide in a molecule.

0046As a compound (B) of the above-mentioned self-emulsifiability, it is polyethylene-glycols #400 diacrylate (EO9mol), for example, Polyethylene-glycols #600 diacrylate (EO14mol), Polyethylene-glycols #1000 diacrylate (EO23mol), Ethoxy Turn bisphenol A diacrylate (EO10mol), ethoxy Turn bisphenol A diacrylate (EO20mol), Ethoxy Turn glyceryl triacrylate (EO9mol), polyethylene-glycols #1000 dimethacrylate (EO23mol), etc. mention, and it is Raruru. These may be used independently, and may be combined and used.

0047As the compound (B) which may be emulsified or distributed with the above-mentioned polyamine resin (A), For example, polyethylene-glycols #200 glycol diacrylate (EO4mol), Ethoxy Turn bisphenol A diacrylate (EO3mol), ethoxy Turn bisphenol A diacrylate (EO4mol), Propoxy-ized bisphenol A diacrylate (PO3mol), 1, 10-Decanji all diacrylate, Tricyclodecane dimethanol diacrylate, ethoxy Turn 2-methyl 1, 3-pro pansy all diacrylate (EO2mol), Neopentyl glycol diacrylate, 1, 6-hexanediol diacrylate, 1,9-Nonanji all diacrylate, dipropylene glycol diacrylate (PO2mol), Tripropylene glycol diacrylate (PO3mol), polypropylene glycol #400 diacrylate (PO7mol), Polypropylene glycol #700 diacrylate (PO12mol), ethoxy Turn trimethylolpropane triacrylate (EO3mol), ethoxy Turn trimethylolpropane triacrylate (EO9mol), Trimethylolpropane triacrylate, propoxy-ized trimethylolpropane triacrylate (PO3mol), A Penta erythritol Triacli rate, ethoxy Penta erythritol tetraacrylate (EO4mol), Ditrimethylolpropanetetraacrylate, propoxy-ized Penta erythritol tetraacrylate (PO4mol), Propoxy-ized bisphenol A diacrylate (PO4mol), ethylene glycol dimethacrylate (EO1mol), Diethylene glycol dimethacrylate (EO2mol), triethylene glycol dimethacrylate (EO3mol), Tetraethylene glycol dimethacrylate (EO4mol), polyethylene-glycols #400 dimethacrylate (EO9mol), Polyethylene-glycols #600 dimethacrylate (EO14mol), 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanedioldimethacrylate, 1,9-Nonanji all dimethacrylate, ethoxy Turn bisphenol A dimethacrylate (EO2.6mol), Ethoxy Turn bisphenol A dimethacrylate (EO4mol), ethoxy Turn bisphenol A dimethacrylate (EO6mol), Ethoxy Turn bisphenol A dimethacrylate (EO10mol), Ethoxy Turn bisphenol A dimethacrylate (EO17mol), Neopentyl glycol dimethacrylate, ethoxy Turn polypropylene glycol #700 dimethacrylate (PO12mol, EO6mol), Glycerin dimethacrylate, tripropylene glycol dimethacrylate (PO3mol), Polypropylene glycol #400 dimethacrylate (PO7mol), trimethylolpropanetrimethacrylate, ethoxy Turn trimethylolpropanetrimethacrylate (EO9mol), etc. are mentioned. These may be used independently, and may be combined and used.

0048The above-mentioned compound (B) is preferably used as these mixtures combining a water-soluble compound and a non-water solubility compound. Thus, if the mixture of a water-soluble compound and a non-water solubility compound is used, a non-water solubility compound can be easily introduced to the system of reaction with a water-soluble compound. The paint obtained is excellent in cold cure nature. As a water-soluble compound which has one or more acrylyl groups (meta), an above-mentioned water-soluble compound (B) is mentioned in a molecule, for example. As a non-water solubility compound which has one or more acrylyl groups (meta), the compound which propoxy-ized bisphenol A diacrylate (PO4mol) etc. do not make aqueous completely, for example is mentioned in a molecule. The mixing ratio (water solubility / non-water solubility) of a water-soluble compound (B) and the compound (B) of non-water solubility is 1 / 9 - 9/1 preferably, and, still more preferably is 2 / 8 - 8/2.

0049In one embodiment, a compound (B) may be diluted with the organic solvent, before mixing the above-mentioned compound (B) with the above-mentioned polyamine resin (A). As the organic solvent concerned, ethylene glycol Monobuchi ether (BC), diethylene glycol monobutyl ether (BDG), etc. are mentioned, for example. Thus, if a compound (B) is beforehand diluted with the organic solvent, polyamine resin (A) and a compound (B) can be mixed, without using a special mixed device, and the paint constituent excellent in dispersibility can be obtained. As a result, polyamine resin (A) and a compound (B) can be made to react mutually efficiently.

0050In another embodiment, the above-mentioned compound (B) is an emulsification thing. That is, before mixing the above-mentioned compound (B) with the above-mentioned polyamine resin (A), a compound (B) may be made to mix an emulsifier, and the compound (B) may be emulsified or distributed by a dispersing agent, an emulsifier, or water resin. When the distemper constituent of the present invention is a two-component distemper constituent, the above-mentioned hardening agent may be made to further contain an emulsifier. If these processings are performed, polyamine resin (A) and a compound (B) can be mixed, without using a special mixed device, and the paint constituent excellent in dispersibility can be obtained. As a result, polyamine resin (A) and a compound (B) can be made to react mutually efficiently. If these processings are performed, a compound (B) can be dealt with as a non-dangerous object. As the above-mentioned emulsifier, a Nonion system emulsifier, an anionic system emulsifier, etc. are used, for example. As a Nonion system emulsifier, it is polyoxy ethylene Alkyl phenol ether, for example, Polyoxy ethylene styrene-ized phenyl ether, polyoxyethylene alkyl ether, a polyoxyethylene polyoxypropylene blockpolymer, sorbitan fatty acid ester, etc. are mentioned. As an anionic system emulsifier, it is dodecylbenzenesulfonic acid salt, for example, Dial kill succinate sulfonic acid salt, polyoxyethylene-alkyl-ether sulfate ester salt, polyoxy ethylene styrene-ized phenyl ether sulfate ester salt, Alkyl diphenyl ether disulfon acid chloride, etc. are mentioned. As the above-mentioned dispersing agent, polyacrylic acid soda salt, the ammonium salt of the half ester of a styrene maleic acid copolymer, etc. are mentioned, for example. As the above-mentioned water resin, the soda salt of polyacrylic ester, etc. are mentioned, for example.

0051In another embodiment, before mixing the above-mentioned compound (B) with the above-mentioned polyamine resin (A), a compound (B) may be distributed in the dispersing element of different resin from polyamine resin (A). As a dispersing element of the above-mentioned resin, an emulsion, dispersion, etc. of the emulsion of an acrylic resin, dispersion, and urethane resin are mentioned, for example. Thus, if a compound (B) is beforehand distributed in the dispersing element of resin, polyamine resin (A) and a compound (B) can be mixed, without using a special mixed device, and the paint constituent excellent in dispersibility can be obtained. As a result, polyamine resin (A) and a compound (B) can be made to react mutually efficiently.

0052D. Coating method<br />The distemper constituent of the present invention can be painted to arbitrary suitable coated objects. Typically, it is the iron surface.

0053As a coating method of the distemper constituent of the present invention, brush coating, an air spray, an airless spray, roller paint, etc. are mentioned, for example.

0054As an amount of applications of the distemper constituent of the present invention, it can set to the arbitrary suitable amounts of applications according to a use. Generally, it is 10-300g/m.^２It comes out and a certain thing is preferred.

0055Arbitrary suitable drying methods may be adopted as a drying method of the distemper constituent of the present invention. Preferably, they are natural seasoning or drying by heating. That is, the distemper constituent of the present invention may be used as a normal temperature hardening type paint constituent, and may be used as a heating hardening type paint constituent. In the case of natural seasoning, drying time is one week or more still more preferably preferably for 24 hours or more.

<p num="0056">Hereinafter, although an example explains the present invention in detail, the present invention is not limited to these examples. Unless it writes clearly in particular, the part and % in an example are a weight standard. The evaluation criteria in an example are as follows.</p><p num="0057">(Coat state)<br />Viewing estimated abnormalities in a coat, such as gloss of a coat, transparency, and Swordfish, for the glass board which painted and dried the paint obtained by the example and the comparative example under 25 (24 hours).<br />Gloss O: High thing of gloss<br />: The thing of a [ half ] or a grade<br />x: That dim<br />　<br />Transparency O: What does not completely or almost have muddiness<br />: What has muddiness a little<br />x: The large thing of muddiness<br /> <br />Abnormalities in a coat O: What does not completely or almost have Swordfish<br />: What has Swordfish for a while<br />x: What has Swordfish in the whole surface<br />(Hardenability) <br />After painting and drying the paint obtained by the example and the comparative example to a glass board under 25 and 5 (24 hours) and obtaining a coat, the coat concerned is set under the respectively same temperature as the time of paint and dryness, It rubbed with the gauze in which methyl ethyl ketone (MEK) was included, and measured the number of times of a round trip until glass foundation is exposed. The notation of "&gt;200" in front means that glass foundation was not exposed in addition even if it went back and forth 200 times. The number of times of a round trip until it exposes is [ 100 times or more of coats ] success.<br />(Anti-corrosiveness) <br />It is 200g/m to a sandblast board about the paint obtained in the example.^２The specimen was obtained by applying with the brush and making it dry for seven days at 20 so that it might become. The cycle corrosion test provided in JIS K 5600 7-7 was carried out to the specimen concerned, and the coat state of 120 cycles after was checked based on the following standard.<br />The rate of the rust area which arose in the coat to the surface of a specimen<br />O : less than 0.05%<br />O : 0.05% or more, less than 0.1%<br />: Less than [ more than 0.1%0.3% ]<br />x: More than 0.3%</p><p num="0058">[Example 1 of manufacture] Production of polyamine resin (epoxy system polyamine resin)<br />702 copies of epoxy resins of epoxy equivalent 188 compounded from bisphenol A and epichlorohydrin to the reaction vessel provided with the stirrer, the condensator, the nitrogen introducing pipe, and the thermometer, 269 copies of bisphenol A, 108 copies of dimer acid, and 190 copies of methyl isobutyl ketone (henceforth "MIBK") are taught, and it was made to react at 117 under 1 copy of Benzyl dimethylamine existence until it became epoxy equivalent 1270. Then, 255 copies of ketimine compounds (73 mass %MIBK solution) of aminoethylethanolamine were added, and it was made to react at 117 for 1 hour. Then, it diluted until it became 75% of non-volatile matter content by MIBK, and epoxy system polyamine resin of number average molecular weight 2400 and amine this quantity 1184 was obtained.</p><p num="0059">[Example 2 of manufacture] Emulsification of epoxy system polyamine resin<br />Added acetic acid to the epoxy system polyamine resin obtained in example 1 of manufacture, it is made to become 20.0% (neutralization rate to the amine machine of resin) of a neutralization rate, and ion exchange water was added and diluted. Then, the mixture of MIBK and water was removed under decompression until solid content became 40 mass %, and emulsion I was prepared.</p><p num="0060">[Example 3 of manufacture] Production of polyamine resin (acrylic polyamine resin)<br />670 copies of MIBK(s) were taught to the reaction vessel provided with a stirrer, the condensator, the nitrogen introducing pipe, the thermometer, and the dropping funnel, and it Temperature rising(ed) at 110 . The dropping funnel was used for this reaction vessel, and the solution which consists of 540 copies of styrene, 400 copies of acrylic acid n-butyl, 140 copies of glycidyl methacrylate, 100 copies of MIBK(s), and 20 copies of t-butyl peroctoate was dropped at it over 3 hours. After holding at 110 over [ after / the end of dropping ] 30 minutes, the solution which consists of two copies of t-butyl peroctoate and 50 copies of MIBK(s) was dropped in 30 minutes. After this end of dropping, the reaction was made to continue at 110 and the acrylic resin varnish of 60% of the non-volatile matter content containing an epoxy group was obtained for 1 hour. Added 255 copies of ketimine compounds (73 mass %MIBK solution) of aminoethylethanolamine to 1920 copies of obtained varnishes, it was made to react to them at 117 for 1 hour, and acrylic polyamine resin of number average molecular weight 10000 and amine this quantity 1184 was obtained.</p><p num="0061">[Example 4 of manufacture] Emulsification of acrylic polyamine resin<br />Added acetic acid to the acrylic polyamine resin obtained in example 3 of manufacture, it is made to become 20.0% (neutralization rate to the amine machine of resin) of a neutralization rate, and ion exchange water was added and diluted. Then, the mixture of MIBK and water was removed under decompression until solid content became 40 mass %, and emulsion II was prepared.</p><p num="0062">[Example 5 of manufacture] Production of polyamine resin (epoxy system polyamine resin)<br />742 copies of epoxy resins of epoxy equivalent 188 compounded from bisphenol A and epichlorohydrin to the reaction vessel provided with the stirrer, the condensator, the nitrogen introducing pipe, and the thermometer, 336 copies of bisphenol A and 190 copies of MIBK(s) are taught, and it was made to react at 117 under 1 copy of Benzyl dimethylamine existence until it became epoxy equivalent 1270. Then, 350 copies of ketimine compounds (73 mass %MIBK solution) of diethylene triamine were added, and it was made to react at 117 for 1 hour. Then, 27 copies of ion exchange water and 188 copies of neo decanoic acid glycidyl ester (car Jura E10-P) were taught, and it was made to react at 100 for 2 hours. Then, it diluted until it became 75% of non-volatile matter content by MIBK, and epoxy system polyamine resin of number average molecular weight 2600 and amine this quantity 947 was obtained.</p><p num="0063">[Example 6 of manufacture] Emulsification of epoxy system polyamine resin<br />Added acetic acid to the epoxy system polyamine resin obtained in example 5 of manufacture, it is made to become 20.0% (neutralization rate to the cationic machine of resin) of a neutralization rate, and ion exchange water was added and diluted. Then, the mixture of MIBK and water was removed under decompression until solid content became 40 mass %, and emulsion III was prepared.</p><p num="0064">[Example 1]<br />While agitating by Disper to the emulsion I2960 copy obtained in example 2 of manufacture as polyamine resin (A), After adding 118 copies of Zypro pyrene glycol n-butyl ether (DPnB), while carrying out Disper churning further, 392 copies of ethoxy Turn trimethylolpropane triacrylate (EO20mol) ( brand name by the Aranaka village chemicals company "AT-20E") was added as a compound (B), and it agitated for 10 minutes, and obtained the clear paint. The obtained paint was painted to the glass board by a 6-mil applicator under environment (25 and 5 ), was dried under the same environment as the time of paint for 24 hours, and the coat was obtained. Then, the coat state and hardenability of the coat which were acquired were evaluated. A result is shown in Table 2.</p><p num="0065">[Examples 2-10]<br />The compound (B) was replaced with 392 copies of ethoxy Turn trimethylolpropane triacrylate (EO20mol), and the coat was obtained like Example 1 except having used the compound (B) shown in Table 1 by the content shown in Table 2. Then, the coat state and hardenability of the coat which were acquired were evaluated. A result is shown in Table 2.</p><p num="0066">[Example 11]<br />Polyamine resin (A) was replaced with emulsion I, and the coat was obtained like Example 10 except having used emulsion II obtained in example 4 of manufacture. Then, the coat state and hardenability of the coat which were acquired were evaluated. A result is shown in Table 2.</p><p num="0067">[Example 12]<br />Agitated 159 copies of ion exchange water, and new call 740 (NIPPON NYUKAZAI CO., LTD. make, Nonion system emulsifier) 16 copy in Disper, it was made to dissolve uniformly, and emulsifier solution was adjusted. Then, 143 copies of ethoxy Turn trimethylolpropane triacrylate (EO3mol) which is a compound (B) is added, and it agitated for 10 minutes and made it rough-distribute in Disper. It distributed until it became 350 nm of mean particle sizes in the ultrasonic homogenizer, and the emulsification thing of the compound (B) was obtained.<br />While agitating by Disper to 2367 copies of emulsions III obtained in example 6 of manufacture as polyamine resin (A), After adding 118 copies of Zypro pyrene glycol n-butyl ether (DPnB), further, carrying out Disper churning, 318 copies (143 copies of content of a compound (B)) of emulsification things of the compound (B) obtained previously were added, and it agitated for 10 minutes, and obtained the clear paint. About the obtained paint, the coat was obtained like Example 1. Then, the coat state and hardenability of the coat which were acquired were evaluated. A result is shown in Table 2.</p><p num="0068"><tables num="1"><img file="WO2010035641A1_D0001.tif" /></tables></p><p num="0069"><tables num="2"><img file="WO2010035641A1_D0002.tif" /></tables></p><p num="0070">[Example 13]<br />100 copies of tap water, DISPERBYK-190 ( pigment agent by big Chemie) 34 copy, BYK-019( antifoaming agent by big Chemie)2 copy, 170 copies of calcium carbonate, 185 copies of titanium oxide, and the pigment dispersion constituent consisting of two copies of calcium series antirust paints were distributed for 30 minutes in Disper. Subsequently, the emulsion I450 copy obtained in example 2 of manufacture as polyamine resin (A), 18 copies of DPnB(s), and Adecanol UH-420 (product [ made by Adeka ] meeting type thickener) 10 copy were added, and it mixed, and considered it as base resin paint liquid. Agitating by Disper, what dissolved 41 copies of propoxy-ized bisphenol A diacrylate (PO4mol) in 41 copies of DPnB(s) as a compound (B) was added, and it agitated for 10 minutes, and obtained the enamel coating. The obtained paint was painted to the glass board by a 6-mil applicator under environment (25 and 5 ), was dried under the same environment as the time of paint for 24 hours, and the coat was obtained. Then, the coat state, hardenability, and anti-corrosiveness of the obtained coat were evaluated. A result is shown in Table 3.</p><p num="0071">[Example 14]<br />It replaces with 41 copies of propoxy-ized bisphenol A diacrylate (PO4mol), The coat was obtained like Example 13 except having used 33 copies of ethoxy Turn glyceryl triacrylate (EO9mol) ( brand-name [ A-GLY-9 ] "E" compound (B) No.6 by the Aranaka village chemicals company). Then, the coat state, hardenability, and anti-corrosiveness of the obtained coat were evaluated. A result is shown in Table 3.</p><p num="0072">[Example 15]<br />It replaced with the emulsion I450 copy obtained in example 2 of manufacture as polyamine resin (A), and obtained the coat like Example 13 except having used 450 copies of emulsions II obtained in example 4 of manufacture. Then, the coat state, hardenability, and anti-corrosiveness of the obtained coat were evaluated. A result is shown in Table 3.</p><p num="0073">450 copies of emulsions III which replaced with the emulsion I450 copy obtained in example 2 of manufacture, and were obtained in example 6 of manufacture were used as polyamine resin (A), And as a compound (B), 41 copies of propoxy-ized bisphenol A diacrylate (PO4mol) is replaced with what was dissolved in 41 copies of DPnB(s), The coat was obtained like Example 13 except having used 61 copies of emulsification things of the ethoxy Turn trimethylolpropane triacrylate (EO3mol) manufactured in Example 12. Then, the coat state, hardenability, and anti-corrosiveness of the obtained coat were evaluated. A result is shown in Table 3.</p><p num="0074"><tables num="3"><img file="WO2010035641A1_D0003.tif" /></tables></p><p num="0075">[Comparative example 1]<br />The coat was obtained like Example 1 except not having used a compound (B). Then, the coat state and hardenability of the coat which were acquired were evaluated. A result is shown in Table 4.</p><p num="0076">[Comparative example 2]<br />It replaced with the compound (B) and obtained the coat like Example 1 except having used 2100 copies of urethane acrylate with molecular weight 4200, viscosity 30,000 mPa-s, and two functional groups (UA-W2 Shin-Nakamura Chemical Co., Ltd. make). Then, the coat state and hardenability of the coat which were acquired were evaluated. A result is shown in Table 4.</p><p num="0077">[Comparative example 3]<br />It replaced with the compound (B) and obtained the coat like Example 1 except having used 94 copies of dipentaerythritol hexaacrylate with molecular weight 562, viscosity 6600 mPa-s, and six functional groups. Then, the coat state and hardenability of the coat which were acquired were evaluated. A result is shown in Table 4.</p><p num="0078">[Comparative example 4]<br />It replaced with the compound (B) and obtained the coat like Example 1 except having used 255 copies of screw phenol type epoxy resins with molecular weight 510, viscosity 100,000 mPa-s, and two acrylyl groups (Lipoxy VR-77 Showa High Polymer Co., Ltd. make). Then, the coat state and hardenability of the coat which were acquired were evaluated. A result is shown in Table 4.</p><p num="0079"><tables num="4"><img file="WO2010035641A1_D0004.tif" /></tables></p><p num="0080">[Comparative example 5]<br />Adeka resin EM-101-50 (water epoxy resin emulsion by Adeka; epoxy equivalent-amount 1000, 50% of solid content) 1000 copy and 50 copies of DPnB(s) were mixed, and it was considered as base resin paint liquid.<br />Next, the Sanmide WH-900 (air products company make trans fat fellows polyamine and 60% of non-volatile matter content amine value 220) 200 copy was added to base resin paint liquid as a hardening agent, and it mixed by Disper churning. The obtained paint was painted to the glass board by a 6-mil applicator under environment (25 and 5 ), was dried under the same environment as the time of paint for 24 hours, and the coat was obtained. When the hardenability of the obtained coat was evaluated, the hardenability at 25 is good (MEK-proof &gt; 200 times), and it had not hardened it at all in 5 (it melted easily in MEK).</p><p num="0081">According to the distemper constituent of the present invention, with conventional distemper (comparative example 5), sufficient hardenability under the low temperature which was not acquired can be acquired so that more clearly than Table 2 and 3.</p><p num="0082">If epoxy system polyamine resin is used as polyamine resin so that more clearly than the result (Table 3) of Examples 13, 14, and 16, in addition to cold cure nature, the distemper constituent in which the coat which shows the outstanding anti-corrosiveness is obtained can be obtained.</p>

0083The distemper constituent of the present invention may be used as a construction paint and a heavy anticorrosion paint suitably for anticorrosives, such as a bridge, the building exterior, a floor, and building materials, Sheeler, a primer, etc.