WO2006082623A1

WO2006082623A1 - Process for production of polyurethane emulsion for aqueous one-package coating materials

Info

Publication number: WO2006082623A1
Application number: PCT/JP2005/001385
Authority: WO
Inventors: Naotaka Izumi; Takeshi Morishima; Iku Ohki; Mitsushige Ikemoto
Original assignee: Nippon Polyurethane Industry Co., Ltd
Priority date: 2005-02-01
Filing date: 2005-02-01
Publication date: 2006-08-10

Abstract

[PROBLEMS] To provide a process for the production of a polyurethane emulsion for aqueous one-package coating materials which are safe with concern for the environment and excellent in productivity and storage stability and in the water resistance and solvent resistance of film. [MEANS FOR SOLVING PROBLEMS] A process for the production of a polyurethane emulsion for aqueous one-package coating materials, characterized by reacting an organic diisocyanate (a1) with a high-molecular polyol (a2) and a carboxyl-containing low-molecular glycol (a3) to prepare a carboxyl-containing isocyanato-terminated urethane prepolymer (A), mixing the prepolymer (A) with a nonanionic polyisocyanate (B), blocking the whole or part of the isocyanato groups of the mixture with a blocking agent (C), neutralizing the carboxyl groups contained in the system with a neutralizing agent (D), emulsifying the resulting mixture in water, and, if necessary, subjecting the mixture to chain lengthening reaction.

Description

Specification

Method for producing polyurethane emulsion for aqueous one-component coating agent

Technical field

The present invention relates to a method for producing a polyurethane emulsion for aqueous one-component coating. More specifically, the present invention relates to a process for producing a polyurethane emulsion for an aqueous one-component coating agent that is safe in consideration of the environment, and has excellent productivity, storage stability, water resistance of a coating film, and solvent resistance. .

Background art

[0002] Coating agents containing a large amount of organic solvents have adverse effects on the human body, safety and health problems such as explosion and fire, and pollution problems such as air pollution. In order to improve these problems, water-based system development has been actively conducted in recent years. On the other hand, urethane-based coating IJ shows good adhesion to various substrates. Therefore, there is an increasing demand for 7-type urethane coating agents.

[0003] In Patent Document 1, a urethane prepolymer having a carboxyl group and an isocyanate group, which becomes water-dispersible by neutralizing the carboxyl group with a basic compound, and a non-water-emulsifiable polyisocyanate are mixed. An aqueous polyurethane resin obtained by emulsifying this in water and extending the chain is shown.

[0004] Patent Document 1: Japanese Patent Laid-Open No. 7-188371

[0005] However, it has been found that the aqueous urethane resin described in Patent Document 1 still has insufficient film properties.

Disclosure of the invention

The invention's effect

[0006] According to the present invention, it is possible to provide an aqueous one-component coating agent that is safe in consideration of the environment and that is excellent in productivity, storage stability, water resistance of a coating film, solvent resistance, and the like. Problems to be solved by the invention

[0007] An object of the present invention is to provide an aqueous one-component coating agent that is safe in consideration of the environment and is excellent in productivity, storage stability, water resistance of a coating film, solvent resistance, and the like. Means for solving the problem

[0008] The present invention has been studied in order to solve the above-mentioned problems, and a polyurethane emulsion obtained by emulsifying a specific polyisocyanate in water and carrying out a chain extension reaction is an aqueous one-component coating. The present invention has been found to be suitable for the agent, and the present invention has been completed.

That is, the present invention is shown in the following (1) -one (5).

[0010] (1) An organic diisocyanate (al), a polymer polyol (a2), and a carboxyl group-containing low molecular glycol (a3) are reacted to produce a carboxyl group-containing isocyanate group-terminated urethane prepolymer (A). And nonanionic polyisocyanate (B) are mixed, then all isocyanate groups in the mixture are blocked with blocking agent (C), and carboxy groups in the system are blocked with neutralizing agent (D). After neutralizing, the mixture is emulsified in water, and a method for producing a polyurethane emulsion for an aqueous one-component coating agent.

[0011] (2) Organic diisocyanate (al), polymer polyol (a2), and carboxyl group

A low molecular weight glycol (a3) containing is reacted to produce a carboxyl group-containing isocyanate group-terminated urethane prepolymer (A), which is mixed with a non-anionic polyisocyanate (B), and then the mixture. A part of the isocyanate group is blocked with a blocking agent (C), and the carboxynole group in the system is neutralized with a neutralizing agent (D). A process for producing a polyurethane emulsion for an aqueous one-component coating agent.

[0012] (3) The production method of the above (1) or (2), which is an organic diisocyanate (al), an aliphatic diisocyanate and Z or an alicyclic diisocyanate.

[0013] (4) The production method of (1) and (3) above, wherein the polymer polyol (a2) has a carbonate skeleton or a phthalate skeleton.

(5) The nonanionic polyisocyanate (B) is an isocyanurate-modified product or a modified compound containing an isocyanurate-modified product of an aliphatic diisocyanate and / or an alicyclic diisocyanate, (1) One (4) manufacturing method.

BEST MODE FOR CARRYING OUT THE INVENTION

[0015] The present invention will be described in more detail.

Carboxanol group-containing isocyanate group-terminated urethane prepolymers constituting the present invention ( A) is obtained by reacting an organic diisocyanate (al), a high molecular polyol (a2), and a carboxyl group-containing low molecular weight darikol (a3).

[0016] The carboxylate content in (A) is preferably 0 · 1-2 mmol / g, particularly preferably 0.2-1 · 8 mmol / g. If the carboxylate content is too low, it is difficult to obtain the desired polyurethane emulsion. If it is too much, it may contribute to an increase in viscosity during emulsification and a decrease in the durability of the coating.

[0017] The organic diisocyanate (al) used in the present invention is 2, 4_tolylene diisocyanate,

2, 6_tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4, monodiphenylmethane diisocyanate, 2, A'-diphenylmethane diisocyanate, 4 , —Diphenyl ether diisocyanate, 2_nitrodiphenyl _4, A ′ —diisocyanate, 2, 2 ′ —diphenylpropane—4, A ′ —diisocyanate,

3, 3 ^; —Dimethyldiphenylmethane— 4, '—Diisocyanate, 4, —Diphenylpropyl pandiisocyanate, m-Phenylene diisocyanate, p-Phenylene diisocyanate, naphthylene 1,4-diiso Aromatic diisocyanates such as cyanate, naphthylene 1,5-diisocyanate, 3,3′-dimethoxydiphenyl 4,4′-diisocyanate, polyphenylene polymethylene polyisocyanate, crude tolylene diisocyanate Aromatic decamethylene diisocyanate, Aliphatic diisocyanate such as lysine diisocyanate, Isophorone diisocyanate, Hydrogenated tolylene diisocyanate, Hydrogenated xylene diisocyanate, Hydrogenated diphenylmethane Alicyclic diisocyanates such as isocyanate and tetramethylxylene diisocyanate Examples include sorbate. These urethane modified products

Allophanate-modified, urea-modified, biuret-modified, uretdione-modified, and isocyanurate-modified may be used in combination.

[0018] Preferred organic diisocyanates in the present invention are hexamethylene diisocyanate and isophorone diisocyanate, among which aliphatic diisocyanate and alicyclic diisocyanate are preferred, considering the strength and weather resistance of the coating. I like it.

[0019] The polymer polyol (a2) used in the present invention includes a number average molecular weight of 500-10, 00.

0, preferably f 5,000 to 5,000 polyester, polyester, polyester, polyester , Polyether polyols, polyether 'ester polyols, polycarbonate polyols, polyolefin polyols, and the like. These polymer polyols may be used alone or in combination.

[0020] Polyester polyols and polyester amide polyols include polycarboxylic acid derivatives such as polycarboxylic acids, acid esters, acid anhydrides, and acid halides, and low molecular polyols, low molecular weight polyamines, low molecular weights having a molecular weight of less than 500 (number average). It is obtained by reaction with molecular amino alcohol.

[0021] Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid and the like.

[0022] (Number average) Low molecular polyols having a molecular weight of less than 500 include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1, 4 Butanediol, 1,5-pentanediol, 1,6 xanthdiol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, 3,3-dimethylol Heptane, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2_ethyl 1,3 propanediol, 2 normal propyl 1,3 propanediol, 2 isopropyl 1,3 propane Diol, 2 Normal Butinoleol 1, 3 Propanediol, 2-Sibutinolele 1, 3 Propanediol, 2 Tertiary 1-, 3-propanediol, 2-methyl-2-ethylol, 2,2-jetinore, 1,3-propanediol, 2-ethinoreol 2-normalpropinole 1, 3-propanediol, 2—Ethinole 1—Normal Butinore 1, 3_Propanediol, 2—Ethinole _3—Ethinole _1, 4_Butanol, 2—Metinore _3—Ethinore 1,4_Butanediol, 2,3_Jetinore _1,5_Pentanediol, 2,4-Gethinole 1,5_Pentanediol, 2,3,4-Triethyl _1,5-pentanediol, Trimethylolpropane, dimethylolpropionic acid, dimethylolbutanoic acid, dimer acid Examples include diol, glycerin, pentaerythritol, and an alkylene oxide adduct of bisphenol A.

[0023] (Number average) Low molecular weight polyamines having a molecular weight of less than 500 include ethylenediamine and hexame. Examples include tylenediamine, xylylenediamine, isophorone diamine, diethylenetriamine and the like.

[0024] Examples of the low molecular weight amino alcohol having a (number average) molecular weight of less than 500 include monoethanolamine, diethanolamine, and monopropanolamine. Also, polyester polyols such as latatin polyester polyols obtained by ring-opening polymerization of cyclic ester (latatane) monomers such as _ε -force prolacton, alkyl-substituted _ε -force prolatatone, δ-valerolataton, alkyl-substituted δ-valerolataton Can also be suitably used.

[0025] Examples of the polyether polyol include polyethylene glycol, polypropylene ether polyol, and polytetramethylene ether polyol.

[0026] Examples of the polyether ester polyol include the above-described polyether polyol and the above-described polyester polyol produced by the polycarboxylic acid derivative.

[0027] Polycarbonate polyol is generally deethanol condensation reaction of low molecular weight polyol and jetyl carbonate, dephenol condensation reaction of low molecular weight polyol and diphenyl carbonate, or deethylene glycol condensation reaction of low molecular weight polyol and ethylene carbonate. Etc. Examples of the low molecular polyol used here include the low molecular polyol used to obtain the above-described polyester polyol.

[0028] Specific examples of the polyolefin polyol include a hydroxyl group-terminated polybutadiene, a hydrogenated product thereof, and a hydroxyl group-containing chlorinated polyolefin.

[0029] In view of various durability and adhesion of the polyurethane emulsion film obtained in the present invention, the polymer polyol (a2) preferably has a carbonate skeleton or a phthalate skeleton.

[0030] Examples of the low molecular weight glycol (a3) containing carboxynole group used in the present invention include 2,2-dimethylolpropionic acid, 2,2_dimethylolbutanoic acid, 2,2_dimethylolbutyric acid, 2,2- Examples include dimethylol valeric acid.

[0031] Examples of the non-anionic polyisocyanate (B) used in the present invention include non-modified polyisocyanates such as polyphenylene polymethylene polyisocyanate and crude tolylene diisocyanate, as well as the aforementioned organic diisocyanates. Urethane modified, urea modified, alofa Examples thereof include nate-modified products, biuret-modified products, uretdione-modified products, isocyanurate-modified products, and composite modified products thereof.

In consideration of various durability and adhesion of the polyurethane emulsion layer obtained by the present invention, the non-anionic polyisocyanate (B) is an aliphatic diisocyanate and / or an alicyclic diisocyanate. An isocyanurate-modified product or a complex modified product containing an isocyanurate-modified product (hereinafter collectively referred to as isocyanurate-modified non-yellowing polyisocyanate) is preferable. Hexamethylene diisocyanate is preferred as the aliphatic diisocyanate, and isophorone diisocyanate is preferred as the alicyclic diisocyanate.

[0033] The isocyanurate-modified non-yellowing polyisocyanate will be described in more detail.

The process for producing isocyanurate-modified non-yellowing polyisocyanate is as follows: 1) Add isocyanurate catalyst to aliphatic diisocyanate and Z or alicyclic diisocyanate, and then carry out the isocyanurate reaction, and then unreact 2) urethanation of the aliphatic diisocyanate and / or alicyclic diisocyanate and the low molecular polyol used to obtain the above-mentioned polyester polyol. After the reaction, an isocyanurate catalyst is added to carry out an isocyanuration reaction, and then unreacted aliphatic diisocyanate and / or alicyclic diisocyanate is removed. 3) The above 1) or 2 ) And some monoisocyanate groups of the polyisocyanate obtained by And a further urethane reaction.

[0034] Examples of the isocyanurate catalyst used in the production methods 1) and 2) include tetramethylammonium hydride mouth oxide, tetraethylammonium hydride mouth oxide, and tetraptylammonium hydride mouthpiece. Tetraalkylammonium hydride mouth such as oxide Oxide, tetramethylammonium acetate, tetraethylammonium acetate, organic weak acid salt such as tetraptylammonium acetate, trimethylhydroxypropyl ammonium hydride mouthpiece, trimethyl Trialkylhydroxyalkyl ammonium such as hydroxyethyl ammonium hydroxide and triammonium hydroxide

Muhide mouth oxide, trimethyl hydroxypropyl ammonium salt, trimethyl acetate Organic weak acid salts such as trihydroxyethyl ammonium salt, triethyl hydroxypropyl ammonium salt, triethyl hydroxyethyl ammonium salt, tertiary amine such as triethylamine, triethylenediamine, acetic acid, Examples thereof include metal salts of alkyl carboxylic acids such as caproic acid, octylic acid and myristic acid.

[0035] The amount of catalyst added in the isocyanurate reaction is preferably 10-10, OOOppm for the reaction system. The reaction rate is preferably 40% or less, more preferably 35% or less. The reaction temperature of isocyanurate is preferably 0-120 ° C, particularly preferably 20-100 ° C.

[0036] The blocking agent (C) used in the present invention is not particularly limited, and one or more kinds of known forces can be appropriately selected and used. Examples of the block group include phenol, alcohol, active methylene, mercaptan, acid amide, ratatam, acid imide, imidazole, urea, oxime, and amine compounds. .

[0037] More specifically, for example, as the blocking agent, phenol-based compounds such as phenol, cresol, ethyl phenol, butyl phenol, etc .; 2-hydroxypyridine, butyl acetone sorb, propylene glycol monomethyl ether, ethylene glycol, benzyl alcohol, Alcohol compounds such as methanol, ethanol, n-butanol, isobutanol, 2-ethyl hexanol; active methylene compounds such as dimethyl malonate, jetyl malonate, methinoacetate acetate, cetyl acetate acetate, and acetylacetone ; Mercaptan compounds such as butyl mercaptan and dodecyl mercaptan; acid amide compounds such as acetoanilide and acetic acid amide; ; Acid imide compounds such as succinimide and maleic imide; imidazole compounds such as imidazole and 2-methylimidazole; urea compounds such as urea, thiourea and ethyleneurea; formaldoxime, acetoaldoxime, Oxime compounds such as acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime; and amine compounds such as diphenylaniline, aniline, carbazole, ethyleneimine, and polyethyleneimine.

[0038] In the present invention, among the above-mentioned blocking agents, methyl ethyl ketoxime, ε-force prolatatum, and 2_ethyl hexanol are particularly preferable from the viewpoint of versatility, ease of production, and workability. [0039] Examples of the neutralizing agent (D) used in the present invention include ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, triisopropanolamine, N-methyljetanol. Amines, N-phenylethanolamines, Monoethanolamines, N, N-Dimethylethanolamines, N, N-Dethylethanolamines, Monophorins, N_Methylmorpholines, 2-Amino-2-ethyls _ Organic amines such as propanol, alkali metals such as lithium, potassium and sodium, sodium hydroxide, inorganic alkalis such as lithium hydroxide, ammonia, etc. In order to increase the temperature, it is necessary to react with a highly volatile or polyisocyanate curing agent that is easily dissociated by heat. § Mino alcohol preferably tool ammonia, trimethylolpropane Honoré amine, triethyl Chinoreamin, N, N-dimethyl § amino ethanol § Min is preferable to.

[0040] A specific manufacturing process will be described.

First, the above-mentioned organic diisocyanate (al), polymer polyol (a2), and carboxyl group-containing low molecular glycol (a3) are reacted under the conditions of hydroxyl group and isocyanate group to obtain a carboxylate group-containing isocyanate group-terminated urethane preform. Manufacture Rimmer (A). At this time, a known urethanization catalyst may be used. The reaction temperature is preferably 0-100 ° C, particularly preferably 20-90 ° C.

[0041] At the time of preparation of the prepolymer, it is preferable to dilute to an arbitrary solid content with an organic solvent that is inactive with respect to the isocyanate group in view of the stirring efficiency and the like. Examples of the organic solvent include toluene, xylene, Suzo Monore (aromatic hydrocarbon solvent manufactured by Cosmo Oil Co., Ltd.), Solvesso (aromatic hydrocarbon solvent manufactured by Exxon Chemical Co., Ltd.), etc. Aromatic solvents, aliphatic hydrocarbon additives such as hexane, alicyclic hydrocarbon solvents such as cyclohexane and isophorone, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, Ester solvents such as ethyl acetate, butyl acetate, and isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol-mono-monomethyl etherate acetate, propylene glycol 3-methylol 3-methoxybutyl acetate, ethylene glycol Glycol ether esthetics such as rutile 3_ethoxypropionate System solvent, ethylene glycol dimethyl ether, Jefferies Chile ring Ricoh Honoré dibutyltin Honoré ether Honoré, propylene glycol Honoré dibutyltin Honoré ether Honoré, dipropionate Examples include glycol ether solvents such as pyrene glycol dimethyl ether, ether solvents such as tetrahydrofuran and dioxane, and aprotic polar solvents such as N-methylpyrrolidone. The solvent may contain one kind or two or more kinds.

[0042] In the present invention, a Dalicol ether ester solvent, a glycol ether solvent, an aprotic solvent which does not exhibit a flash point even when present in an emulsion having a low vapor pressure and has a film-forming effect. Polar solvents are preferred, with glycol ether solvents and aprotic polar solvents being particularly preferred for hydrolysis resistance.

[0043] After the non-anionic polyisocyanate (B) is mixed with the obtained carboxylate group-containing isocyanate group-terminated urethane prepolymer (A), a part or all of the isocyanate group in the system is blocked ( After blocking with C), the carboxyl group is neutralized with a neutralizing agent (D). In addition, the non-anionic polyisocyanate (B) may be mixed after blocking or neutralizing the carboxyl group-containing isocyanate group-terminated urethane prepolymer. It is preferable to carry out the mixing first, because the viscosity of the mixture increases and the mixing operation with (B) becomes difficult. In addition, it is important to perform neutralization before emulsification. If neutralization is carried out at the same time as emulsification or after emulsification, precipitates and suspended matter are likely to be generated.

[0044] The mass blending ratio of (B) is preferably (A) / (B) = 100 / 10—100 / 100 with respect to (A), particularly (A) / (B) = 100 / 20—100 / 100 is preferred. If the amount of (B) is too small, the strength and durability of the coating tends to be insufficient. When (B) is too much, emulsification tends to be difficult.

[0045] The blocking reaction can be carried out according to the usual blocking reaction conditions of 20-100 ° C, preferably 30-90 ° C. At this time, a known urethanization catalyst may be used. The blocking rate is preferably 20 mol% or more, especially 30-50 mol%. If the blocking rate is too low, the strength and durability of the coating tends to be insufficient. Neutralization can be carried out according to normal neutralization reaction conditions of 20 50 ° C.

Next, the mixture is emulsified in water, and in the case of a partial block, a chain extension reaction is performed.

As chain extender during chain extension reaction, water, ethylenediamine, hexylenediamine, xylylenediamine, isophoronediamine, diethylenetriamine, N_aminoethyl N-ethanolamine, etc. (number average) Examples include low molecular weight polyamines with molecular weights less than 500 It is done.

[0047] In the case of using a low molecular weight polyamine, a method in which the polyamine is dissolved in water in advance, and this polyamine aqueous solution is added to the mixture of the above (A) and (B) to perform emulsification and chain extension reaction. For example, after the mixture of (A) and (B) described above is emulsified in water, an aqueous solution of polyamine in which polyamine is dissolved in water is added to perform a chain extension reaction.

[0048] During the chain extension reaction, since a decarbonation reaction may occur due to a reaction between the isocyanate group and water, it is important that the reaction system is not sealed.

[0049] The end point of the reaction is the time when the generation of carbon dioxide gas ceases and no isocyanate group remains. The reaction temperature during chain extension is preferably 20 50 ° C.

[0050] The average particle size of the polyurethane emulsion obtained by the present invention is preferably 500 nm or less, particularly preferably 300 nm or less. If the average particle size is too large, precipitates and suspended matter may be generated.

[0051] Additives and auxiliaries commonly used in aqueous systems can be blended with the aqueous polyurethane emulsion obtained by the present invention. Examples of such additives and auxiliaries include pigments, dyes, preservatives, antifungal agents, antibacterial agents, thixotropic agents, antiblocking agents, dispersion stabilizers, viscosity modifiers, film forming aids, and leveling agents. , Anti-gelling agents, light stabilizers, antioxidants, ultraviolet absorbers, inorganic and organic fillers, plasticizers, lubricants, antistatic agents, reinforcing materials, catalysts and the like.

[0052] The aqueous coating agent using the polyurethane emulsion obtained by the present invention will be described.

[0053] As a method of using the aqueous coating agent using the polyurethane emulsion obtained by the present invention, it is applied to a substrate, dried and heated to form a film. The temperature at which the substrate is applied is less than 80 ° C, preferably room temperature, in order to prevent sagging during application. The substrate is preferably heat-resistant because it is heat-cured after coating the coating agent. Specifically, a substrate having a heat distortion temperature of 80 ° C or higher is preferable. Examples of such base materials include metal base materials such as iron, copper, aluminum, and stainless steel, heat resistant plastics such as epoxy resin, phenol resin, polyamide resin, and polysulfone resin, ceramics, glass, concrete, and stone materials. It is done. In the present invention, a metal base material is preferred. The coating amount of the coating agent is 1 to 300 gZm ^{2 in} terms of solid content of 100% by mass. In particular, it is preferably 1 to 200 g / m ² .

[0054] As the coating method, known methods such as doctor blade, reverse roll, gravure roll, spinner coat, etastruder, spray coat, dip coat, flow coat, wire coat and the like are used.

[0055] After the coating agent is applied to the substrate, it is cured by heating at a temperature of 80 to 300 ° C, preferably 100 to 280 ° C. The heating time is preferably 10 minutes for 10 seconds, particularly preferably 15 minutes for 20 seconds. Since the present invention can develop the coating strength in a short time, an excessively long heating time not only wastes energy but also gives an unnecessary heat history to the coating agent layer.

[0056] The conventional one-pack type aqueous coating agent has a film physical property that is not always sufficient, and is particularly unsatisfactory in durability. The aqueous one-component coating agent using the polyurethane emulsion of the present invention is The film properties are comparable to the two-component type. In addition, since one liquid has sufficient physical properties, there is an advantage that a step of liquid blending immediately before use is unnecessary, and film physical properties are not deteriorated due to a blending error.

Example

[0057] The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “%” means “% by mass”.

[Production of isocyanurate-modified non-yellowing polyisocyanate]

Synthesis example 1

Capacity equipped with stirrer, thermometer, nitrogen seal tube, and condenser: A 500 ml reactor was charged with 300 g of hexamethylene diisocyanate (HDI) and 1,3_butanediol (1,3-BD) 2 After charging 8 g, the inside of the reactor was purged with nitrogen, heated to a reaction temperature of 80 ° C. with stirring, and reacted at the same temperature for 2 hours. The isocyanate content of this reaction solution was measured and found to be 48.6%. Next, 0.06 g of force potassium phosphate as a catalyst and 0.3 g of phenol as a cocatalyst were added, and an isocyanurate reaction was performed at 60 ° C. for 6 hours. To this reaction solution, 0.042 g of phosphoric acid was added as a stopper, stirred for 1 hour at the reaction temperature, free HDI was removed by thin film distillation at 120 ° C and 1.3 kPa, and isocyanurate-modified polyisocyanate. Nate NC Got 00__11. . NNCCOO——l1 is a light yellowish yellow transparent transparent liquid liquid, isosocyanate content 2211 .. 33%, viscosity of 2255 ° CC 22 ,, 220000mmPPaa '' ss, free and released HHDDII-containing content was 00 .. 33 %%. .

[[00005599]] Synthesis example 22

In a device similar to that of Synthetic Synthesis Example 11, add NNCCOO--11 to 330000 gg and a number average average molecular weight of 440000. Introduce 4488gg of nguligrico koruru, replace the inside of the reaction reactor with nitrogen nitrogen, and react the reaction while stirring and stirring. Warm the temperature to 880 ° C and allow it to react for 22 hours at the same temperature to change the temperature. Denatured polypolyisocyanate NN CCOO—-22 was obtained. . NNCCOO——22 is a light, pale yellow, yellow, transparent, clear liquid liquid, lysocyanate content 1166 .. 55%, 2255. . The viscosity of CC was 22,330000mmPPaa''ss, and the free content of HHDDII was 00..33 %%. .

[[00006600]] Synthesis example 33

After charging HHDDII330000gg into a device similar to the synthesis example example 11, the inside of the reaction reactor was replaced with nitrogen nitrogen. I did it. . Next, as a catalytic catalyst medium, power paprika phosphate kalyliumum 00 .. 0066gg, and as an auxiliary catalytic catalyst medium Fuenoenonorere 00 .. 33gg were added, The reaction was conducted at 6600 ° C for 66 hours. . 00 .. 00 4422 gg of phosphoric acid was added to the reaction reaction solution as a stopping agent, and stirred at the reaction reaction temperature for 11 hours. After that, the free and released HHDDII was removed and removed by thin-film distillation distillation under the conditions of 112200 ° CC, 11..33kkPPaa. The solubilizer modified poly (polyisoisocyanate) NNCCOO--33 was obtained. . NNCCOO——33 is a light yellowish yellow transparent transparent liquid liquid, isocyanic acid salt content 2255 .. 11%, viscosity of 2255 ° CC 11, , 220000mmPPaa '' ss, free and released HHDDII-containing content was 00 .. 33 %%. .

Example 1

Capacity equipped with stirrer, thermometer, nitrogen seal tube, and condenser: A 1,000 ml reactor was equipped with 117 · 7 g of Poly-Noroi 1 and 2, 2-dimethylololebutanoic acid (DMBA) 34 · 8 g and 75 g of dipropylene glycol dimethyl ether (DMFDG) were charged and dissolved in calo heat at 90 ° C for 10 minutes. 60. After cooling to C, 135.8 g of isophorone diisocyanate (IPDI) and 0.02 g of dioctyltin dilaurate (DOTDL) were added and reacted at 80 ° C for 2 hours to obtain a carboxyl group-containing isocyanate group-terminated prepolymer. A solution was obtained. The isocyanate content of this prepolymer solution was 3.3%. Next, 57.7 g of NCO-1 was charged and mixed uniformly, and then 10.0 g of methyl ethyl ketoxime (MEKO) was charged and reacted at 80 ° C for 1 hour. After that, 23.8 g of triethylamine (TEA) was added to neutralize the carboxyl group, and then 555 g of water was added with stirring, and the chain extension reaction with emulsified water was performed at 30 ° C. I went for 12 hours. During the reaction, generation of carbon dioxide gas was confirmed. When the presence of isocyanate groups was no longer confirmed by FT IR, filling was performed to obtain an aqueous polyurethane emulsion PU-1. The solid content of PU-1 is 35.2

%, The average particle size was 52 nm, and the viscosity at 25 ° C. was 107 mPa's.

[0062] Example 2

In the same reactor as in Example 1, 115.8 g of polyol 1-1, 34.3 g of DMBA, and 75 g of DMF DG were charged and dissolved by heating at 90 ° C. for 10 minutes. After cooling to 60 ° C, 133.6 g of IPDI was charged and reacted at 80 ° C for 3 hours to obtain a carboxyl group-containing isocyanate group-terminated prepolymer solution. The isocyanate content of this prepolymer solution was 3.3%. Next, 56.7 g of NCO-1 was charged and mixed uniformly, and then 14.8 g of MEKO was charged and reacted at 80 ° C. for 1 hour. Thereafter, 23.4 g of TEA was added to neutralize the carboxyl group, and then 555 g of water was added with stirring, and the chain extension reaction with emulsified water was performed at 30 ° C. for 12 hours. During the reaction, generation of carbon dioxide gas was confirmed. When the presence of isocyanate groups was no longer confirmed by FT IR, filling was performed to obtain an aqueous polyurethane emulsion PU-2. Solids of PU-2 is 35.1%, average particle size and the viscosity 51 nm, 25 ° C was 109mPa 's _Q

[0063] Example 9

In the same reactor as in Example 1, 112.lg of polyol 1, 33.2g of DMBA, and 75g of DMF DG were charged and dissolved by heating at 90 ° C for 10 minutes. After cooling to 60 ° C., 129.5 g of IPDI and 0.02 g of DOTDL were charged and reacted at 80 ° C. for 2 hours to obtain a carboxyl group-containing isocyanate group-terminated polymer solution. The isocyanate content of this prepolymer solution was 3.2%. Next, NCO-1 was charged with 55. Og and mixed uniformly, and then 14.3 g of ME KO was charged and reacted at 80 ° C for 1 hour. Thereafter, 22.7 g of TEA was added to neutralize the force lpoxyl group, and then 518 g of water was added and emulsified with stirring. Thereafter, an aqueous amine solution in which 5.4 g of ethylenediamine (EDA) and 0.6 g of monoethanolamine (MEA) were dissolved in 34 g of water was charged in advance, and chain extension reaction was carried out at 30 ° C. for 1 hour. When the presence of isocyanate group was no longer confirmed by FT-IR, water-based polyurethane emulsion PU-9 was obtained. The solid content of PU-9 is 35.1% and the average particle size is 205η The viscosity at m and 25 ° C was 162 mPa's.

[0064] Examples 3, 5, 6, 11

Using the raw materials shown in Tables 1 and 2, aqueous polyurethane emulsions PU-3, 5, 6, and 11 were obtained in the same manner as in Example 1.

[0065] Examples 4, 7, 8, 10, 12

Using the raw materials shown in Tables 1 and 2, aqueous polyurethane emulsions PU-4, 7, 8, 10, and 12 were obtained in the same manner as in Example 2.

[0066] Comparative Example 1

In the same reactor as in Example 1, 140.5 g of polyol-1, 41.6 g of DMBA and 75 g of DMF DG were charged and dissolved by heating at 90 ° C. for 10 minutes. After cooling to 60 ° C, 162.2 g of IPDI and 0.02 g of DOTDL were charged and reacted at 80 ° C for 2 hours to obtain a carboxyl group-containing isocyanate group-terminated polymer solution. The isocyanate content of this prepolymer solution was 3.4%. Next, 8.8 g of MEKO was charged and reacted at 80 ° C for 1 hour. Thereafter, 28.4 g of TEA was added to neutralize the carboxyl group, and then 549 g of water was added while stirring, and the chain extension reaction with emulsified water was performed at 30 ° C. for 12 hours. During the reaction, generation of carbon dioxide gas was confirmed. When the presence of isocyanate group was not confirmed by FT-IR, filling was performed to obtain an aqueous polyurethane emulsion PU-13. The solid content of PU-13 was 34.8%, the average particle size was 31 nm, and the viscosity at 25 ° C was 167 mPa's.

[0067] Comparative Example 2

In the same reactor as in Example 1, 121.7 g of polyol 1-4, 36.0 g of DMBA, and 75 g of DMF DG were charged and dissolved by heating at 90 ° C. for 10 minutes. After cooling to 60 ° C, 140.4 g of IPDI and 0.02 g of DOTDL were charged and reacted at 80 ° C for 2 hours to obtain a carboxyl group-containing isocyanate group-terminated polymer solution. The isocyanate content of this prepolymer solution was 3.3%. Next, 59.6 g of NCO-1 was charged and mixed uniformly. Thereafter, 24.6 g of TEA was charged to neutralize the carboxyl group, and then 556 g of water was added with stirring, and the chain extension reaction with emulsified water was performed at 30 ° C. for 12 hours. During the reaction, generation of carbon dioxide was confirmed. When the presence of isocyanate group was no longer confirmed by FT-IR, water-based polyurethane emulsion PU-14 was obtained. The solid content of PU-14 is 35. The average particle size was 1%, the average particle size was 51 nm, and the viscosity at 25 ° C was l lOmPa's.

[0068] Comparative Example 3

In the same reactor as in Example 1, 115.8 g of polyol 1-1, 34.3 g of DMBA, and 75 g of DMF DG were charged and dissolved by heating at 90 ° C. for 10 minutes. After cooling to 60 ° C., 133.6 g of IPDI and 0.02 g of DOTDL were charged and reacted at 80 ° C. for 2 hours to obtain a carboxyl group-containing isocyanate group-terminated polymer solution. The isocyanate content of this prepolymer solution was 3.3%. Next, 56.7 g of NCO-1 was charged and mixed uniformly, and then 14.8 g of ME KO was charged and reacted at 80 ° C. for 1 hour. Thereafter, an aqueous amine solution in which 23.4 g of TEA was dissolved in 555 g of water was charged in advance with stirring, and an emulsification / chain extension reaction was carried out at 30 ° C. for 12 hours while neutralizing. During the reaction, generation of carbon dioxide gas was confirmed. When the presence of isocyanate group was no longer confirmed by FT_IR, filling was carried out to obtain an aqueous polyurethane emulsion PU-15. Since precipitation was confirmed in PU-15, further evaluation was not performed.

[0069] Comparative Example 4

In the same reactor as in Example 1, 100 g of DMFDG and 313 · Og of NCO-1 were charged and mixed uniformly, and then 41.3 g of MEKO was charged and reacted at 80 ° C. for 1 hour. Thereafter, 570 g of water was charged with stirring, and the chain extension reaction with emulsified water was performed at 30 ° C. for 12 hours. During the reaction, generation of carbon dioxide gas was confirmed. When the presence of isocyanate group was no longer confirmed by FT-IR, water-based polyurethane emulsion PU-16 was obtained. Since a precipitate of PU-16 was confirmed, further evaluation was not performed.

[0070] Comparative Example 5

In the same reactor as in Example 1, 100 g of DMFDG and 32.6 g of NCO-2 were charged and mixed uniformly, and then 32.9 g of MEKO was charged and reacted at 80 ° C. for 1 hour. Thereafter, 566 g of water was charged with stirring, and the chain extension reaction with emulsified water was performed at 30 ° C. for 12 hours. During the reaction, generation of carbon dioxide gas was confirmed. When the presence of isocyanate groups was no longer confirmed by FT-IR, water-based polyurethane emulsion PU-17 was obtained. The solid content of PU-17 is 35.0%, the average particle size is 200nm, 25. The viscosity of C was lOmPa's. [0071] Tables 11 and 13 show the charged amounts of raw materials and production results of Examples and Comparative Examples.

[0072] [Table 1]

[0073] [Table 2]

Out 1

8 9 1 0 1 1 1 2 Polymer polyol (g)

Polyol 1 1 115.5 112.1

Polyol 1 2 95.0

Polyol 1 3 95.0 Polyol 4 4 115.8 Low molecular weight glycol (g)

DMB A 34.2 33.2 28.1 28.1 34.3 Organic diisocyanate (g)

I P D I 133.3 129.5 109.7 109.7 133.6 Urethane catalyst (g)

DO T D L 0.02 0.02 Diluent (g)

DM F DG 75 75 100 100 75 Prepolymer solution isocyanate content (¾) 3.3 3.2 2.9 2.9 3.3 Non-anionic polyisocyanate (g)

N CO- 1 55.0 58.2 58.2 56.7

N CO- 3 56.6

Prepolymer / Nonionic Polyisocyanate 100/20 100/20 100/25 100/25 100/20 Blocking agent (g)

ME KO 16.1 14.3 13.7 13.7 14.8 Blocking rate (¾) 30 30 30 30 30 Neutralizing agent (g)

T EA (added before emulsification) 23.3 22.7 19.2 19.2 23.4 Dispersion medium ■ Chain extender (g)

Water 556 518 584 584 555 A Dispersion medium Chain extender (g)

Wed 34

Chain extender (g)

Water EDA 5.4

Dissolution stop agent (g)

Liquid M E A 0.6

Manufacturing result

Name of aqueous polyurethane resin PU-8 PU-9 PU-10 PU-11 PU-12 Appearance Good Good Good Good Good Solid content 0 34.9 35.1 30.0 30.1 34.9

Viscosity at 25 ° C (mPa's) 107 205 17 21 110 Average particle size (nm) 48 162 131 74 53 Storage stability Good Good Good Good Good 3] Comparison

1 2 3 4 5 Polymer polyol (g)

Polyol 1 1 140.5 115.8

Polyol — 4 121.7

Carboxyl group-containing low molecular weight glycol (g)

DMB A 41.6 36.0 34.3

Organic diisocyanate (g)

I P D I 162.2 140.4 133.6

Urethane catalyst (g)

DO T D L 0.02 0.02 0.02

Diluent (g)

DM F DG 75 75 75 100 100 Prepolymer solution isocyanate content 3.4 3.3 3.3

Non-anionic polysoicate (g)

N CO- 1 59.6 56.7 313.0

N CO-2 320.6 Prepolymer / non-anionic polyisocyanate 100/0 100/20 100/20 0/100 0/100 Blocking agent (g)

M E KO 8.8 14.8 41.3 32.9 Blocking rate (¾) 30 0 30 30 30 Neutralizing agent (g)

T EA (added before emulsification) 28.4 24.6

T EA (aqueous solution added) 23.4

Dispersion medium Chain extender (g)

Water 549 556 555 570 566 Manufacturing result

Water-based polyurethane emulsion PU-13 PU-14 PU-15 PU-16 PU-17 Appearance Good Good Bad Bad Good Solid (¾) 34.8 35.1 ― ― 35.0

Viscosity at 25 ° C (mPa-s) 167 110 ― ― 10 Average particle size (nm) 31 51 ― ― 200 Storage stability Good Good ― ― Good Example 1 1-12, Comparative example 1 1-5, Table 1 1 3 In

Polyol 1

Polycarbonatediol with a number average molecular weight of 500 obtained from 1,6-hexanediol and jetyl carbonate

Polyol 1 2:

Polyester diol with a number average molecular weight of 500 obtained from ethylene glycol and mixed dicarboxylic acid of terephthalic acid / isophthalic acid = 1/1 (molar ratio) Polyol—3:

Polyester diol with a number average molecular weight of 500 obtained from a mixed dicarboxylic acid of ethylene glycol / neopentyl glycol = 1/1 (molar ratio) and terephthalic acid / isophthalic acid = 1/1 (molar ratio)

Polio I nore _4:

Polyester Noregio Monore obtained from 1,6-hexanediol and adipic acid with a number average molecular weight of 500

DMBA:

2, 2_dimethylolbutanoic acid

IPDI:

Isophorone diisocyanate

DOTDL:

Dioctyltin dilaurate

DMFDG:

Dipropylene glycol dimethyl ether

MEKO:

Methylethyl ketoxime

TEA:

Tolytilamine

EDA:

Ethylenediamine

MEA:

Monoethanolamine

* Storage stability test

The appearance after adding 30 g of water to 100 g of the obtained aqueous polyurethane emulsion was evaluated. “Good” if there is no change in appearance.

[Evaluation of aqueous one-component coating agent]

Application Example 1 PU-1 was applied to an aluminum plate to a dry film thickness of 10 μm, allowed to stand at room temperature for 2 hours, and baked at 220 ° C. for 150 seconds to form a film. Got. The following evaluation tests were performed using this evaluation sample. The results are shown in Table 4. Pencil hardness test

The pencil drawing force of JIS K5400, the manual strength of the threshold test, were performed according to the method.

Water resistance test

Evaluation Sampnore was immersed in warm water at 50 ° C for 240 hours to evaluate the appearance of the coating.

Solvent resistance test

Absorbent cotton was soaked with methyl ethyl ketone and the surface of the coating was rubbed 200 times to evaluate the appearance of the coating.

[0077] Application Example 2-12, Application Comparative Example 1 1 3

PU-2-14 and 17 were evaluated in the same manner as in Application Example 1. The results are shown in Tables 4 and 5.

[0078] [Table 4]

[0079] [Table 5]

All of the aqueous one-part coating agents using the aqueous polyurethane emulsion of the examples gave good results. On the other hand, in the comparative example, when PU-2 and PU-13 are compared, PU-13, which does not use non-anionic polyisocyanate, has poor film hardness and durability. It turned out to be sufficient. In addition, comparing PU-12 and PU-14, it was found that PU-14, which was not blocked, had insufficient film hardness. It was also found that PU-17 without prebolimer has insufficient film hardness and water resistance.

Claims

The scope of the claims

[1] An organic diisocyanate (al), a high molecular polyol (a2), and a low molecular weight glycol (a3) containing a carboxynole group are reacted to produce a carboxyl group-containing isocyanate-terminated urethane prepolymer (A). And non-anionic polyisocyanate (B) are mixed, then all isocyanate groups in the mixture are blocked with blocking agent (C), and the carboxylate group in the system is converted to neutralizing agent (D). And then neutralizing the mixture, and then emulsifying the mixture in water. A method for producing a polyurethane emulsion for an aqueous one-component coating agent.

[2] An organic diisocyanate (al), a high-molecular polyol (a2), and a low-molecular-weight glycol (a3) containing a carboxyl group are reacted to produce a carboxyl group-containing isocyanate group-terminated urethane prepolymer (A). And nonanionic polyisocyanate (B) are mixed, and then a portion of the isocyanate group of the mixture is blocked with a blocking agent (C), and the carboxylate group in the system is neutralized with a neutralizing agent (D). A method for producing a polyurethane emulsion for an aqueous one-component coating agent, wherein the mixture is neutralized with water and then the mixture is emulsified in water to carry out a chain extension reaction.

[3] Organic diisocyanate (al) power The production method according to claim 1 or 2, wherein the diisocyanate is an aliphatic diisocyanate and / or an alicyclic diisocyanate.

[4] Polymer polyol (a2) force The production method according to any one of claims 1 to 3, wherein the polymer polyol has a carbonate skeleton or a phthalate skeleton.

[5] The non-anionic polyisocyanate (B) is an isocyanurate-modified product or a complex-modified product containing an isocyanurate-modified product of an aliphatic diisocyanate and Z or an alicyclic diisocyanate. 4. The production method according to 1 above, wherein any force from 1 to 4.