KR20210125673A - Water dispersed polyurethane resin composition and the method preparing the same - Google Patents

Abstract

The present invention relates to an aqueous polyurethane dispersion and a method for preparing the same. More specifically, the present invention relates to an aqueous polyurethane dispersion, from which a polyurethane resin having excellent flame retardancy, thermal stability and low gloss effect, but also excellent mechanical properties, can be obtained, by preparing an aqueous polyurethane dispersion including a flame-retardant polyol containing phosphorus, and a method for preparing the same.

Description

Polyurethane aqueous dispersion and manufacturing method thereof

The present invention relates to an aqueous polyurethane dispersion and a method for preparing the same. Specifically, the present invention relates to a polyurethane aqueous dispersion that can obtain a polyurethane resin having excellent flame retardancy, thermal stability and matte effect, while also having excellent mechanical properties, by preparing a polyurethane aqueous dispersion including a flame-retardant polyol containing phosphorus, and It relates to a manufacturing method thereof.

Water-dispersed polyurethane resin can be widely applied to general coatings and textile coatings, as well as vehicles and adhesives for paints, based on the excellent elongation, elasticity, and durability of existing polyurethanes. In addition, the water-dispersible polyurethane resin is characterized by introducing an internal emulsifier to induce dispersion and dissolution of the urethane polymer using water as a medium. It has the advantage of being eco-friendly because there is little generation of volatile organic compounds (VOCs).

Conventional water-dispersed polyurethane is mainly developed as a coating and adhesive to improve the performance, but as it is widely applied to the surface treatment of the adherend, in addition to the high physical properties of the adherend, in order to prevent possible fire propagation in the material. Consideration of flame retardant performance is increasing.

In the conventional polyurethane resin composition, flame retardancy was secured by applying a composition containing a polymer resin containing halogen, aluminum hydroxide, and inorganic material containing phosphorus. In the case of the inorganic material, there was a problem in that it was difficult to secure sufficient flame-retardant performance due to a low proportion of the adhesive.

Therefore, there is a need for research and development for a new water-dispersible polyurethane resin and a method for manufacturing the same, which can secure flame retardant performance including inorganic materials, and can also prevent deterioration of mechanical properties including inorganic materials.

Republic of Korea Patent Publication No. 10-2019-0136281 (2019.12.10.)

An object of the present invention is to provide a polyurethane aqueous dispersion capable of preventing deterioration of mechanical properties including phosphorus and excellent flame retardancy and thermal stability by including phosphorus in the polyurethane structure, and a method for producing the same do it with

In addition, an object of the present invention is to provide an environmentally friendly polyurethane aqueous product and a method for manufacturing the same, which do not use an organic solvent, and generate less volatile organic compounds (VOCs).

In addition, an object of the present invention is to provide a polyurethane aqueous dispersion that can be used as a matte coating agent due to the matte effect and a method for producing the same.

One aspect of the present invention is a polyurethane aqueous product introduced with an ionic group, wherein the polyurethane is prepared from a polyurethane prepolymer polymerized including a flame retardant polyol containing phosphorus, a polycarbonate-based diol, and a polyisocyanate. It provides a water product.

In one aspect, the polyurethane may be prepared by reacting the polyurethane prepolymer with a chain extender.

In one embodiment, the aqueous polyurethane product introduced with the ionic group may be prepared by reacting dimethylol propionic acid, which is a compound having an ionic group, with the polyurethane prepolymer.

In one embodiment, the aqueous polyurethane product introduced with the ionic group may be neutralized with a neutralizing agent.

In one embodiment, the flame-retardant polyol containing phosphorus may be of Formula 1 below.

[Formula 1]

(n is an integer from 1 to 50.)

In one embodiment, the urethane prepolymer may be prepared by including 2 parts by weight to 15 parts by weight of a flame-retardant polyol containing phosphorus based on 100 parts by weight of a polycarbonate-based diol.

Another aspect of the present invention comprises the steps of preparing a urethane prepolymer by polymerizing a flame retardant polyol containing phosphorus, a polycarbonate-based diol, and a polyisocyanate; preparing a urethane prepolymer having an ionic group by introducing a compound having an ionic group into the urethane prepolymer; After neutralizing the urethane prepolymer having an ionic group with a neutralizing agent, dispersing by adding water; After the dispersing step, reacting by adding a chain extender; It is to provide a method for producing a polyurethane aqueous product comprising a.

In another embodiment, the flame-retardant polyol containing phosphorus may be of Formula 1 below.

[Formula 1]

(n is an integer from 1 to 50.)

In another embodiment, the compound having an ionic group may be dimethylol propionic acid.

Another aspect of the present invention is to provide a water-dispersible polyurethane resin having a tensile strength of 20 MPa or more.

In another embodiment, the water-dispersible polyurethane resin may have a particle size of 300 nm to 800 nm.

The present invention has the advantage of being able to significantly improve flame retardancy and thermal stability by including phosphorus in the polyurethane structure, and can prevent deterioration of mechanical properties including phosphorus.

In addition, since water is used as an organic solvent when synthesizing the conventional polyurethane, the generation of volatile organic compounds (VOCs) is small, so that an environmentally friendly polyurethane aqueous product can be provided.

In addition, since it has a matte effect, there is an advantage that it can be used as a matte coating agent.

1 is an FT-IR graph that can confirm whether the polyurethane aqueous product is synthesized.

Hereinafter, the present invention will be described in more detail. However, the following specific examples or examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is for the purpose of effectively describing particular embodiments only and is not intended to limit the invention.

Also, the singular forms used in the specification and appended claims may also be intended to include the plural forms unless the context specifically dictates otherwise.

In addition, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

An object of the present invention is to provide a polyurethane aqueous dispersion and a method for producing the same, which are excellent in flame retardancy and thermal stability by being included in the polyurethane structure, and at the same time, which can prevent deterioration of mechanical properties including phosphorus. In addition, the present invention has the advantage that it is environmentally friendly because it does not use an organic solvent by preparing polyurethane as an aqueous dispersion, and it is eco-friendly as there is little generation of volatile organic compounds, and it can be used for matte coating.

One aspect of the present invention is a polyurethane aqueous product having an ionic group introduced therein, wherein the polyurethane is prepared from a polyurethane prepolymer polymerized including a flame retardant polyol containing phosphorus, a polycarbonate-based diol, and a polyisocyanate. To provide an aqueous urethane product.

Hereinafter, the present invention will be described in detail.

In one embodiment, the polyurethane prepolymer is polymerized including a flame-retardant polyol containing phosphorus, a polycarbonate-based diol, and a polyisocyanate, and the flame-retardant polyol containing phosphorus may be of Formula 1 below.

[Formula 1]

(n is an integer from 1 to 50.)

The flame-retardant polyol containing phosphorus represented by Formula 1 is prepared according to the following method. The method for preparing the flame-retardant polyol containing phosphorus may be prepared by polycondensation of phenyl phosphonic dichloride and ethylene glycol, preferably solution polymerization. After the polycondensation reaction, filtering the reactant to remove salts; and removing impurities from the reactant from which the salt has been removed by using an extraction solvent; and washing the reactant from which the impurities are removed with an organic solvent and vacuum drying. The reaction molar ratio of the phenylphosphonic dichloride and the ethylene glycol may be 1:1 to 2. In addition, the extraction solvent is water, dichloromethane, anhydrous or hydrous lower alcohol having 1 to 4 carbon atoms, propylene glycol, butylene glycol, glycerin, acetone, ethyl acetate, chloroform, butyl acetate, diethyl ether, hexane, and these It may be any one selected from the group consisting of mixtures. The organic solvent may be any one ether-based organic solvent selected from the group consisting of tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl ether, and dibutyl ether.

In the flame-retardant polyol containing phosphorus, n is an integer of 1 to 50, preferably 15 to 45. Flame-retardant polyols containing phosphorus having a repeating unit in the above range are more preferred because they have excellent thermal stability and flame retardancy, while also improving tensile strength and having a matting effect.

The polycarbonate-based diol is a reaction product of a polyester glycol such as polycaprolactone polyol and an alkylene carbonate; and a reaction product of the reaction mixture obtained after reacting ethylene carbonate with a polyhydric alcohol and organic dicarboxylic acid. Specific examples include 1,3-propanediol, 1,4-butanediol, 1,6 - Diols such as hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol and/or polytetramethylene glycol, and phosgene, diallyl carbonate (eg, diphenyl carbonate) or cyclic carbonate (eg, propylene carbonate) ) and the like, and specific reaction products include polyhexamethylene carbonate diol, 3-methyl-1,5-pentanediol carbonate diol, and the like. By using the polycarbonate-based diol, thermal stability and tensile strength are improved, and when prepared as a water-dispersible polyurethane with the phosphorus-containing flame-retardant polyol, there is an effect of increasing water dispersibility. Using polyether-based diol, etc. more preferred than

The said polyisocyanate is not specifically limited, The polyisocyanate compound which has a diisocyanate compound or 3 or more isocyanate groups may be sufficient. Examples of the diisocyanate compound include tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3' - Aromatic diisocyanate, such as dimethyldiphenyl-4,4'- diisocyanate, dianisidine diisocyanate, and tetramethylxylylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, trans and/or cis-1,4-cyclohexanediisocyanate, norbornene diisocyanate; aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate, 2,2,4 and/or (2,4,4)-trimethylhexamethylene diisocyanate and lysine diisocyanate; and mixtures thereof. Examples of the polyisocyanate having three or more isocyanate groups include triphenylmethane triisocyanate, 1-methylbenzol-2,4,6-triisocyanate, dimethyl triphenylmethane tetraisocyanate, and a mixture thereof. The above isocyanates, modified products such as carbodiimide-modified, isocyanurate-modified, and biuret-modified isocyanates of these trifunctional or higher functional isocyanates, blocked isocyanates in which these are blocked as various blocking agents, isocyanurate trimers and biurets of the above diisocyanates A trimer etc. are mentioned.

The urethane prepolymer is prepared by adding a reaction catalyst such as dibutyltin dilaurate, stanasoctoate, dibutyltin-2-ethylhexoate, triethylamine, triethylenediamine, N-methylmorpholine, etc. as needed. it may be

The urethane prepolymer may react with a compound having an anionic group to prepare an aqueous urethane product into which an anionic group is introduced, and then the aqueous polyurethane product to which the anionic group is introduced may be neutralized with a neutralizing agent.

In one embodiment, the compound having an ionic group may be dimethylol propionic acid. Examples of introducing the ionic group include introducing an anionic group or a cationic group. An anionic group was introduced to produce the effect the present invention aims at, for example, polyols containing a carboxyl group, such as dimethylol propionic acid, dimethylol butanoic acid, dimethylol butyric acid, and dimethylol valeric acid, 1,4- Polyols containing a sulfonic acid group such as butanediol-2-sulfonic acid can be mentioned, but in particular, by using dimethylol propionic acid, the water dispersibility of the polyurethane can be significantly improved, and the tensile strength can also be excellent, so it is more preferred. . When the compound having the ionic group is used in an amount of 20 to 40 parts by weight, preferably 30 to 40 parts by weight, based on 100 parts by weight of the polycarbonate-based diol, the water dispersibility of the polyurethane can be significantly improved, and the tensile strength is lowered. It is more preferred because it has the effect of preventing it from happening.

In one embodiment, the aqueous polyurethane product introduced with the ionic group may be neutralized with a neutralizing agent. The neutralizing agent is a neutralizing agent that neutralizes anionic groups. Trialkylamines such as trimethylamine, triethylamine, and tributylamine, N,N-dimethylethanolamine, N,N-dimethylpropanolamine, N,N-dipropylethanol amine, N,N-dialkylalkanolamines such as 1-dimethylamino-2-methyl-2-propanol, N-alkyl-N,N-dialkanolamines, and trialkanolamines such as triethanolamine amine compounds; and basic compounds such as ammonia, trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide and lithium hydroxide. The amount of the neutralizing agent used is preferably 0.2 to 2, preferably 0.5 to 1.5 moles, based on 1 mole of the anionic group. When the neutralizing agent is used in the above range, the desired effect of the present invention can be achieved.

In one aspect, the urethane prepolymer may be prepared by including 2 to 15 parts by weight of a flame-retardant polyol containing phosphorus, preferably 3 to 10 parts by weight, based on 100 parts by weight of the polycarbonate-based diol. In the case of preparing the urethane prepolymer by including the flame-retardant polyol containing phosphorus in the above range, it is possible to improve flame retardancy and heat resistance, and at the same time, the tensile strength is also improved, and it is more preferred because it allows to have a matting effect.

Another aspect of the present invention comprises the steps of preparing a urethane prepolymer by polymerizing a flame retardant polyol containing phosphorus, a polycarbonate-based diol, and a polyisocyanate; preparing a urethane prepolymer having an ionic group by introducing a compound having an ionic group into the urethane prepolymer; After neutralizing the urethane prepolymer having an ionic group with a neutralizing agent, dispersing by adding water; After the dispersing step, reacting by adding a chain extender; It is to provide a method for producing a polyurethane aqueous product comprising a.

First, a step of preparing a urethane prepolymer by polymerizing a flame-retardant polyol containing phosphorus represented by the following Chemical Formula 1, a polycarbonate-based diol, and a polyisocyanate; will be described.

The step of preparing the urethane prepolymer includes a process of evenly dispersing the mixed polyol by adding a flame-retardant polyol containing phosphorus represented by the following Chemical Formula 1 and a polycarbonate-based diol into a reactor, followed by stirring at 75 to 95°C. Thereafter, polyisocyanate is added to the mixed polyol under stirring and reacted at 70 to 90° C. for 1 to 2 hours to prepare a urethane prepolymer. The flame-retardant polyol containing phosphorus represented by the following Chemical Formula 1 is omitted because it is prepared by the same manufacturing method as described above.

[Formula 1]

(n is an integer from 1 to 50.)

In addition, in the step of preparing the urethane prepolymer, a reaction catalyst such as dibutyltin dilaurate, stanas octoate, dibutyltin-2-ethylhexoate, triethylamine, triethylenediamine, N-methylmorpholine is used. It may be input as needed.

Next, introducing a compound having an ionic group to the urethane prepolymer to prepare a urethane prepolymer having an ionic group; explain about

The step of preparing the urethane prepolymer having the ionic group is a process of dissolving the compound having the ionic group in an organic solvent to prepare a solution, and adding the solution to a reactor containing the urethane prepolymer and stirring.

The compound having the ionic group may be dimethylol propionic acid. Examples of introducing the ionic group include introducing an anionic group or a cationic group. An anionic group was introduced to produce the effect the present invention aims at, for example, polyols containing a carboxyl group, such as dimethylol propionic acid, dimethylol butanoic acid, dimethylol butyric acid, and dimethylol valeric acid, 1,4- Polyols containing a sulfonic acid group, such as butanediol-2-sulfonic acid, can be mentioned, but in particular, by using dimethylol propionic acid, the water dispersibility of the polyurethane can be significantly improved, and the tensile strength can also be excellent, so it is more preferred. . The organic solvent may be any one or a mixture selected from dimethylformamide, dimethylacetamide, dimethyl sulfoxide, methylpyrrolidone, and the like, but is not limited thereto.

Next, after neutralizing the urethane prepolymer having an ionic group with a neutralizing agent, dispersing by adding water; explain about In the above step, the neutralizing agent is added to the urethane prepolymer having an ionic group to neutralize, and then water is slowly dropped. At this time, the stirring speed is 900 rpm or more, preferably 1000 rpm or more, and the upper limit is 2000 rpm for 0.5 hours to 2 hours. By vigorous stirring, the urethane prepolymer having the ionic group can be better dispersed in water.

The neutralizing agent is an anionic group neutralizing agent, trialkylamines such as trimethylamine, triethylamine, and tributylamine, N,N-dimethylethanolamine, N,N-dimethylpropanolamine, N,N-dipropylethanolamine, 1 tertiary amine compounds such as N,N-dialkylalkanolamines such as dimethylamino-2-methyl-2-propanol, N-alkyl-N,N-dialkanolamines, and trialkanolamines such as triethanolamine; and basic compounds such as ammonia, trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide and lithium hydroxide. The amount of the neutralizing agent used is preferably 0.2 to 2, preferably 0.5 to 1.5 moles, based on 1 mole of the anionic group. When the neutralizing agent is used in the above range, the desired effect of the present invention can be achieved.

Next, after the dispersing step, the step of reacting by adding a chain extender; will be described. The above step is a step of adding a chain extender to the urethane prepolymer dispersed in water, reacting for 0.5 to 2 hours, terminating the reaction, and finally obtaining a urethane polymer dispersed in water.

The chain extender may be exemplified by commonly used chain extenders such as low molecular weight polyol compounds and low molecular weight polyamine compounds having a weight average molecular weight of less than 200. In addition, specifically ethylenediamine, propylenediamine, hexamethylenediamine, tolylene low molecular weight diamines such as diamine, piperazine and 2-methylpiperazine; polyether diamines such as polyoxypropylene diamine and polyoxyethylene diamine; Monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, N-(2-hydroxypropyl)aminomethanol, 2-(hydroxymethylamino)ethanol, 2-(2-aminoethylamino)ethanol, etc. amino alcohols; Mensendiamine, isophoronediamine, norbornenediamine, bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, 3,9-bis(3- alicyclic diamines such as aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane; m-xylenediamine, α-(m-/p-aminophenyl)ethylamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldimethyldiphenylmethane, diaminodiethyl polyamines such as aromatic diamines such as diphenylmethane, dimethylthiotoluenediamine, diethyltoluenediamine, α,α′-bis(4-aminophenyl)-p-diisopropylbenzene; Dihydrazide succinate, dihydrazide adipate, dihydrazide sebatate, dihydrazide phthalate, hydrazine hydrazine, 1,6-hexamethylenebis(N,N-dimethylsemicarbazide), 1, and hydrazines such as 1,1',1'-tetramethyl-4,4'-(methylene-di-paraphenylene)disemicarbazide, and water.

Another aspect of the present invention is to provide a water-dispersible polyurethane resin having a tensile strength of 20 MPa or more. The water-dispersed polyurethane resin of the present invention has a tensile strength of 20, preferably 22 Mpa or more, and includes a large amount of phosphorus in the structure and can improve the tensile strength that can be weakened by manufacturing by dispersing in water.

In another embodiment, the water-dispersible polyurethane resin may have a particle size of 300 nm to 800 nm. The water-dispersed polyurethane resin of the present invention may have a particle size of 300 to 700 nm, and thereby has a matte effect and can be applied to matte coating.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the following Examples and Comparative Examples are merely examples for explaining the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples.

[Method of measuring physical properties]

<Film production>

Water-dispersed polyurethane was diluted in water to prepare a 20 wt% solution, and then poured into a Petri dish and dried in a drying oven at 50°C for 15 hours and in a vacuum oven at 70°C for 5 hours or more to prepare a film.

1. Tensile strength

The prepared polyurethane film was prepared as a specimen with a width of 35 mm, a length of 6 mm, and a width of 2 mm, and a tensile test was performed in accordance with ISO 37 type-4 using a universal testing machine (UTM LloydbLF Plus).

2. Flame retardant

The maximum heat release rate (HRR) and total HRR were measured using a pyrolysis combustion flow calorimeter (PCFC) tester developed by Lyon and Walters. The PCFC was pyrolyzed by heating the sample from 100°C to 900°C at a rate of 1°C/s in a nitrogen atmosphere after mounting it in a pyrolyser. At this time, the amount of oxygen consumed _{was measured by an O 2} analyzer, and the maximum heat release rate was measured based on this.

3. Thermal stability

TGA analysis was performed to measure thermal stability through weight change of water-dispersed polyurethane according to temperature change. Using Instrument TGA Q500 equipment, nitrogen was flowed at a rate of 60 ml/min, and analysis was performed at a temperature increase rate of 10°C/min from 25°C to 800°C.

4. Particle size

In order for the water-dispersed polyurethane resin of the present invention to exhibit a matting effect during coating, it should have a particle size of about 300 to 800 nm, and use a particle size analyzer (Mastersizer 3000) equipment to check whether it can be used as a matte coating agent. The particle size of each water-dispersed polyurethane according to the amount of all propionic acid and the weight of the flame-retardant polyol was measured.

5. FT-IR Analysis

Through FT-IR analysis, it was confirmed whether the aqueous dispersion polyurethane resin of the present invention was synthesized, and the results are shown in FIG. 1 .

6. GPC Analysis

The aqueous dispersion polyurethane film was dissolved in tetrahydrofuran (with 1wt% toluene) using Gel Permeation Chromatograph (Agilent technologies, 1260 infinity Ⅱ LC) equipment, filtered using a syringe filter, and the weight average molecular weight was measured.

[Example 1] Synthesis of water-dispersed polyurethane

Based on 100 parts by weight of a polycarbonate diol having a molecular weight of 2000 g/mol, 5 parts by weight of a flame-retardant polyol containing phosphorus represented by the following Chemical Formula 2 was put into a reactor, dissolved at 80 to 90° C. for about 30 minutes, and then dispersed evenly by stirring.

[Formula 2]

After filling the reactor with nitrogen gas, a solution obtained by diluting 37 parts by weight of isophorone diisocyanate and 1.5 parts by weight of dibutyltin dilaurate in acetone and 37 parts by weight of isophorone diisocyanate was added to the mixed polyol under stirring, followed by stirring at 80° C. at 150 rpm. . After a certain reaction time, dimethylol propionic acid was dissolved in 33 parts by weight of methylpyrrolidone (N-Methyl-2-pyrrolidone, NMP) and added. Then, 20 parts by weight of acetone was added, and 23 parts by weight of triethylamine was added to neutralize, and then 200 parts by weight of water was slowly dropped. At this time, the stirring speed was set to 1000 rpm or more so that the synthesized polyurethane could be better dispersed in water. Finally, 2 parts by weight of ethylenediamine was added and reacted, and acetone was evaporated to remove the reaction, and then the reaction was terminated to obtain an aqueous dispersion polyurethane dispersed in water. (Weight average molecular weight: 40778 g/mol)

[Example 2]

It was carried out in the same manner as in Example 1, except that a flame-retardant polyol containing phosphorus represented by the following [Formula 3] was added. (Weight average molecular weight: 42190 g/mol)

[Formula 3]

[Comparative Example 1] Excluding the flame retardant polyol containing phosphorus

It was carried out in the same manner as in Example 1, except that the flame-retardant polyol containing phosphorus was not added. (Weight average molecular weight: 36427 g/mol)

[Comparative Example 2] Excluding polycarbonate diol

It was carried out in the same manner as in Example 1, except that polycarbonate diol was not added. (Weight average molecular weight: 37126 g/mol)

Example 1 Example 2 Comparative Example 1 Comparative Example 2 tensile strength
(Mpa) 23.8 19 15.7 17.5 Barrel heat release (KJ/g) 29.5 26.1 25.5 25.1 T _d at 20% weight loss/℃ 305 295 290 287 Particle size (nm) 650 950 1021 1007

In Table 1, Examples 1 and 2, which are aqueous polyurethane dispersions of the present invention, have excellent flame retardancy and thermal stability than Comparative Examples 1 and 2, which are not of the aqueous polyurethane dispersion of the present invention, and have high tensile strength. that can be checked In addition, Example 1 prepared by including the flame-retardant polyol containing phosphorus of the present invention is less flame retardant than Example 2 prepared with a flame-retardant polyol containing phosphorus other than the flame-retardant polyol containing phosphorus of the present invention. It was confirmed that the stability and tensile strength were excellent, and the grain size was small so that a matte effect could be produced.

As described above, the present invention has been described by specific matters and limited examples, but these are provided to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and the field to which the present invention belongs Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described later, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (11)

As an aqueous polyurethane product incorporating an ionic group,
The polyurethane is an aqueous polyurethane dispersion prepared from a polyurethane prepolymer polymerized including a flame retardant polyol containing phosphorus, a polycarbonate-based diol, and a polyisocyanate. The method of claim 1,
The polyurethane is an aqueous polyurethane product prepared by reacting the polyurethane prepolymer with a chain extender. The method of claim 1,
The aqueous polyurethane product introduced with the ionic group is a polyurethane aqueous product prepared by reacting dimethylol propionic acid, a compound having an ionic group, with the polyurethane prepolymer. The method of claim 1,
The aqueous polyurethane product to which the ionic group is introduced is neutralized with a neutralizing agent. The method of claim 1,
The flame-retardant polyol containing phosphorus is a polyurethane aqueous product of the formula (1).
[Formula 1]

(n is an integer from 1 to 50.) The method of claim 1,
The urethane prepolymer is an aqueous polyurethane dispersion prepared by containing 2 to 15 parts by weight of a flame-retardant polyol containing phosphorus in an amount of 2 to 15 parts by weight based on 100 parts by weight of a polycarbonate-based diol. preparing a urethane prepolymer by polymerizing a flame retardant polyol containing phosphorus, a polycarbonate-based diol, and a polyisocyanate;
preparing a urethane prepolymer having an ionic group by introducing a compound having an ionic group into the urethane prepolymer;
After neutralizing the urethane prepolymer having an ionic group with a neutralizing agent, dispersing by adding water;
After the dispersing step, reacting by adding a chain extender;
A method for producing a polyurethane aqueous product comprising a. 8. The method of claim 7,
The flame-retardant polyol containing phosphorus is a method for producing a polyurethane aqueous product of the formula (1).
[Formula 1]

(n is an integer from 1 to 50.) 8. The method of claim 7,
A method for producing an aqueous polyurethane product wherein the compound having an ionic group is dimethylol propionic acid. Water-dispersible polyurethane resin with a tensile strength of 20 MPa or more. 11. The method of claim 10,
The water-dispersed polyurethane resin is a water-dispersed polyurethane resin having a particle size of 300 nm to 800 nm.

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