KR101950220B1 - Urethane modified polymer resin having anti-fouling, aqueous polyurethane resin dispersion and method of manufacturing the same - Google Patents

Abstract

There is provided a urethane-modified polymer resin comprising a chain moiety comprising structural units of a fluoroalkylene oxide having 1 to 2 carbon atoms.
There is provided an aqueous polyurethane resin dispersion in which a urethane-modified polymer resin containing a chain moiety comprising structural units of a fluoroalkylene oxide having 1 to 2 carbon atoms is dispersed in several media.
A polymeric polyol, dimethylpropionic acid, dimethylbutanoic acid, polyoxyethylene glycol, a polycaprolactone diol containing a carboxyl group in the side chain, a polyether diol having a sulfonic acid group in the side chain, and a polyoxyethylene group substituted with an alkoxy group in the side chain Polyol, and combinations thereof, an isocyanate compound, and a fluorine compound to form a urethane-modified polymer resin; Dispersing the urethane-modified polymer resin in an aqueous medium; And reacting the dispersed urethane-modified polymer resin with a chain extender. The present invention also provides a process for producing an aqueous polyurethane resin dispersion.

Description

TECHNICAL FIELD The present invention relates to a urethane-modified polymer resin having an antifouling property, an aqueous polyurethane resin dispersion having an antifouling property and an aqueous polyurethane resin dispersion, and a process for producing the same. BACKGROUND ART [0002] Urethane-

A urethane-modified polymer resin having an antifouling property, an aqueous polyurethane resin dispersion, and a process for producing the same.

The aqueous polyurethane resin dispersion is widely used as a raw material for paints and coating materials, for example, as a raw material for paints and coatings for interior and exterior use for aircraft, automobiles, exterior walls of houses, flooring and the like. In addition, the coating layer formed of the aqueous polyurethane resin dispersion not only exhibits the beauty of appearance but also serves to protect the base material, so that it is necessary to have hardness, strength, durability and stain resistance.

Accordingly, there is an increasing need for studies on an aqueous polyurethane resin dispersion which simultaneously exhibits hardness, strength, durability and stain resistance.

An embodiment of the present invention provides a urethane-modified polymer resin into which a chain moiety having antifouling property is introduced.

Another embodiment of the present invention provides an aqueous polyurethane resin dispersion in which the urethane-modified polymer resin is dispersed in several media.

Another embodiment of the present invention provides a process for producing the aqueous polyurethane resin dispersion.

In one embodiment of the present invention, there is provided a urethane-modified polymer resin comprising a chain moiety comprising structural units of a fluoroalkylene oxide having 1 to 2 carbon atoms.

The urethane-modified polymer resin may be crosslinked with a chain extender.

The content of the chain moiety may be about 1 wt% to about 20 wt%.

The urethane-modified polymer resin may have a weight average molecular weight of about 5,000 to about 30,000.

The molar ratio of the isocyanate group (-NCO) to the hydroxyl group (-OH) of the urethane modified polymer resin may be from about 0.5 to about 3.0.

In another embodiment of the present invention, there is provided an aqueous polyurethane resin dispersion in which a urethane-modified polymer resin containing a chain moiety containing structural units of a fluoroalkylene oxide having 1 to 2 carbon atoms is dispersed in several media.

The particle diameter of the aqueous polyurethane resin dispersion may be about 10 nm to about 300 nm.

The number average molecular weight of the aqueous polyurethane resin dispersion may be about 25,000 to about 1,000,000.

In another embodiment of the present invention, a polymeric polyol, dimethylpropionic acid, dimethylbutanoic acid, polyoxyethylene glycol, a polycaprolactone diol containing a carboxyl group in the side chain, a polyether diol having a sulfonic acid group in the side chain, At least one compound selected from the group consisting of a polyol having a polyoxyethylene group substituted with an alkoxy group, and a combination thereof, an isocyanate compound, and a fluorine compound are reacted to form an urethane-modified polymer resin; Dispersing the urethane-modified polymer resin in an aqueous medium; And reacting the dispersed urethane-modified polymer resin with a chain extender. The present invention also provides a process for producing an aqueous polyurethane resin dispersion.

The fluorine compound may be represented by the following formula (1).

[Chemical Formula 1]

_{X-CF 2 O- (CF 2} CF 2 O) m- (CF 2 O) n-CF 2 -X

(Wherein X is selected from C1-C10 alkyl group and a C2-C10 alkenyl group containing at least one -NH ₂ and -NR'H with a substituent;

Wherein R ' is selected from H and C1-C10 alkyl groups;

And m and n are each at least 1.)

The fluorine compound may have a weight average molecular weight of about 500 to about 2,000.

The polymeric polyol may be at least one selected from the group consisting of a polyester polyol having 2 to 4 hydroxyl groups, a polycarbonate polyol, a polyether polyol, and combinations thereof.

From about 20% to about 80% by weight of the polymeric polyol, the dimethylpropionic acid, dimethylbutanoic acid, polyoxyethylene glycol, polycaprolactone diol containing a carboxyl group in the side chain, polyether diol having a sulfonic acid group in the side chain, About 5% to about 50% by weight of the isocyanate compound, about 2% to about 20% by weight of at least one compound selected from the group consisting of a polyol having a polyoxyethylene group substituted with an alkoxy group in the side chain, From about 0.1 wt% to about 20 wt% may be reacted to form the urethane modified polymer resin.

From about 1% to about 20% by weight of the solvent, and from about 2% to about 20% by weight of the neutralizing agent, and then react to form the urethane-modified polymer resin.

The urethane-modified polymer resin improves antifouling property and cleaning performance, and can be introduced without deterioration in physical properties when synthesized with other materials, thereby realizing excellent reliability.

The aqueous polyurethane resin dispersion prepared by the method for producing an aqueous polyurethane resin dispersion can be used as a binder of the contamination coating liquid composition and as an aqueous dispersion additive exhibiting antifouling property.

Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Urethane modification Polymer  Suzy

In one embodiment of the present invention, there is provided a urethane-modified polymer resin comprising a chain moiety comprising structural units of a fluoroalkylene oxide having 1 to 2 carbon atoms.

Urethane resins are generally used in a wide range of artificial leather and textile processing fields because of their excellent elongation and excellent adhesion and adherence.

However, due to the molecular structure characteristic of the urethane / urea structure, it is vulnerable to contamination. To improve this, a material exhibiting resistance to contamination is added. However, the contamination resistance is not semi-permanently implemented, there was.

In order to overcome the above-mentioned problems, one embodiment of the present invention is a method for manufacturing a urethane resin composition, which comprises introducing a material having an antifouling property, for example, a fluorine compound or the like during polymerization of urethane polymer resin to semi-permanently maintain stain resistance, Modified polymer resin.

The urethane-modified polymer resin can introduce reliability into the main chain of the resin by introducing a chain moiety having antifouling property, without deteriorating the physical properties of the urethane-modified polymer resin due to introduction of the chain moiety and securing excellent abrasion resistance .

The chain moiety may include a structural unit of a fluoroalkylene oxide having 1 to 2 carbon atoms.

Specifically, the chain moiety may comprise - [RO] - structural units, wherein R is a fluoroalkylene having 1 to 2 carbon atoms. More specifically, - [RO] - can be - [CF ₂ CF ₂ O] -, - [CF ₂ O] -.

The urethane-modified polymer resin can be crosslinked with a chain extender, and the molecular weight can be controlled and the molecular structure can be controlled by introducing the chain extender. For example, the urethane-modified polymer resin may be dispersed in several media and then crosslinked with an introduced chain extender to form a network into which the chain moiety is introduced.

The chain extender serves to control the molecular weight of the urethane-modified polymer resin, and may include a compound having reactivity with an isocyanate group.

Specifically, there may be mentioned ethylene diamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, Aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, piperazine, adipoyl hydrazide, hydrazine, 2,5-dimethylpiperazine, di Amine compounds such as ethylenetriamine and triethylenetetramine; diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; polyalkylene glycols such as polyethylene glycol; Can be used.

The content of the chain moiety may be about 1 wt% to about 20 wt%. The chain moiety content has the greatest influence on the stain resistance and abrasion resistance of the urethane-modified polymer resin. When the chain moiety content is less than about 1% by weight, only the surface modification effect due to the low content is exhibited. And when it exceeds about 20% by weight, non-uniformity may increase due to compatibility with other constituents, and polymerization may not be possible.

Therefore, by including the content of the chain moiety in the above range, the stain resistance and the chemical resistance through the surface modification effect can be easily realized.

The urethane-modified polymer resin may have a weight average molecular weight of about 5,000 to about 30,000. The molecular weight is directly related to the viscosity of the resin, and by maintaining the above range, it is possible to perform a stable molecular weight distribution when dispersed in an aqueous medium. Further, by maintaining the molecular weight of the resin, the particle diameter of the formed aqueous polyurethane resin dispersion can be about 300 nm or less, which can maximize the stability of the particles.

The molar ratio of the isocyanate group (-NCO) to the hydroxyl group (-OH) of the urethane modified polymer resin may be from about 0.5 to about 3.0. When the molar ratio is less than about 0.5, the overall physical properties including the hardness of the resin are deteriorated. When the molar ratio is more than about 3.0, the hardness of the resin is improved but may be too hard and broken. Therefore, the coating layer formed by the resin and the base layer such as wallpaper can easily realize the adhesion performance and the bending performance, including the molar ratio within the above range, and the coating layer can realize excellent abrasion resistance and chemical resistance as a cured product have.

Aqueous polyurethane resin Dispersant

Another embodiment of the present invention provides an aqueous polyurethane resin dispersion in which a urethane-modified polymer resin containing a chain moiety containing structural units of a fluoroalkylene oxide having 1 to 2 carbon atoms is dispersed in several media.

Normally, in order for the aqueous polyurethane resin dispersion to exhibit stain resistance, additives other than the polyurethane resin are usually added, but the durability of the dispersion is lowered due to the addition of additives.

However, since the dispersion contains the resin containing the chain moiety, the stain resistance and the durability can be secured simultaneously without deteriorating the physical properties.

The dispersion may be formed by dispersing or dispersing the resin in several media and reacting with a chain extender. The dispersion may be contained as a binder or an aqueous dispersion additive in an anti-fouling coating composition, Can be used to coat the interior film surface.

As the aqueous medium, water may be used. For example, the water may include water, ion-exchanged water, distilled water, ultrapure water, etc., and may be appropriately selected in consideration of instability of particles due to availability or salt, .

The particle diameter of the aqueous polyurethane resin dispersion may be about 10 nm to about 300 nm. The particle diameter can be measured by a dynamic scattering particle measuring instrument with " average particle diameter ". It can not be produced with a particle diameter of less than about 10 nm, and when the particle diameter exceeds about 300 nm, the inter-particle stability is lowered to cause sedimentation, leading to phase separation of the urethane-modified polymer resin.

The number average molecular weight of the aqueous polyurethane resin dispersion may be about 25,000 to about 1,000,000. The resin reacts with the chain extender to grow the molecular weight of the dispersion. By first crosslinking a part of the particles of the dispersion, the molecular weight in the above range can be obtained, and the chemical resistance and abrasion resistance can be improved.

Aqueous polyurethane resin Dispersant  Manufacturing method

Another embodiment of the present invention is a polyether polyol having a side chain comprising a polymeric polyol, dimethylpropionic acid, dimethylbutanoic acid, polyoxyethylene glycol, a polycaprolactone diol containing a carboxyl group in the side chain, a polyether diol having a sulfonic acid group in the side chain, At least one compound selected from the group consisting of a polyol having a polyoxyethylene group substituted with an alkoxy group, and a combination thereof, an isocyanate compound, and a fluorine compound are reacted to form an urethane-modified polymer resin; Dispersing the urethane-modified polymer resin in an aqueous medium; And reacting the dispersed urethane-modified polymer resin with a chain extender. The present invention also provides a process for producing an aqueous polyurethane resin dispersion.

The fluorine compound may be represented by the following formula (1).

_{X-CF 2 O- (CF 2} CF 2 O) m- (CF 2 O) n-CF 2 -X

(Wherein X is C1-C10 alkyl group and a C2-C10 alkenyl group is selected from the comprising at least one -NH ₂ and the substituent -NR'H; it is selected from the R 'is selected from H and C1-C10 alkyl group; wherein m And n are each at least 1.)

A polymeric polyol, dimethylpropionic acid, dimethylbutanoic acid, polyoxyethylene glycol, a polycaprolactone diol containing a carboxyl group in the side chain, a polyether diol having a sulfonic acid group in the side chain, and a polyoxyethylene group substituted with an alkoxy group in the side chain At least one compound selected from the group consisting of a polyol, a polyol and a combination thereof, an urethane-modified polymer comprising a chain moiety containing a structural unit of a fluoroalkylene oxide having 1 to 2 carbon atoms by incorporating the fluorine compound together with an isocyanate compound A resin can be formed. For example, the fluorine compound may have a weight average molecular weight of about 500 to about 2,000.

The polymeric polyol may be at least one selected from the group consisting of polyester polyols having from about 2 to about 4 hydroxyl groups, polycarbonate polyols, polyether polyols, and combinations thereof.

The isocyanate compound may be at least one selected from the group consisting of toluene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and combinations thereof.

Specifically, the polymeric polyol may be present in an amount of about 20% to about 80% by weight, such as dimethylpropionic acid, dimethylbutanoic acid, polyoxyethylene glycol, polycaprolactone diol containing a carboxyl group in the side chain, poly About 2% to about 20% by weight of at least one compound selected from the group consisting of ether diols, polyols having a polyoxyethylene group substituted with an alkoxy group in the side chain, and combinations thereof, from about 5% to about 50% by weight of the isocyanate compound, About 0.1 wt% to about 20 wt% of the fluorine compound may react to form an urethane modified polymer resin.

Further, the solvent may further contain about 1 wt% to about 20 wt% of the solvent and about 2 wt% to about 20 wt% of the neutralizing agent, and then react to form the urethane-modified polymer resin.

The neutralizing agent may be selected from the group consisting of trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, , Organic amines such as pyridine; Inorganic alkalis such as sodium hydroxide, potassium hydroxide and the like, ammonia and the like, and neutralization can be further carried out by further including a neutralizing agent having the same mol number as the number of moles of the hydrophilic ionizing group of the dispersion.

The solvent is included for controlling the viscosity of the resin, and includes a lower monohydric alcohol such as methanol, ethanol, propanol, etc .; Polyhydric alcohols such as ethylene glycol and glycerin; A non-protonic hydrophilic organic solvent such as N-methylmorpholine, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone, acetone or tetrahydrofuran, The above-mentioned molecular weight of the dispersion can be obtained, and the viscosity control effect can be easily realized.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

≪ Examples and Comparative Examples &

Example  One

190 g of polycarbonate diol (UBE PH-200), 10 g of dimethylpropionic acid, 4 g of a fluorine compound (Solvay D10 / H) and 60 g of N-methylpyrrolidone were added and sufficiently stirred at 100 ° C to form a mixture . After the mixture was cooled to 80 ° C, 60 g of isophorone diisocyanate was added and reacted for 4 hours to form a reaction product. The reaction product was cooled at 50 ° C. and 5 g of triethylamine was added to form a urethane-modified polymer resin .

410 g of water was gradually dropped into the urethane-modified polymer resin and vigorously stirred for 30 minutes. Thereafter, 8.6 g of ethylenediamine was added and stirred for 30 minutes. The final solid content was adjusted to 30% to prepare an aqueous polyurethane resin dispersion having a particle size of 53 nm and a number average molecular weight of 34,000.

Wherein the urethane-modified polymer resin comprises 3 wt% chain moieties, the chain moieties comprise structural units of - [CF ₂ CF ₂ O] -, and the weight average molecular weight is 23,000.

Example  2

140 g of polycarbonate diol (UBE PH-200), 8.5 g of dimethylpropionic acid, 20.7 g of a fluorine compound (Solvay E10 / H) and 90 g of N-methylpyrrolidone were charged and sufficiently stirred at 100 ° C to obtain a mixture . The mixture was cooled to 80 ° C, 64 g of isophorone diisocyanate was added and reacted for 4 hours to form a reaction product. The reaction product was cooled at 50 ° C, and then 5 g of triethylamine and 90 g of acetone were added thereto to obtain a urethane- To form a resin.

410 g of water was gradually dropped into the urethane-modified polymer resin and vigorously stirred for 30 minutes. Thereafter, 9.2 g of ethylenediamine was added and stirred for 30 minutes, and the final solid content was adjusted to 30% to prepare an aqueous polyurethane resin dispersion having a particle size of 110 nm and a number average molecular weight of 37,000.

In this case, the urethane-modified polymer resin comprises a chain moiety of 12% by weight, and the chain moiety - [CF ₂ O] - containing a structural unit of and a weight average molecular weight was 23,000.

Comparative Example  One

An aqueous polyurethane resin dispersion having a particle size of 45 nm and a number average molecular weight of 32,000 was prepared in the same manner as in Example 1, except that the urethane-modified polymer resin was not formed.

< Experimental Example > - aqueous polyurethane resin Dispersion  Stain resistance

8 g of a curing agent (CARBODILITE ^™ SV-02, manufactured by Nissinbo), 3.5 g of diisocyanate, 0.6 g of wetting agent (OFX-5211, Dow Corning) 0.6 0.6 g of a defoamer (Foamex 825, Evonik Corp.) and 1.2 g of a quencher (acematt 3300, Evonix Corp.) were added and sufficiently stirred to form first, second and third coating liquid compositions.

Comparative Example 1 was dissolved in 100 g of water and mixed with 3.6 g of a fluorine additive (Dyneen THV 340C, 3M), 8 g of a curing agent (CARBODILITE ^™ SV-02, Nissinbo), 3.5 g of diisocyanate, 0.6 g of wetting agent (OFX- , 0.6 g of a defoaming agent (Foamex 825, Evonik Corp.) and 1.2 g of a light-quenching agent (acematt 3300, Evoniksha) were added and sufficiently stirred to form a fourth coating liquid composition.

1) Abrasion resistance: An anti-fouling coating composition formed using the above Examples and Comparative Examples was applied on PVC foamed wallpaper using a bar coater and then dried at 150 ° C for 1 minute to form a coating layer. The weight was weighed using a weight of 100 g, and the weight was applied 100 times using a sponge brush, and the extent of wear was visually evaluated. (O: no wear,?: Abrasive wear, X: abrasive wear)

2) Stain Resistance: The antifouling coating composition formed using the above Examples and Comparative Examples was applied on PVC foam wallpaper using a bar coater and then dried at 150 ° C for 1 minute to form a coating layer. After the graffiti, graffiti was removed using a cloth, and the degree of graffiti removal was visually evaluated. (O: excellent graffiti removal degree,?: Graffiti removal degree average, X: poor graffiti removal degree)

Coating liquid composition Abrasion resistance Stain resistance Example 1 The first coating liquid composition O O Example 2 The second coating liquid composition O O Comparative Example 1 The third coating liquid composition △ X The fourth coating liquid composition X △

Referring to Table 1, it can be seen that Examples 1 and 2 are more excellent in abrasion resistance and stain resistance than Comparative Examples.

In addition, in Comparative Example 1, the fourth coating liquid composition was obtained by separately introducing a fluorine-containing additive, which is superior in stain resistance to the third coating liquid composition, but it has poor physical properties due to fluorine additives and poor wear resistance.

Claims (15)

delete delete delete delete delete A urethane-modified polymer resin containing a chain moiety containing a structural unit of a fluoroalkylene oxide having 1 to 2 carbon atoms is dispersed in an aqueous medium,
The urethane-modified polymer resin has a weight average molecular weight of 5,000 to 30,000,
Wherein the aqueous polyurethane resin dispersion has a particle diameter of 53 nm to 110 nm,
Having a number average molecular weight of 25,000 to 34,000
Aqueous polyurethane resin dispersion.
delete delete Polycarbonate polyol; At least one compound selected from the group consisting of a polycaprolactone diol having a carboxyl group in a side chain, a polyether diol having a sulfonic acid group in a side chain, a polyol having a polyoxyethylene group substituted with an alkoxy group in the side chain, and a combination thereof; Isocyanate compounds; And a fluorine compound to form an urethane-modified polymer resin;
Dispersing the urethane-modified polymer resin in an aqueous medium; And
Reacting the dispersed urethane-modified polymer resin with ethylenediamine to prepare an aqueous polyurethane resin dispersion,
Wherein the fluorine compound is represented by the following formula (1)
The urethane-modified polymer resin has a weight average molecular weight of 5,000 to 30,000,
Wherein the aqueous polyurethane resin dispersion has a particle diameter of 53 nm to 110 nm,
The aqueous polyurethane resin dispersion has a number average molecular weight of 25,000 to 34,000
A method for producing an aqueous polyurethane resin dispersion.

[Chemical Formula 1]
_{X-CF 2 O- (CF 2} CF 2 O) m- (CF 2 O) n-CF 2 -X
(Wherein X is selected from C1-C10 alkyl group and a C2-C10 alkenyl group containing at least one -NH ₂ and -NR'H with a substituent;
Wherein R ' is selected from H and C1-C10 alkyl groups;
And m and n are each at least 1.)
delete 10. The method of claim 9,
Wherein the fluorine compound has a weight average molecular weight of 500 to 2,000
A method for producing an aqueous polyurethane resin dispersion.
10. The method of claim 9,
Wherein the polycarbonate polyol has from 2 to 4 hydroxyl groups
A method for producing an aqueous polyurethane resin dispersion.
delete 10. The method of claim 9,
20% to 80% by weight of the polycarbonate polyol; At least one compound selected from the group consisting of a polycaprolactone diol having a carboxyl group in the side chain, a polyether diol having a sulfonic acid group in a side chain, a polyoxyethylene group having a polyoxyethylene group substituted with an alkoxy group in the side chain, weight%; 5% to 50% by weight of the isocyanate compound; 0.1 to 20% by weight of the fluorine compound is reacted to form the urethane-modified polymer resin
A method for producing an aqueous polyurethane resin dispersion.
10. The method of claim 9,
1 to 20% by weight of a solvent and 2 to 20% by weight of a neutralizing agent are further contained and then reacted to form a urethane-modified polymer resin
A method for producing an aqueous polyurethane resin dispersion.