KR101787964B1 - Environment-friendly surface coating materials comprising waterborne urethane binder having improved storage stability - Google Patents

Abstract

Disclosed herein is a composition for preparing a water-dispersible urethane binder for a film-like flooring, and a process for producing a binder using the same. The binder prepared from the composition for preparing a water-dispersible urethane binder for a coating flooring according to one aspect of the present invention is superior in dispersibility to conventional water-dispersible urethane binders, and does not cause sedimentation even when stored for a long period of time. In addition, the composition has a short drying time after coating and is excellent in the smoothness of the formed coating film. In addition, the binder is more environmentally friendly than the hydrophobic polyurethane binder and has excellent physical properties.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a water-dispersible urethane binder having improved water-solubility,

Disclosed herein is an environmentally friendly film-based flooring containing a water-dispersible urethane binder having improved storage stability.

Generally, a binder such as a hydrophobic polyester resin, an epoxy resin, an acrylic resin, a urethane resin or the like is used for the production of a coating layer type flooring. However, such hydrophobic binders are problematic in that the volatile organic compounds (VOC) used to dissolve these pollute the environment and cause the wave name phenomenon of the packaging material due to the organic solvents such as thinner in the high temperature summer Which is not suitable for use as a coating material for a film.

In order to solve such a problem, recently, efforts have been made to render the hydrophobic binder water-soluble. As a technique for making the hydrophobic binder water-soluble, there are disclosed in JP-A-4-328187, JP-A-5-43642, JP-A-39-5989, JP-A-45-10957, 10-0662510, etc. However, these methods have a problem that it takes a long time to prepare the coating material, and the physical properties of the coating material such as abrasion resistance and weather resistance of the coating material deteriorate.

Korean Patent Laid-Open Publication No. 10-0662510 improves the physical properties of such a water-soluble binder, but the dispersibility of the water-soluble binder deteriorates, thereby causing a problem of separation of formulations such as precipitation of the binder during storage.

KR10-1480802B

In one aspect, an object of the present invention is to provide a water-dispersible urethane binder for a coating-type flooring having improved dispersibility.

In one aspect, an object of the present invention is to provide a composition for producing a water-dispersible urethane binder for a film-like flooring having a short curing time.

In one aspect, an object of the present invention is to provide a water-dispersible urethane binder for a coating-type floor material which improves the smoothness of a coating film.

In one aspect, an object of the present invention is to prepare a water-dispersible urethane binder for a coating-type flooring material which minimizes the amount of volatile organic compounds used and improves adhesion strength, weather resistance, abrasion resistance and slip resistance.

In order to achieve the above object, the present invention relates to a polyester polyol; Urethane intermediates; Carboxylic acid; Alcohols; Isocyanate; Wherein the polyester polyol comprises a polyester polyol having a number average molecular weight of 700 to 1500 and the urethane intermediate is a urethane intermediate obtained by polymerizing a urethane intermediate obtained by polymerizing monoethanolamine and propylene carbonate in an equivalent ratio of 1: A composition for the production of a water-dispersible urethane binder for a floor covering material comprising an intermediate and a process for producing the same.

The binder prepared from the composition for preparing a water-dispersible urethane binder for a coating flooring according to one aspect of the present invention is superior in dispersibility to conventional water-dispersible urethane binders, and does not cause sedimentation even when stored for a long period of time. In addition, the composition has a short drying time after coating and is excellent in the smoothness of the formed coating film. In addition, the binder is more environmentally friendly than the hydrophobic polyurethane binder and has excellent physical properties.

1 is a graph showing a result of a comparison experiment with KR10-1480802B (left: Comparative Example 7, right: Example 1).

Hereinafter, the present invention will be described in detail.

In the present specification, the term "water dispersion" means a material in which water-insoluble resin is dispersed in water as fine particles.

In the present invention, the term 'polyurethane' means a polymer compound which realizes various physical properties and functionality by mixing and reacting an isocyanate, which is an organic compound, with a polyol, followed by mixing additives and the like.

Herein, the term 'organic solvent' refers to a liquid organic chemical substance which is volatile and toxic and can be dissolved in a certain substance.

As used herein, the term " intermediate " means a chemical species that is in the course of the reaction pathway from a reactant to a product in a chemical reaction.

In the present specification, the term "amine value" refers to a numerical value represented by the amount of KOH consumed by titrating an -NH2 group in an amine with KOH, and a value indicating the amount of KOH consumed per gram of the amine in mg.

In this specification, the term 'abrasion resistance' means a property of abrasion and wear resistance even if rubbed.

In the present specification, the term 'accelerated weathering' refers to a property which is exhibited by promoting weatherability, that is, a weather-resistant state. That is, it means the durability of the sample when the sample is set to a more severe condition than the actual climate (temperature, humidity, rainfall, etc.).

In the present specification, 'NCO%' means that the polyurethane is prepared by reacting a diisocyanate with a polyol, a diol, or the like to have an urethane bond. The NCO% indicates that the NCO group of the diisocyanate is the Means the NCO, i.e., the residual NCO.

In one aspect, the present invention relates to a polyester polyol; Urethane intermediates; Carboxylic acid; Alcohols; Isocyanate; Wherein the polyester polyol comprises a polyester polyol having a number average molecular weight of 700 to 1500 and the urethane intermediate is a urethane intermediate obtained by polymerizing a urethane intermediate obtained by polymerizing monoethanolamine and propylene carbonate in an equivalent ratio of 1: Dispersible urethane binder composition for a coating-type flooring material, which comprises an intermediate.

The above composition may be prepared by using a urethane intermediate formed from a monoethanolamine and propylene carbonate by using a polyester polyol which is not a polyether polyol unlike a conventional water-dispersible urethane binder, especially a polyester polyol having a number average molecular weight of 700 to 1500 , Improved dispersibility and formulation stability can be obtained.

The urethane intermediate may preferably be obtained by polymerizing monoethanolamine and propylene carbonate at an equivalent ratio of 1: 1.

Urethane is a generic term for carbamic acid esters, usually ethyl carbamate, and its chemical formula is NH ₂ COOC ₂ H ₅ . Urethane Bond is formed by reaction of an alcohol having an active hydroxyl group (-OH) and an isocyanate group (Isocyanate Group, -N = C = O) by an addition polymerization reaction As shown in FIG.

Polyurethane (PU) is a general term for a polymer compound containing urethane bonds in a certain amount or more. It is composed of an isocyanate having at least one isocyanate group (-N = C = O) and at least one hydroxyl group (-OH) is called a polyfunctional, and a functional group having a structure of [-NHCOO-] n is generated by dissolving heat at a high temperature under a proper condition. This alcohol is called a urethane bond, Quot; refers to a molecule having 1000 or more molecules bound thereto.

In one aspect, the urethane intermediate may comprise one or more of the following properties:

i) an amine value of 14 to 20 mg KOH / g, ii) a flow time of 25 to 30 seconds measured at 20 DEG C by DIN53211.

In addition, the carboxylic acid may include dimethylolpropionic acid, and the alcohols may include ethoxypropanol; And 1,4 butanediol, the isocyanate may comprise 4,4'-dicyclohexylmethane diisocyanate, and the amines may be selected from the group consisting of triethylamine; And adelendiamine. ≪ / RTI >

Said composition comprising, based on the total weight of the composition, from 12 to 30% by weight of a polyester polyol; 1 to 20% by weight of a urethane intermediate; 0.01 to 10% by weight of carboxylic acid; 0.01 to 15% by weight of alcohols; 10 to 30% by weight of isocyanate; And 0.01 to 12% by weight of amines.

The polyester polyol may preferably be contained in an amount of 13 to 17% by weight, more preferably 14 to 16% by weight, based on the total weight of the composition.

The urethane intermediate may be contained in an amount of preferably 1 to 10% by weight, more preferably 3 to 7% by weight, based on the total weight of the composition.

Further, the carboxylic acid may be contained in an amount of preferably 0.1 to 1% by weight, more preferably 0.3 to 0.7% by weight, based on the total weight of the composition.

The ethoxypropanol may be contained in an amount of 0.1 to 12% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 2.0% by weight based on the total weight of the composition. The 1,4-butanediol may be contained in an amount of 0.01 to 2% by weight, preferably 0.01 to 1% by weight, more preferably 0.05 to 0.3% by weight, based on the total weight of the composition. have.

The isocyanate may be contained in an amount of 10 to 20% by weight, more preferably 13 to 18% by weight, based on the total weight of the composition.

The composition may comprise from 0.1 to 3% by weight of chromosomal DNA. In one embodiment, the composition may comprise from 0.5 to 1.5% by weight of chromogein, and in this case, excellent physical properties can be obtained compared to the embodiments that do not contain chromogens.

The triethylamine may be contained in an amount of 0.01 to 5% by weight, preferably 0.01 to 1% by weight, and more preferably 0.01 to 0.3% by weight based on the total weight of the composition. The ethylenediamine may be contained in an amount of 0.1 to 7% by weight, preferably 0.1 to 3% by weight, more preferably 0.1 to 0.7% by weight, based on the total weight of the composition.

In one embodiment, the composition can further comprise a bismuth carboxylate, wherein the bismuth carboxylate can be included in an amount of 0.001 to 1% by weight, preferably 0.01 To 0.1% by weight.

In one aspect, the present invention is a process for producing a water-dispersible urethane binder for a coated flooring comprising the step of mixing the composition.

Wherein the mixing step comprises: a first mixing step of mixing a polyester polyol, a urethane intermediate, a carboxylic acid, and alcohols; Reacting the mixture of the first mixing step with nitrogen gas; A second mixing step of further adding and mixing isocyanate, bismuth carboxylate, alcohols and amines; And a third mixing step in which alcohols, distilled water, and amines are further added and mixed.

The mixing method is optimized for producing the binder of the present invention. For example, when the nitrogen gas reaction step is omitted or the order of the first mixing to the third mixing is changed, a binder excellent in dispersibility can not be produced .

The first mixing step may include performing in an inert gas atmosphere and at 110-130 < 0 > C. The step of reacting the mixture of the first mixing step with the nitrogen gas may include performing the reaction for 30 to 120 minutes. The temperature of the first mixing step may preferably be 115 to 125 캜.

In the second mixing step, the isocyanate and the bismuth carboxylate are reacted at a temperature of 80 to 85 ° C., and when the NCO content is 17 to 18%, an alcohol is added; And adding NCO% after adding the alcohol to 14.5 to 15.5%, adding the amine and reacting for 30 to 120 minutes.

In one aspect, the third mixing step comprises: cooling the mixture of the second mixing step to 45-55 占 폚; Adding the alcohol after cooling; Adding distilled water at 20 to 30 DEG C while stirring at 60 to 80 rpm; And amines, followed by stirring.

In the third mixing step, the binder can be produced without adding high-temperature distilled water unlike the conventional aqueous binder manufacturing method, thereby simplifying the manufacturing process.

The alcohols in the first mixing step may include ethoxy propanol, the alcohols in the second mixing step may include 1,4-butanediol, and the amines in the second mixing step may be triethyl Amine, and the alcohols in the third mixing step may include ethoxy propanol, and the amines in the third mixing step may include ethylenediamine.

In addition, the inert gas may be selected from the group consisting of nitrogen, helium, neon, argon, krypton, xenon, and radon, preferably nitrogen.

Hereinafter, the constitution and effects of the present invention will be described in more detail with reference to examples and test examples. However, these examples and test examples are provided for illustrative purposes only in order to facilitate understanding of the present invention, and the scope and scope of the present invention are not limited by the following examples.

[Preparation Example 1] Preparation of water-dispersible urethane binder

[Production Example 1-1] Synthesis of urethane intermediate

Urethane intermediate was prepared by synthesizing monoethanolamine and propylene carbonate. The urethane intermediate was prepared by mixing 84 g of monoethanolamine and 102 g of propylene carbonate and then gradually elevating the temperature to 120 캜. The amine value (mgKOH / g) was 14 to 20 mgKOH / g and the viscosity It was measured at time intervals from 20 ° C to 25-30 sec (Din53211). When it satisfied the standard, it was cooled at 20-30 ° C.

Here, 'amine value' means a numerical value indicating the amount of KOH consumed by titrating the -NH2 group possessed by the amine with KOH, and expressing the amount of KOH consumed per gram of the amine in mg. That is, when the consumption of KOH is high, the activity of the amine is high, and conversely, when the amine value is low, the activity of the amine is low.

The amine value (mgKOH / g) was measured by adding about 0.5 g of the above sample in Flask and dissolving in neutralized Acetone. After cooling the solution, the solution was cooled to room temperature with a Bromophenol blue indicator Titrate with Hcl. Amine value (mgKOH / g) is calculated as follows.

Amine value (mgKOH / g) = mol 0.1 N HCl X 100 X 5.61 / sample weight X NV (non volitile)

In the above equation, NV (non volitile, hereinafter referred to as "solid content") was prepared by weighing 0.8-1.0 g of a resin on a 7.5 cm diameter tin lid and drying it in an air circulator drying oven at 125 ° C. for 60 minutes, As follows.

N.V. (DIN 53216)% = Final Weight / Weight Out x 100

[Production Example 1-2] Preparation of water-dispersible urethane binder

A water-dispersible urethane binder was prepared according to the process shown in Table 1 below.

(1) The raw materials 1 to 4 shown in the following Table 1 were placed in a reactor completely filled with nitrogen (N ₂ ) as an inert gas, heated to 120 ° C to completely dissolve them, and reacted for 1 hour while injecting nitrogen gas.

(2) The raw materials 5 to 6 shown in the following Table 1 were added and mixed at 80 to 85 ° C, respectively. When the NCO content became 17 to 18%, the raw material 7 was added. When the NCO content fell to 14.5 to 15.5% The raw material 8 was added and reacted for 1 hour.

(3) When the temperature dropped to 50 캜, the raw material 9 was added. When the temperature dropped to 40 캜, the raw material 10 was slowly added for 20 minutes while stirring at 60 to 80 RPM using a high-speed stirrer (HS- While stirring, the raw material 11 was slowly added for 20 minutes, and after performing the physical property test, the high-speed stirrer was maintained at 80 to 60 RPM.

number Raw material name Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 One Polyester polyol 15 20 25 10 35 15 15 15 15 2 Urethane materials
(Urethane intermediate) 5 15 10 5 5 0.5 25 5 5 3 Dimethylol propionic acid 0.5 One 5 0.5 0.5 0.5 0.5 0.5 0.5 4 ethoxy propanol One 2 5 One One One One One One 5 4-4'-dicyclohexyl
메탄 이 시산산 15 20 25 15 15 15 15 5 31 6 bismuth carboxylate 0.01 0.1 0.05 0.01 0.01 0.01 0.01 0.01 0.01 7 1,4-Butanediol 0.1 0.3 0.5 0.1 0.1 0.1 0.1 0.1 0.1 8 Triethyl amine 0.1 0.8 3 0.1 0.1 0.1 0.1 0.1 0.1 9 ethoxy propanol 0.5 One 5 0.5 0.5 0.5 0.5 0.5 0.5 10 Cool water (20 ~ 30) 62.79 39.8 11.45 Balance Balance Balance Balance Balance Balance 11 Ethylene diamine 0.5 One 5 0.5 0.5 0.5 0.5 0.5 0.5 Total (% by weight) 100 100 100 100 100 100 100 100 100

KR10-1480802B was used as Comparative Example 7, and the case where the molecular weights of the polyester polyol were 300, 550, 1600 and 1800 were referred to as Comparative Examples 11 to 14, respectively.

Comparative Examples 8 to 10 were the cases where the temperatures in the above step (1) were 90 ° C, 110 ° C and 130 ° C, respectively.

[Production Example 2] Production of a film-like flooring material

In order to evaluate the physical properties of the coated flooring prepared using the water-dispersible urethane binder of the present invention, a coating-type flooring material was prepared at a blending ratio shown in Table 2 below. At this time, as a comparative example for comparing the water-dispersible urethane binder, a water-dispersible acrylic binder was used to prepare a coating type flooring material.

Water-dispersed urethane binder Examples 1 to 3 Each 10 kg Comparative Examples 1 to 14 Each 10 kg water 5kg cement 3kg No. 8 Silk 5kg No. 6 silica sand 5kg Pigment 0.5kg

[Experimental Example] Confirmation of physical properties

[Experimental Example 1] Dispersion stability test

To a 1 L measuring cylinder, 500 ml of water were mixed with the compositions of Examples 1 to 3 and Comparative Examples 1 to 14, respectively, and then stored at 25 占 폚 for 30 days. It was judged that the stability was poor when the sedimentation state was severe (1 m / m or more).

[Table 3]

 As a result, it was found that the composition of the present invention did not cause sedimentation during storage for a long period of time, and that the compositions of Comparative Examples 1 to 14 were precipitated and poor in water dispersibility.

[Experimental Example 2] Evaluation of physical properties

The physical properties of the test items listed in Table 3 below were measured according to the respective standard test methods.

Test Items Test Methods Quality criteria for coated flooring Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 Compare to 13 Comparative Example 14 Bond strength After standard curing
(N / mm ² ) KSF4936
: 2008 1.2 or higher 3.5 3.2 3.3 2.1 1.5 1.2 1.5 1.0 1.2 2.5 1.2 1.0 1.0 1.5 1.2 1.0 1.0 After on and cold repeated test (N / mm ² ) KSF4936
: 2008 3.0 2.8 2.8 1.8 1.4 1.0 1.0 1.0 1.0 2.0 1.0 1.0 1.0 1.2 1.0 1.0 1.0 heavy metal lead KSM ISO3856-1 0.1 or less Not detected cadmium KSM ISO3856-4 0.1 or less Not detected Hexavalent chromium KSM ISO3856-5 0.1 or less Not detected Mercury KSM ISO3856-7 0.1 or less Not detected VOCs Content (g / l) Air Quality Conservation Act 16-2 Aqueous 170 or less 4 5 5 7 8 8 8 8 8 8 7 8 8 8 8 8 8 Abrasion resistance (cs-17, 1000 g, 1000 times) (mg) KSF 2813 Within 200 121 123 125 137 155 149 160 155 150 145 160 165 160 170 165 180 180 Slip resistance (BPN) KSF 2375 40 or more 63 61 58 48 47 45 45 45 45 48 30 35 35 35 30 35 30 Promoting weatherability (after WS-A, 300h) Appearance KSF 2274 No cracking after 300 hours. clear clear clear A slight crack A slight crack A slight crack A slight crack A slight crack A slight crack A slight crack Severely cracked Severely cracked Severely cracked Severely cracked Severely cracked Severely cracked Severely cracked The color difference (DELTA E ^* _ab ) KSF 2274 Color difference less than 3.0 0.7 0.8 0.7 1.0 1.2 1.3 1.2 1.1 1.1 1.0 1.2 1.5 1.3 1.6 1.5 1.5 1.8

As a result, it was found that the composition of the present invention has excellent physical properties in the content range of each component, and that it has improved physical properties as compared with conventional water-dispersible binders.

Claims (16)

A composition for preparing a water-dispersible urethane binder for a floor coating material,
The composition may comprise,
Polyester polyols; Urethane intermediates; Carboxylic acid; Alcohols; Isocyanate; Bismuth carboxylate; And amines,
The polyester polyol is a polyester polyol,
A polyester polyol having a number average molecular weight of 700 to 1500,
The urethane intermediate may contain,
A composition for the production of a water-dispersible urethane binder for a coating flooring material, which comprises a urethane intermediate obtained by polymerizing monoethanolamine and propylene carbonate in an equivalent ratio of 1: 0.5 to 2. The method according to claim 1,
Wherein the urethane intermediate comprises at least one of the following characteristics: a composition for preparing a water-dispersible urethane binder for a film-
i) an amine value of 14 to 20 mg KOH / g, ii) a flow time of 25 to 30 seconds measured at 20 DEG C by DIN53211. The method according to claim 1,
Wherein the carboxylic acid comprises dimethylol propionic acid,
The alcohols include ethoxypropanol; And < RTI ID = 0.0 > 1,4-butanediol < / RTI >
Wherein said isocyanate comprises 4,4'-dicyclohexylmethane diisocyanate,
The amines include triethylamine; And adelendiamine, wherein the composition for forming a water-dispersible urethane binder for a film-like flooring comprises at least one of polyvinyl alcohol, The method according to claim 1,
The composition may comprise, based on the total weight of the composition,
12 to 30% by weight of a polyester polyol; 1 to 20% by weight of a urethane intermediate; 0.01 to 10% by weight of carboxylic acid; 0.01 to 15% by weight of alcohols; 10 to 30% by weight of isocyanate; And 0.01 to 12% by weight of an amine, based on the total weight of the composition. The method according to claim 1,
The alcohols may be present in an amount of, based on the total weight of the composition,
0.1 to 12% by weight of ethoxypropanol; And 0.01 to 2% by weight of 1,4-butanediol, for the preparation of a water-dispersible urethane binder for a film-like flooring. The method according to claim 1,
The amines may be present in the composition in an amount, based on the total weight of the composition,
0.01 to 5% by weight of triethylamine; And 0.1 to 7% by weight of ethylenediamine. The composition for the preparation of a water-dispersible urethane binder for a film-like flooring. delete The method according to claim 1,
Wherein the bismuth carboxylate is contained in an amount of 0.001 to 1 wt% based on the total weight of the composition. A method for producing a water-dispersible urethane binder for a floor covering film, which comprises mixing the composition of any one of claims 1 to 6 and 8. 10. The method of claim 9,
Wherein the mixing comprises:
A first mixing step of mixing a polyester polyol, a urethane intermediate, a carboxylic acid, and alcohols;
Reacting the mixture of the first mixing step with nitrogen gas;
A second mixing step of further adding and mixing isocyanate, bismuth carboxylate, alcohols and amines; And
And a third mixing step of further adding alcohols, distilled water, and amines and mixing them. 11. The method of claim 10,
Wherein the first mixing step comprises:
An inert gas atmosphere, and a temperature in the range of 110 to 130 占 폚. 11. The method of claim 10,
Wherein the step of reacting the mixture of the first mixing step with nitrogen gas is carried out for 30 to 120 minutes. 11. The method of claim 10,
Wherein the second mixing step comprises:
Reacting isocyanate and bismuth carboxylate at 80 to 85 占 폚 and adding an alcohol when the NCO% becomes 17 to 18%; And
And adding an amine when the NCO% after the addition of the alcohol is 14.5 to 15.5%, and reacting the mixture for 30 to 120 minutes. 11. The method of claim 10,
Wherein the third mixing step comprises:
Cooling the mixture in the second mixing step to 45-55 占 폚;
Adding the alcohol after cooling;
Adding distilled water at 20 to 30 DEG C while stirring at 60 to 80 rpm; And
And then adding an amine and stirring the resultant mixture to form a water-dispersible urethane binder. 11. The method of claim 10,
Wherein the alcohols in the first mixing step comprise ethoxypropanol,
Wherein the alcohols in the second mixing step comprise 1,4-butanediol,
Wherein the amines in the second mixing step comprise triethylamine,
Wherein the alcohols in the third mixing step comprise ethoxypropanol,
Wherein the amines in the third mixing step comprise ethylenediamine. 12. The method of claim 11,
Wherein the inert gas is selected from the group consisting of nitrogen, helium, neon, argon, krypton, xenon, and radon.

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