KR101195107B1 - Method for manufacturing floor mateial comprising polyurethane and floor material prepared therefrom - Google Patents

Abstract

PURPOSE: A manufacturing method of polyurethane floor material is provided to be easily constructible and to contain extremely contents of heavy metal. CONSTITUTION: A manufacturing method of polyurethane floor material comprises: a step of forming polyol by mixing diol and triol; a step of forming dry polyol by vacuum-dehydrating the polyol to make the moisture content 0.001-0.2 weight%; a step of preparing an urethane prepolymer of number average molecular weight of 10,000-20,000 g/mol by putting isocyanate into the dry polyol with equivalent ratio of 1:1.2-1.3; and a step of adding carbon dioxide absorber comprising hydroxide calcium and chain extender into the urethane prepolymer.

Description

Polyurethane flooring manufacturing method and the flooring manufactured thereby {METHOD FOR MANUFACTURING FLOOR MATEIAL COMPRISING POLYURETHANE AND FLOOR MATERIAL PREPARED THEREFROM}

The present invention relates to a polyurethane flooring manufacturing method and a flooring manufactured thereby, and more particularly, to a flooring manufacturing method using a polyol formed by mixing a diol and a triol using a one-component urethane resin and a flooring manufactured thereby.

In general, the flooring is prepared by mixing or laminating other materials to polyvinyl chloride (PVC) or vinyl chloride. Flooring is usually composed of a plurality of layers, such as transparent layer, printed layer, resin impregnated dimensional reinforcement layer, foam layer and easy layer, where the transparent layer serves to protect the ink surface printed on the printed layer, the printing layer is a color or pattern The impregnated dimensional reinforcement layer is a glass-fiber impregnated with urethane resin to reinforce the dimensional safety of the product, and the foam layer provides a cushion, and the easy layer is reinforced. And a seating function with the bottom surface.

Polyurethane material is produced in the production plant divided into isocyanate prepolymer and polyol mixture and processed at various stages of weighing, blending, stirring, and construction according to the mixing ratio set at the construction site. It is a cause of the increase in labor costs because it requires, and the problem of reducing the construction efficiency by raising the construction cost as a whole may be pointed out as a disadvantage. Moreover, there was a problem that swelling of the coating film frequently occurred due to the carbonic acid gas generated when the water and the isocyanate group reacted during curing.

In general, two-component polyurethane materials have to use both agitated waterproofing materials within a limited pot life, so the time interval between agitation and construction must be well controlled, and if the time is not correct, the amount of material loss increases. Therefore, in order to maintain the excellent physical and chemical properties of these polyurethane materials and to compensate for the shortcomings as a two-component type, one-component formulation of polyurethane building materials has been studied.

However, through the above research, the storage stability and the swelling of the coating film due to the carbon dioxide generated by the reaction of the water and the isocyanate have been partially improved. There was a problem falling.

In order to solve the above problems, isocyanate is added and synthesized with a dihydric polyhydric alcohol to prepare a flooring material using a urethane resin containing free isocyanate (-N = C = O) in a one-component urethane resin. It provides a method and a floor material produced thereby.

The flooring manufacturing method does not cause environmental pollution because heavy metals are not detected in the flooring, unlike the conventional metal catalyst.

In preparing the flooring material, the ratio of polyol and isocyanate may be optimized to provide a one-component urethane resin having an improved reaction rate.

Polyurethane flooring manufacturing method according to embodiments of the present invention is a step of forming a polyol by mixing diol (triol) and triol (triol), by vacuum dehydration of the polyol to a water content of 0.001 to 0.2% by weight Forming a dried polyol, preparing a urethane prepolymer by adding isocyanate to the dried polyol, and adding a carbon dioxide absorbent and a chain extender to the urethane prepolymer. .

The diol may include one or more selected from neopentyl glycol, ethylene adiphate, and 1,2-propanediol (1,2-propanediol).

The triol may include one or more selected from trimethylol propane and glycerol.

The polyol may include 60 to 70 wt% of the diol and 30 to 40 wt% of the triol.

Moisture content of the dried polyol may be 0.01 to 0.08% by weight.

The isocyanate may include at least one selected from toluene diisocyanate, diphenyl methane diisocyanate, and isopropyl diisocyanate.

The carbon dioxide absorbent may include calcium hydroxide, and the calcium hydroxide may be added in an amount of 3 to 5 wt% based on the total weight.

Forming the dried polyol is characterized in that the polyol is vacuum dehydrated at 100 ℃ for 6 hours, the step of preparing the prepolymer is the reaction of the dried polyol and the isocyanate at 70 to 90 ℃ 7 to 11 hours You can.

The preparing of the urethane prepolymer may have an equivalent ratio of the isocyanate and the polyol in a ratio of 1.2 to 1.3: 1, and an average molecular weight of the urethane prepolymer may be 10,000 to 20,000 g / mol.

The chain extender includes 0.01 to 2% by weight of one or more selected from 1,4-butanediol, 1,6-hexandiol, 1,6-hexanediol, and ethylen glycol. can do.

The flooring manufacturing method may further comprise 5 to 7% by weight of adipic acid polyester (adipic acid polyester) as a plasticizer.

The polyurethane may be characterized by absorbing moisture and curing.

Flooring according to embodiments of the present invention can be manufactured by the flooring manufacturing method.

The flooring material may have (a) tensile strength of 0.8 to 4.5 MPa, (b) elongation of 70 to 150%, and (c) tensile stress of 0.5 to 1.5 MPa.

Flooring according to embodiments of the present invention provides a flooring that can be easily installed without the need to separately mix the main (polyisocyanate) and the curing agent (polyol). The flooring material can improve productivity, extremely low content of carcinogens and heavy metals is an excellent eco-friendly product that can be installed in school playgrounds, children's play facilities, and walkways.

The method of manufacturing the flooring may reduce the occurrence of pinholes that may occur during curing.

1 is a pulverized polyurethane flooring prepared according to embodiments of the present invention.
Figure 2 shows a urethane elastic packaging material prepared according to the embodiments of the present invention.
3 is a test report according to the quality standards of the foamed elastic packaging material.
Figure 4 shows the content of the body residue by the size of the polyurethane chip.
5 and 6 are test reports for testing the degree of inclusion of harmful substances after grinding the polyurethane in powder form.

Hereinafter, the present invention will be described in more detail with reference to the following examples. The objects, features and advantages of the present invention will be easily understood by the following embodiments. The present invention is not limited to the embodiments described herein, but may be embodied in other forms. The embodiments disclosed herein are provided so that the disclosure may be thorough and complete, and that those skilled in the art will be able to convey the spirit of the invention to those skilled in the art. Therefore, the present invention should not be limited by the following examples.

Polyurethane flooring manufacturing method according to an embodiment of the present invention is a step of forming a polyol by mixing diol (triol) and triol (triol), the step of vacuum dehydrating the polyol to form a dried polyol, Isocyanate may be added to the dried polyol to prepare a urethane prepolymer, and to add a carbon dioxide absorbent and a chain extender to the urethane prepolymer.

The flooring manufacturing method according to the embodiments of the present invention can obtain a catalytic effect by optimizing the ratio of the polyol and the isocyanate, and can be free from environmental problems because it does not use a metal catalyst.

The manufacturing method relates to a method for producing a flooring material using a one-component polyurethane resin, and may use a latent catalyst or a moisture scavenger.

Unlike the two-component polyurethane resin, the one-component polyurethane resin does not separately prepare and contain isocyanates and polyols, but rather blends the isocyanates and polyols in an appropriate ratio to overcome the problems of poor curing.

Forming the polyol may include mixing a diol and a triol.

The diol may include one or more selected from neopentyl glycol, ethylene adiphate, and 1,2-propanediol (1,2-propanediol), wherein the triol is trimethylol It may include one or more selected from propane (trimethylol propane) and glycerol (glycerol).

A ratio of the diol and the triol may include 60 to 70 wt% of the diol, and 30 to 40 wt% of the triol.

When the ratio of the diol and the triol was as described above, the curing progress was excellent, and the curing failure was lower than when diol or triol were included alone.

The polyol may be introduced into a stainless steel reactor to which an invert is attached and the stirring speed may be controlled. The reactor can control temperature and pressure.

The polyol introduced into the reactor may be vacuum dehydrated at 100 ° C. for 6 hours. When the polyol is dehydrated to have a water content of 0.05% or less, the isocyanate may be added and reacted at 70 to 90 ° C. for 7 to 11 hours to prepare a prepolymer.

The isocyanate may include at least one selected from toluene diisocyanate, diphenyl methane diisocyanate, and isopropyl diisocyanate.

The prepolymer prepared in the reactor has a lower NCO / OH equivalent ratio than a conventional two-component prepolymer, and thus has a high molecular weight and a free NCO group content of 2 to 3 wt% based on the total weight.

Polyurethane flooring according to the embodiments of the present invention has a ratio of 1.2 to 1.3: 1 equivalent ratio of the isocyanate and the polyol, the average molecular weight of the urethane prepolymer may be 10,000 to 20,000 g / mol.

The flooring according to the embodiments of the present invention may add a latent catalyst or a moisture scavenger, and the latent catalyst or the moisture absorbent may be hydrolyzed to water to regenerate the amine to increase the curing rate of the polyurethane. Can be improved.

The formula below shows that the latent catalyst reacts with water to regenerate the diamine.

Formula 1

R ₁ -C = N-R-N = C-R ₂ + 2H ₂ O → H ₂ N-R-NH ₂ + OCN-R ₂ -NCO

The amine group may react with NCO to form a urea reaction.

The room temperature-curing one-component polyurethane resin is reacted by moisture in the air, and the amine produced by the reaction of isocyanate with water is substantially involved.

The moisture-curable polyurethane resin according to the embodiments of the present invention may proceed to the following steps.

(end)

(I)

(All)

(la)

(hemp)

When RNCO reacts with water, carbarnic acid can be produced. Since the decarbonation reaction of (B) the carbanic acid is significantly faster than that of the carbanic acid, the carbanic acid produced by the reaction of water and isocyanate is not intact and proceeds directly to (A). do.

Therefore, the first step of the moisture curing reaction of the polyisocyanate can be seen as (b) amine formation reaction. In addition, the actual curing of the coating film may occur by cross-linking reaction due to the production of urea competition in (C) or the formation of biurets in (D).

Such a reaction can be handled like a polyurethane because polyisocyanate is used as a vehicle without actually producing a urethane bond (R-NHCOO-R ').

The prepolymer of the moisture-curable polyurethane resin may form a coating film by reacting with one isocyanate four isocyanates. Thus, when a small amount of moisture is present, the curing reaction proceeds, so care should be taken in handling.

Hardening time is affected by humidity, and the higher the humidity, the shorter the curing time, but too high may cause bubbles or pinhole phenomenon.

Polyurethane flooring manufacturing method according to embodiments of the present invention may further comprise the step of adding a carbon dioxide absorbent.

In order to reduce the carbon dioxide, the polyurethane flooring material may include 3 to 5% by weight of calcium hydroxide (Ca (OH) ₂ ), based on the total weight. It may be represented as shown below.

(2)

Ca (OH) ₂ + CO ₂ → CaCO ₃ + H ₂ O

In the preparation of the prepolymer according to the embodiments of the present invention, in order to maintain initial reaction conditions in weak acidity, it may include one or more of phosphoric acid (H ₃ PO ₄ ) and phosphorous acid (H ₃ PO ₃ ).

According to embodiments of the present invention may include 5 to 7% by weight of a nonphthalate plasticizer including an adipic acid polyester and Napten oil for elongation of the flooring material. The nonphthalate plasticizer is an environmentally friendly plastic material and does not pose a problem to the atmospheric environment.

Since the inner layer of the flooring material is slow in contact with water, a chain extender may be used to improve this, thereby improving internal curing and initial adhesion. The chain extender includes 0.01 to 2% by weight of one or more selected from 1,4-butanediol, 1,6-hexandiol, 1,6-hexanediol, and ethylen glycol. can do.

The antifoaming agent and the antifoaming agent may be included in an amount of 1% by weight based on the total weight of the anti-UV agent and the anti-foaming agent to improve the weather resistance. (BYK, Tego)

Manufacturing example  One. Prepolymer  Produce

Table 1 below shows the influence of the polyurethane resin according to the content of diols and triols in a table.

PP-3000 PP-2000 and PP-1000 represent bifunctional polyols, and GP-5000 GP-3000 and GP-1000 represent trifunctional polyols. In the composition of the polyether polyol of Table 1 below, (/) was used to indicate the ratio.

The plasticizers of Examples 1 to 12 of Table 1 were all used in 10% by weight.

Polyether Polyol Composition NCO / OH equivalence ratio Plasticizer Type NCO% Viscosity (PS) Total volume Example 1 PP -3000 1.85 / 1 N-15 1.79% 43.6 ps 100% Example 2 PP -2000 1.85 / 1 N-15 2.60% 54.16 ps 100% Example 3 GP -3000 1.85 / 1 N-15 2.65% 128 ps 100% Example 4 GP -5000 / PP -2000
(5/5) 1.85 / 1 N-15 2.09% 73.2 ps 100% Example 5 GP -5000 / PP -2000
(5/5) 1.25 / 1.0 N-15 0.75% 960 ps 100% Example 6 GP -5000 / PP -2000
(5/5) 1.25 / 1.0 N-15 0.65% 256 ps 92.68% Example 7 GP -3000 / PP -3000
(5/5) 1.25 / 1.0 N-15 0.80% 854 ps 96.2% Example 8 GP -1000 / PP -1000
(5/5) 1.09 / 1.0 N-15 0.80% Gelation - Example 9 GP -3000 / PP -3000
(5/5) 1.34 / 1.0 N-15 0.97% 175 ps 88.70% Example 10 GP -1000 / PP -3000
(4/6) 1.30 / 1.0 N-15 0.88% 43.6 ps 89.8% Example 11 GP -1000 / PP -3000
(3/7) 1.30 / 1.0 N-15 0.70% 54.16 ps 100% Example 12 GP -1000 / PP -3000
(4/6) 1.30 / 1.0 N-50 0.89% 128 ps 100%

Referring to Table 1, Examples 1 and 2 are used alone bifunctional polyol (diol), Example 3 is using trifunctional polyol alone. As shown in Examples 1 and 3, it was observed that the curing of the polyurethane did not proceed when the bifunctional or trifunctional groups were added alone.

In the case of Example 4, both the bifunctional polyol and the trifunctional polyol were added, but the hardening was poor because there was still a part that was not cured while curing at room temperature.

In Examples 5 to 9, the elapsed viscosity of synthesizing NCO / OH close to 1.25 was very large, and the molecular weight was tended to be larger than Examples 1 to 4.

When NCO / OH is blended at 1.2 or less, the molecular weight may be increased, and gelation may be performed. Referring to Example 8, it was observed that gelation actually proceeds when NCO / OH is blended at 1.1 or less.

In the case of Example 9, room temperature curing was possible, but when stored at 60 ° C. for 7 days, the viscosity increased 2.5 times during storage, indicating poor storage. (Initial viscosity was 360,000 CPS but was observed 980,000 CPS after 7 days)

In Examples 10 to 12, the ratio of triol was less than that of diol. In this case, the viscosity change was stable within 10%.

Manufacturing example  2. Prepolymer  Preparation of Polyurethane Flooring Containing

Table 2 below is a table showing a configuration for producing a polyurethane comprising the prepolymer.

Testno
Raw material name Example  One Comparative example  One Comparative example  2 Remarks Urethane
Prepolymer 32 32 32 Self Synthetic Iaten catalyst One One One CaCo ₃ (wt%) 50 50 50 Filler Ca ( OH ) ₂ (wt%) 5 5 - UV absorber (wt%) 0.1 0.1 0.1 Defoamer (% by weight) 0.2 0.2 0.2 BYK , TEGO Chain Extender 0.6 - 0.6 Curing degree ○ Internal hardening failure Large amount of bubbles Elapsed time One HR One HR One HR

In Comparative Example 1, the polyurethane flooring material was prepared using Example 12 of the prepolymer, and thus the internal curing degree was poor because the chain extender was not included.

In Comparative Example 2, the polyurethane flooring material was prepared using Example 12 of the prepolymer, and did not include calcium hydroxide (Ca (OH) 2), and it was found that a large amount of bubbles were generated.

In the case of Example 1, both calcium hydroxide (Ca (OH) ₂) and chain extenders were included to show excellent degree of curing.

Table 3 below is a table comparing the one-component prepolymer and the two-component prepolymer.

1-component prepolymer 2-component prepolymer Chemical reaction Reaction With H₂O Reaction with polyol Reaction speed Very fast fast Cost Low High physical property Good Good Mechanics OCN-R-NCO + H₂O OCN-R-NCO + ROH Curing catalyst Latent Catalyst or Moisture
Scavenger Metals, Amine Curing Type Moisture Curing Type Polyol Curing Type Curing method Chain Extender Available Available

Experimental Example

Experimental Example 1 to Experimental Example 3 below is to evaluate the physical properties of the flooring material using the polyurethane as shown in reference to KS F 3888-2: 2011 regulations.

Experimental Example  1. Quality Standards of Polyurethane Powder

Test Items standard Test Methods TEST results A (grass) B (packaging material) importance 1.5 or less KS M ISO 2781 or
KS M 6519 1.27 Chezanbun
(%) Of the eye
size
(mm) 3.5 Less than 27 Less than 7 KS M 0064 0.2 2.8 ~ 3.5 More than 70 1.4-2.8 85 or more 99.8 1 ~ 1.4 Less than 2 Less than 1 Less than 8 0.1

Table 4 shows the content of the body residue by the size of the polyurethane produced according to the embodiments of the present invention as a powder.

A represents the standard of the polyurethane powder to be used where the grass can be planted, and B represents the standard of the polyurethane powder to be used as a packaging material.

Referring to Table 4, the test result showed that the specific gravity was 1,27 or less, which is a reference value of 1.5 or less, and the content of body residue according to the size of the body was found to meet all the criteria.

Experimental Example  2. Quality Standards of Polyurethane Powder Hazardous Substances

Test Items standard Test Methods TEST results heavy metal
(mg / Kg) Pb 90 or less KS M 6956 Not detected CD 50 or less Not detected Cr ^{6 +} 25 or less Not detected Hg 25 or less Not detected

)
(mg/Kg)Volatile Organic Compounds (T-VOCs)

)
(mg / Kg) Benzene 50 or less KS M 6956 0.3 Toluene Ethyl-benzene Xylene Polycyclic Aromatic Hydrocarbons (PAHs)

) (mg / Kg) below 10 KS M 6956 Not detected

Benzene content in T-VOCs should be less than 1 mg / Kg.

The Benzo (a) pyrene content in PAHs should be less than 1 mg / Kg.

Table 5 shows the degree of inclusion of harmful substances after grinding the polyurethane in powder form.

As shown in Table 5, no heavy metals containing lead and the like were not detected in the polyurethane powder. The volatile organic compounds were 0.3 mg / kg or less, which is less than the standard value of 1 mg / kg, and polycyclic aromatic hydrocarbons. Was not detected.

Experimental Example  3. Foaming  Quality Standards for Elastic Packaging Materials

Test Items standard Test Methods TEST results Upper layer Bottom layer Tensile Strength (MPa) 0.6 or more 0.4 or more KS M 6518 1.0 Elongation (%) 60 or more - 121 Tensile stress (MPa) 0.45 or more - KS M 6518 0.69 Hardness State (Hs, 23 ± 2 ℃) 40 or more See KS F 3888 E 69 After aging (Hs, 70 ± 2 ℃) State hardness result within ± 10% E 68 Porosity (%) 20% or more See KS E ISO 1014 22 Accelerated Exposure Test (Grade) Level 3 or higher - KS F 2274 (Method)
KS K 0903 (Compare) 2 Note 1 Tensile strength and tensile stress test values shall be reset by test verification after notification.
Note 2. Accelerated exposure testing is to be done for press only.

Table 6 shows the quality standards of the foamed elastic packaging material.

Test items are tensile strength, elongation, tensile stress, hardness, porosity, and accelerated exposure test.

The tensile strength and elongation were tested by using the KS M 6518 method, the tensile strength was 1.0MPa in both the upper layer and the lower layer was above the standard, the elongation was 121% or more.

The tensile stress was tested using the KS M 6518 method, the tensile stress was 0.69MPa higher than the reference value 0.45, the hardness of both the initial state and aging was above the standard.

In addition, the porosity was tested according to the KS E ISO 1014 method was found to be 22%, exceeding the standard value 20%.

Hereinafter, specific embodiments of the present invention have been described. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.

Claims (14)

A diol selected from the group containing neopentyl glycol, ethylene adipate and 1,2-propanediol and a triol selected from the group containing trimethylol propane and glycerol are mixed to form a polyol Making;
Vacuum dehydrating the polyol to a water content of 0.001 to 0.2 wt% to form a dried polyol;
Preparing a urethane prepolymer having a number average molecular weight of 10,000-20,000 g / mol by adding isocyanate at a ratio of 1: 1.2 to 1.3 equivalents to the dried polyol; And
And adding a carbon dioxide absorbent and a chain extender including calcium hydroxide to the urethane prepolymer.
delete delete The method of claim 1,
The polyol is a polyurethane flooring manufacturing method, characterized in that 60 to 70% by weight of the diol, 30 to 40% by weight of the triol. The method of claim 1,
The moisture content of the dried polyol is a polyurethane flooring manufacturing method, characterized in that 0.01 to 0.08% by weight. The method of claim 1,
The isocyanate is a polyurethane flooring manufacturing method comprising at least one selected from toluene diisocyanate, diphenyl methane diisocyanate, and isopropyl diisocyanate. The method of claim 1,
The carbon dioxide absorbent containing calcium hydroxide is a polyurethane flooring manufacturing method, characterized in that 3 to 5% by weight based on the total weight of the polyurethane flooring composition. The method of claim 1,
Forming the dried polyol is characterized in that for dehydrating the polyol at 100 ℃ for 6 hours,
The preparing of the prepolymer may include reacting the dried polyol with the isocyanate at 70 to 90 ° C. for 7 to 11 hours. delete The method of claim 1, wherein
The chain extender may comprise at least one selected from 1,4-butanediol (1,4-butandiol), 1,6-hexandiol (1,6-hexanediol), and ethylen glycol (polyethylene flooring composition) Polyurethane flooring manufacturing method comprising 0.01 to 2% by weight compared. The method of claim 1,
At least one selected from adipic acid polyester and Napten oil as a plasticizer, and the plasticizer further includes 5 to 7 wt% of the polyurethane flooring composition, based on the total weight of the polyurethane flooring composition. Manufacturing method. The method according to any one of claims 1, 4 to 8, 10 and 11,
The polyurethane is a polyurethane flooring manufacturing method, characterized in that the moisture is absorbed and cured. The method according to any one of claims 1, 4 to 8, 10 and 11,
Polyurethane flooring, characterized in that produced by the manufacturing method. The method of claim 13, wherein the flooring material
(a) tensile strength is 0.8 to 4.5 MPa,
(b) elongation is 70-150%,
(c) Flooring, characterized in that the tensile stress is 0.5 to 1.5 MPa.

Images