KR102396556B1 - Eco-friendly flooring material composition comprising modified urea resin compostion and desulfurized gypsum - Google Patents

Abstract

The present invention relates to a floor covering composition comprising: a modified polyurethane resin composition; and a powder, wherein the modified polyurethane resin composition consists of a main agent and a curing agent. More specifically, the present invention relates to a floor covering composition, which uses an eco-friendly material by comprising a modified polyurethane resin and a powder, wherein the modified polyurethane resin composition includes Ricinus communis oil and an eco-friendly plasticizer, and the powder includes desulfurized gypsum.

Description

A modified urethane resin composition containing vegetable natural oil and an eco-friendly plasticizer and an eco-friendly floor finishing composition comprising desulfurized gypsum.

The present invention relates to a modified urethane resin composition comprising vegetable natural oil and an eco-friendly plasticizer, and an eco-friendly floor finishing material composition comprising desulfurized gypsum, and more particularly, vegetable natural oil and an eco-friendly plasticizer as a component of the subject modified urethane resin composition. It relates to a floor finishing composition using an eco-friendly material containing desulfurized gypsum as a powder.

Floor finishing materials applied to parking lots and roofs of buildings are mostly selected based on the experience of the builder, and it is recognized as a space of low importance as a temporary space in the building code. The underground parking lot is classified as a multi-use facility, and indoor air quality standards have been established and implemented.

As a floor finishing material for such parking lots, organic floor finishing materials such as epoxy, urethane, and polyurea are most often used due to their beautiful appearance. In particular, epoxy-based floor finishing materials are the most widely used because of their advantages in performance and economic feasibility.

Although the composition of epoxy-based floor coverings differs depending on the manufacturer, there is a problem in many cases that the content of volatile organic compounds such as toluene and xylene is high, so that indoor air quality standards are not met.

On the other hand, caster oil, which is a natural vegetable oil, mainly consists of ricinoleic acid and contains a hydroxyl group, so it is a component that can react with isocyanate to form polyurethane. In addition, the castor oil is an eco-friendly material used as a raw material for natural cosmetics or soap because it has moisturizing properties and hygroscopicity to prevent moisture loss from the skin.

In addition, a plasticizer is generally added to a resin composition to lower melt viscosity and glass transition temperature to improve processability and to improve physical properties such as flexibility and cold resistance of products, and phthalate-based plasticizers are widely used. However, the phthalate-based plasticizer is classified as an environmental hormone, and the amount of the plasticizer is reduced or replaced with a non-phthalate-based plasticizer.

In addition, desulfurized gypsum is an industrial by-product obtained in the desulfurization process of a fluidized bed boiler using fuel of petroleum cokes or bituminous coal as fuel, and may serve as a filler for floor finishing materials. In addition, because it contains 30 to 65% of calcium oxide (CaO) component, it reacts with carbon dioxide (CO ₂ ) generated according to the chemical reaction of the modified urethane resin to form calcium carbonate (CaCO ₃ ), so that the surface of the floor finishing material is smoothed Not only that, but it can also improve the performance of the floor finish.

The present invention has been devised in view of the prior art as described above, and as a component of a modified urethane resin composition as a component of a floor finishing material, it contains vegetable natural oil and an eco-friendly plasticizer, which are eco-friendly materials, and an eco-friendly flooring containing desulfurized gypsum as a powder component Its purpose is to provide a finishing material.

In addition, an object of the present invention is to provide a floor finish material that can perform floor construction with excellent physical properties such as impact resistance, adhesion strength, wheel load resistance, and watertight performance by satisfying the physical properties required for floor finishing materials.

The eco-friendly floor finishing composition of the present invention for achieving the above object includes a modified polyurethane resin composition and powder consisting of a main agent and a curing agent, and the modified polyurethane resin composition includes caster oil and an eco-friendly plasticizer, , The powder is characterized in that it contains desulfurized gypsum.

In this case, the subject may be made of castor oil, polyether polyol, an eco-friendly plasticizer, an antifoaming agent, a dispersing agent, and water, and the curing agent may be made of methylene diphenyl diisocyanate (MDI).

In addition, the desulfurized gypsum may contain 60 to 70 mass % of calcium oxide (CaO), and the powder may contain 40 to 50 weight % of desulfurized gypsum based on the total weight of the powder.

In addition, the main agent, the curing agent, and the powder may be formulated in a weight ratio of 1:1:1 to 1:1:3.

The floor finishing material of the present invention contains vegetable natural oils and eco-friendly plasticizers, which are eco-friendly materials, as components of the modified urethane resin composition, and includes desulfurized gypsum as a powder component, thereby providing a floor finishing material using an eco-friendly material.

In addition, it is possible to construct floors with excellent physical properties such as impact resistance, adhesion strength, wheel load resistance, and watertight performance by satisfying the physical properties required for floor finishing materials.

1 is an observation of the surface state of a specimen made of a floor finishing material composition, and is a photograph showing the surface state of specimen 1 (a), specimen 2 (b), and specimen 3 (c).

Hereinafter, the present invention will be described in detail.

The eco-friendly floor finishing composition of the present invention comprises a modified polyurethane resin composition and powder composed of a main agent and a curing agent, and is characterized by containing an eco-friendly material. That is, the modified polyurethane resin composition includes castor oil and an eco-friendly plasticizer, and the powder includes desulfurized gypsum to provide an eco-friendly floor finishing composition.

Castor oil contained in the subject matter is a kind of polyol as a vegetable natural resin, and is used as a polyol component in a polyurethane resin composition. Since the castor oil has a high viscosity and a low coefficient of friction, it is possible to improve tensile strength and compressive strength by forming a modified polyurethane by reaction with a curing agent. In addition, since it is a natural material, it is suitable for use as an eco-friendly floor finishing composition. Castor oil used in the present invention has an OH value of 160 to 163, and it is preferable to use a saponification value of 180 to 185.

The castor oil is used in the range of 20 to 25 parts by weight, which is a range selected in consideration of the reaction with the curing agent. can

In addition, it is known that the ether-based polyol contained in the above-mentioned subject has poor compatibility with castor oil. Accordingly, the polyether polyol is preferably contained in an amount of 1 to 3 parts by weight. That is, if the content of the polyether polyol is too small, the modifying effect is reduced, but if it is too large, storage stability is reduced, so it is preferable to use it within the above range.

In addition, as the eco-friendly plasticizer, a non-phthalate-based plasticizer that does not use o-phthalate, a substance suspected of environmental hormones, as a raw material or the final product is not a regulated material may be used. The non-phthalate-based plasticizers include Aekyung Petrochemical's NEO-T, NEO-T3, NEO-S, PYROCIZER, OLICIZER-10N, OLICIZER-20N, OLI-3, LG Chem's GL-100, GL-300, EBN, BET , BASF's DINCH, EASTMAN KODAK's DOTP, etc. can be used commercially. These eco-friendly plasticizers do not contain regulated substances unlike DEHP, DINP, DIDP, DBP, BBP, DNOP, etc., which are representative phthalate-based plasticizers.

The eco-friendly plasticizer is used in the range of 48 to 53 parts by weight, it is possible to secure the appropriate viscosity of the resin composition in the above range, it is possible to secure the durability of the cured product.

The eco-friendly plasticizer has the advantage that it does not contain environmental hormone components, but there are problems such as cracks or reduced workability due to increased viscosity when applied to a floor finishing material. In addition, when a large amount of eco-friendly plasticizer is used, the possibility of occurrence of a trace amount of phthalate cannot be excluded. Therefore, when 1 to 5 parts by weight of β-cyclodextrin is mixed with respect to 100 parts by weight of the eco-friendly plasticizer, the effect of lowering the viscosity of the resin composition while suppressing the generation of the phthalate component was found to be obtained.

To this end, before mixing the eco-friendly plasticizer with the subject, β-cyclodextrin and hexane are mixed with the eco-friendly plasticizer, dried and treated, and then mixed with the subject to solve the problem of using an eco-friendly plasticizer. was found to be possible.

In addition, the subject matter may include additives such as an antifoaming agent, a leveling agent, a UV stabilizer, an antioxidant, a releasing agent, a dispersing agent, a wetting agent, a pigment, and a dye.

As the curing agent, methylene diphenyl diisocyanate (MDI) may be used, and it is preferable to use a mixture of polymeric MDI (MDI) and monomeric MDI (MDI). Specifically, a curing agent may be formed by mixing 50 to 55% by weight of the polymer MDI and 45 to 50% by weight of the monomer MDI. If the polymer MDI is added, the strength and adhesion of the modified polyurethane composition may be increased, and the monomer MDI may be added. Since it has good reactivity with the polyol constituting castor oil, it is possible to improve the physical properties of the modified polyurethane composition prepared by using the MDI mixture.

In addition, as the powder, it is preferable to use a mixture of desulfurized gypsum and mixed powder. The desulfurized gypsum is an industrial by-product generated in the desulfurization process of a fluidized bed boiler, and contains calcium oxide (CaO), sulfur trioxide (SO ₃ ), silicon oxide (SiO ₂ ), magnesium oxide (MgO), and the like as main components. The desulfurized gypsum is composed of various component ratios according to the occurrence factors. As a result of the experiment, it was found that the best effect can be obtained when the desulfurized gypsum having a calcium oxide (CaO) content of 60 to 70 mass% is used.

Calcium oxide contained in the desulfurized gypsum reacts with carbon dioxide to form calcium carbonate, which has been shown to affect surface flatness. Therefore, when performing floor construction using the floor finishing material composition, when using desulfurized gypsum having a calcium oxide (CaO) content of 60 to 70 mass% compared to when using a flue gas desulfurized gypsum with a low calcium oxide content, a non-slip surface, etc. properties were found to be better.

In addition, as the mixed powder constituting the powder, calcium carbonate (CaCO ₃ ), calcium component such as calcium hydroxide (Ca(OH) ₂ ) and silicon dioxide (SiO ₂ ) A calcium-silicon-based powder mixed can be used. Specifically, the calcium-silicon-based powder is preferably a powder in which 50 to 70% by weight of calcium carbonate and/or calcium hydroxide and 30 to 50% by weight of silicon dioxide are mixed.

In terms of recycling of industrial by-products, it is preferable to use only desulfurized gypsum as powder, but when using only desulfurized gypsum as powder, physical properties deteriorate during floor construction, so it is preferable to use a mixture of the calcium-silicon-based powder . In addition, the desulfurized gypsum may be contained in an amount of 40 to 50% by weight based on the total weight of the powder. If the content of the desulfurized gypsum is too high, there is a problem that the physical properties during floor construction are deteriorated, so that the quality standards cannot be met. It is preferable to do

In addition, it is preferable to use the powder by pulverizing it to a size of 0.1 to 50 μm. The size of the powder is a particle size as a filler contained in the resin composition, and may be classified according to the use.

In addition, the main agent, the curing agent and the powder are preferably mixed in a weight ratio of 1:1:1 to 1:1:3. This mixing ratio is selected in consideration of the reaction of the main agent and the curing agent, workability of the floor finish composition, curing speed, etc., and if it is out of the above ratio, unreacted products or defects that do not satisfy the quality standards after floor construction occur. It was found to be preferable to blend within the above range.

In order to check the difference according to the type of powder, the main agent, curing agent, and powder were mixed in a weight ratio of 1:1:1 to prepare a floor finish composition, and after laying it in a container with a thickness of 5 cm, the surface condition was observed. is the same as in FIG.

In Figure 1, the surface state of the three samples is observed, calcium-silicon-based powder (CaCO ₃ 30 wt%, Ca(OH) ₂ 30 wt%, SiO ₂ 40 wt%) and desulfurized gypsum (CaO 65.1 wt%) ) in the case of using a mixed powder (a), when desulfurized gypsum was used as powder (b), and when flue gas desulfurization gypsum (CaO 32.07 mass%) was used as powder (c), as a result of observing the surface state, the mixture When powder was used, the surface state was smooth and flatness was high. However, when only desulfurized gypsum was used, the surface was flat and some cracks were observed. When flue gas desulfurized gypsum was used, the surface flatness was poor and cracks were also observed. These results support the effect of the content of calcium oxide contained in the desulfurized gypsum and the difference in the surface condition when the desulfurized gypsum and calcium-silicon-based powder are used together.

In order to confirm the effect of the eco-friendly floor finishing composition according to the present invention, a test evaluation was performed as follows.

The floor finish composition was prepared with the components and contents shown in Table 1, and the floor finish composition was prepared by preparing the main agent, curing agent, and powder, respectively, and then mixing them. The main agent, curing agent, and powder were mixed in a weight ratio of 1:1:2.

In addition, as the polyol, KONIX PP-3000 (OH value = 54 to 58, MW = 3,000) was used.

In addition, as the plasticizer 1, NEO-T (bis(2-ethylhexyl) terephthalate) manufactured by Aekyung Petrochemical was used. After adding 3 parts by weight of β-cyclodextrin and 10 parts by weight of hexane to 100 parts by weight of NEO-T, mixing them, and removing hexane as a solvent using a rotary concentrator, an eco-friendly plasticizer treated with β-cyclodextrin was obtained and used. 2, Aekyung Petrochemical's NEO-T was used without additional treatment.

As a result of XRF analysis, the desulfurized gypsum had a CaO content of 65.1 mass% and a SO ₃ content of 27.3 mass%, which was confirmed to have a high calcium oxide content _. It was confirmed that the content of calcium oxide was low as the content of 42.55% by mass.

In addition, as the calcium-silicon-based powder, a powder composed of 40% by weight of CaCO ₃ , 20% by weight of Ca(OH) ₂ , 40% by weight of SiO ₂ was used.

In Table 1, the unit is parts by weight.

ingredient Example Comparative Example 1 Comparative Example 2 Comparative Example 3 subject castor oil 23 23 23 - polyol 2 2 2 25 plasticizer 1 50 - 50 50 plasticizer 2 - 50 - - antifoam 0.4 0.4 0.4 0.4 dispersant 0.6 0.6 0.6 0.6 water 24 24 24 24 hardener polymeric MDI 52 52 - - monomeric MDI 48 48 - - powder Calcium-silicon-based powder 52 52 52 52 Desulfurized gypsum 48 48 - 48 flue gas desulfurization gypsum - - 48 -

The results of analyzing the heavy metal content of the prepared floor finishing composition are shown in Table 2.

heavy metal Test Methods detection limit Example Comparative Example 1 Comparative Example 2 Comparative Example 3 Pb KSM ISO 3856-1:2007 0.0005 nd nd nd nd CD KSM ISO 3856-4:2007 0.0001 nd nd nd nd Hg KSM ISO 3856-5:2007 0.0001 nd nd nd nd Cr ⁶⁺ KSM ISO 3856-7:2007 0.0001 nd nd nd nd

Impact resistance performance, adhesion performance, wheel load resistance performance, watertight performance, and pollutant emission tests were conducted for the floor finishing material composition according to the quality standard test method of KS F 4937 (surface finishing material for parking lot floor). Table 3 shows the quality standards and evaluation results of KS F 4937.

Evaluation items Quality standards Example Comparative Example 1 Comparative Example 2 Comparative Example 3 impact resistance No punctures, cracks, burrs, peeling clear clear clear clear adhesion performance
(N/㎟) >1.2 2.8 2.0 1.5 1.3 Wheel load resistance performance
(300kg, 80,000 times) surface condition There are no abnormalities such as cracks, splintering, peeling, etc., and the lower layer is not exposed. clear clear clear Partial grinding is observed, but overall good Depth of thickness reduction (mm) <3.0 0.5 0.8 1.8 2.2 watertight performance Not permeable to the substrate surface clear clear clear clear Pollutant release test
(mg/m 2 h) TVOC <2.5 0.052 0.155 0.065 0.050 formaldehyde <0.12 non-detection non-detection non-detection non-detection toluene <0.08 0.001 0.008 0.001 0.001

As a result of testing and evaluation in accordance with the performance standards of surface finishing materials for parking lot floors, it was found that the surface finishing materials for floors of Examples and Comparative Examples 1 to 3 met the quality standards according to KS F 4937. However, in Comparative Example 1 in which NEO-T, an eco-friendly plasticizer, was used without a separate treatment, the total VOC content was found to be relatively high. This is presumed to be due to the problem of non-phthalate-based plasticizers, which are known to detect a small amount of phthalate. In addition, the adhesion performance and wheel load resistance performance also showed slightly lower physical properties than in the Examples, so it was judged that there was an effect of treating the eco-friendly plasticizer with β-cyclodextrin in the Examples.

In addition, in Comparative Example 2 using flue gas desulfurization gypsum, the adhesion performance and the wheel load resistance performance were found to be somewhat lower than those of the Example, which is presumed to be a result of reflecting the effect on the surface flatness of calcium oxide as described above.

In addition, in Comparative Example 3 using only polyol without using castor oil, the wheel load resistance performance was somewhat low, indicating that the effect was somewhat lower than when castor oil and polyol were used in combination.

From these results, it was confirmed that high-quality floor construction was possible using the eco-friendly floor finishing composition according to the present invention.

The present invention has been described with reference to a preferred embodiment as described above, but it is not limited to the above embodiment, and various modifications and changes can be made by those skilled in the art to which the present invention pertains without departing from the spirit of the present invention. Changes are possible. Such modifications and variations are intended to fall within the scope of the present invention and the appended claims.

Claims (5)

As an eco-friendly floor finishing composition comprising a modified polyurethane resin composition and powder consisting of a main agent and a curing agent,
The modified polyurethane resin composition includes castor oil and an eco-friendly plasticizer,
The powder is used by mixing desulfurized gypsum and calcium-silicon-based powder having a calcium oxide (CaO) content of 60 to 70% by mass,
The powder is an eco-friendly floor finishing composition, characterized in that it contains 40 to 50% by weight of desulfurized gypsum based on the total weight of the powder.
The method according to claim 1,
The subject consists of castor oil, polyether polyol, eco-friendly plasticizer, defoamer, dispersant, and water,
The curing agent is an environment-friendly floor finishing composition, characterized in that consisting of methylene diphenyl diisocyanate (methylene diphenyl diisocyanate, MDI).
delete delete The method according to claim 1,
The main agent, hardener and powder are an eco-friendly floor finishing composition, characterized in that it is mixed in a weight ratio of 1:1:1 to 1:1:3.

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