KR101596779B1 - Composition of Polymers-Ceramic Hybrid Binders for Environmentally Friendly Floor Materials, Manufacturing Method for the Same and Floor Composition Comprising the Same - Google Patents

Abstract

The present invention relates to a water-soluble polymer-ceramic organic solvent hybrid binder composition comprising an organic water-soluble polymer and a water-soluble sol-state inorganic oxide and can be applied as an eco-friendly flooring or floor coating, a process for producing the same, and a flooring composition comprising the same will be.

Description

 TECHNICAL FIELD [0001] The present invention relates to a polymer-ceramic organic hybrid binder composition for environmentally friendly flooring, a process for producing the same, and a flooring composition comprising the same. ≪ Desc / Clms Page number 1 >

The present invention relates to a water-soluble polymer-ceramic organic-inorganic hybrid binder composition which can be applied as an eco-friendly flooring or floor coating agent capable of replacing or improving inorganic cement mortar or organic epoxy flooring and urethane flooring and the like, To a flooring composition.

The deterioration of the durability of the concrete section due to deterioration factors such as cracks, fractures, neutralization and saltation caused by the external impact which is frequently occurred in the inorganic concrete flooring, the detachment due to the lack of adhesion with the primary concrete construction surface, It has been regarded as a chronic problem of mortar flooring. On the other hand, organic flooring materials such as epoxy and urethane are widely used as a method to improve the appearance of external appearance while protecting the primary concrete construction surface from impacts and the like. These epoxy and urethane resins are advantageous in that they are excellent in flexibility, dustproofness, stain resistance, workability and initial adhesion. However, since epoxy and urethane flooring are mostly based on toxic organic compounds, the primary concern is the hazardous working environment at the time of construction and the long-term risk exposure of constructors and users such as persistence of residual solvent after construction, Due to the organic composition, there is a secondary problem in that a large-scale accident can be called due to a large amount of poisonous gas generated during a fire. In addition, the epoxy and urethane floors are insufficient in resistance due to the concrete surface behavior and remain only adhered to the primary concrete floor. As a result, cracks, peeling, and dropouts with the inorganic cement floor And it is not adaptive to heat change. In a place where high temperature and water are used, a phenomenon of expansion (swelling) of the construction part due to the evaporation pressure of water may occur.

In order to prevent the problems of the inorganic flooring and organic flooring, techniques for maintaining the impact resistance and durability performance of a concrete structure using a cement mortar containing a polymeric binder having a flexible property have been proposed. However, the simple mixing of such polymeric binders with inorganic flooring can be partially effective in solving the problems described above, but on the one hand it does not provide the ultimate solution because it contains all the disadvantages of each.

 The present invention has been conceived in order to solve the problems of conventional inorganic and organic flooring materials or floor coatings, and it is an object of the present invention to provide a hybrid binder composition by mixing organic synthetic resin and inorganic ceramic, To solve problems such as peeling, deterioration, cracks, and long-term durability that occur in existing organic (urethane, epoxy, etc.) or inorganic floor finishes by maximizing adhesion with the construction surface, and 2) improvement of densification 3) Eco-friendly flooring that can completely eliminate environmental harmful factors when manufacturing floors by using 100% water-based synthetic method which does not use any organic solvent at the time of manufacturing organic / inorganic hybrid binders Based hybrid binder composition.

Another object of the present invention is to provide a method for producing the above-mentioned organic or inorganic hybrid hire leader binder composition for environmentally friendly flooring.

Still another object of the present invention is to provide a flooring composition or flooring coating agent containing the above-mentioned organic-inorganic hybrid hirerender binder composition for eco-friendly flooring.

The water-soluble polymer-ceramic organic binder hybrid binder composition for eco-friendly flooring according to the present invention is characterized by comprising an organic water-soluble polymer and an inorganic oxide in a water-soluble sol state.

The method for producing the water-soluble polymer-ceramic organic solvent-based hybrid binder composition of the present invention is characterized by comprising the following steps:

(1) preparing an organic water-soluble liquid polymer,

(2) a step of hydrolyzing an inorganic oxide with a sol-gel method to produce an inorganic oxide in a water-soluble sol state, and

(3) mixing the organic water-soluble polymer obtained in the above step (1) with the inorganic oxide in the water-soluble sol state obtained in the step (2) to prepare a water-soluble polymer-ceramic organic hybrid binder.

The organic water-soluble polymer contained in the binder composition of the present invention may be one obtained from at least one polymer selected from urethane-based polymer, acrylic polymer, polyvinyl alcohol, polyvinyl acetate, polyester, epoxy- And a solid content of 1 to 60% by weight, and the kind of the polymer can be appropriately selected in accordance with the use and the required properties.

In the step (1) of the method for producing a binder composition of the present invention, water is added during the synthesis step of the organic polymer, or water is added after the synthesis, so that the polymer is dissolved or dispersed in water State liquid polymer can be produced. At this time, it is necessary to appropriately adjust the pH of the polymer. The pH range of the polymer should be controlled and adjusted according to the composition of the inorganic oxide in the water-soluble sol state contained in the organic-inorganic hybrid binder composition of the present invention. For example, the pH of the organic-base water-soluble polymer and the inorganic-based oxide sol should be uniformly adjusted by using a pH adjuster in the same system. When the organic water-soluble polymer is in an acidic condition, the pH value is adjusted to 1.5 to 3.0, preferably 1.9 to 3.0, more preferably 2 to 0.5, most preferably 2.0 to 2.5, Examples of the acid include inorganic acids (such as formic acid, acetic acid, nitric acid, citric acid, acetic acid, acetic acid, acrylic acid, glycolic acid, Can be used without limitation. When the organic water-soluble polymer is in a basic condition, the pH value is adjusted to 7.5 to 11.0, preferably 8.0 to 10.0, more preferably 9 ± 0.5, most preferably 8.5 to 9.0, (Sodium chloride, potassium chloride, barium hydroxide, calcium hydroxide, etc.) and free base (ammonium hydroxide, ammonia) or triethylamine, 1,4-diazabicyclo [2.2.2] octane, And tertiary amines such as 1,3,5-trimethylhexahydro-1,3,5-triazine can be used without limitation. If the pH range of the organic water-soluble polymer is out of the above-mentioned range, the stability of long-term storage is deteriorated and phase separation occurs between the polymer and water to cause precipitation phenomenon.

Inorganic oxide of the aqueous sol included in the binder compositions of the present _{invention, SiO 2, Al 2 O 3} , ZrO 2, TiO 2, BeO, SrO, BaO, CoO, NiO, ZnO, CaO, MgO and Fe ₂ O ₃ < / RTI >

In the step (2) of the method for producing a binder composition of the present invention, the inorganic oxide is added to water to have a solid content of 1 to 60% by weight and adjusted to an appropriate pH range with an acid or base, ), Whereby an inorganic oxide in a water-soluble sol state can be produced. When the inorganic oxide in the water-soluble sol state is in an acidic condition, the pH value of the water used in preparing the sol is adjusted to 1.5 to 3.0, preferably 1.9 to 3.0, more preferably 2 to 0.5, and most preferably 2.0 to 2.5 (Acidic, acetic, nitric, citric, acetic, chloroacetic, acrylic, glycolic, anhydrous, perchloric, and butyl acetate) and inorganic acids (such as boric acid, chromic acid, hydrochloric acid , Nitric acid, phosphoric acid, sulfuric acid, etc.) can be used without limitation. When the inorganic oxide in the aqueous sol state is in a basic condition, the pH value is adjusted to 7.5 to 11.0, preferably 8.0 to 10.0, more preferably 9 ± 0.5, most preferably 8.5 to 9.0, (Sodium chloride, potassium chloride, barium hydroxide, calcium hydroxide, etc.) and free base (ammonium hydroxide, ammonia), or triethylamine, 1,4-diazabicyclo [2.2.2 ] Octane, and tertiary amines such as 1,3,5-trimethylhexahydro-1,3,5-triazine can be used without limitation. When the pH range of the inorganic oxide in the sol state is out of the above range, the reaction rate is lowered and the sol preparation time is increased, or the long-term storage stability is lowered when mixed with the organic water-soluble polymer, which is not preferable.

The essential characteristic of the inorganic oxide included in the binder composition of the present invention is that it is a water soluble sol. Since the binder composition of the present invention includes such an inorganic oxide in a water soluble sol state together with the organic water soluble polymer , It can be easily used together with water when re-applying the floor (coating). As the gel step after the drying and curing of the floor material progresses rapidly, the chemical composition with the basic constituents of the floor material such as silica, cement and the like And the mechanical and chemical strength can be remarkably improved.

The organic-inorganic hybrid binder composition of the present invention can be produced by mixing the organic water-soluble polymer and the water-soluble organic oxide in a sol state, as in the step (3) of the method for producing the binder composition of the present invention. The mixing ratio by weight of the polymer: inorganic oxide sol may be 10:90 to 90:10, preferably 20:80 to 80:20, and more preferably 30:70 to 50:50. Is too high, the mechanical strength and the flame retardant performance are not improved. On the other hand, when the content of the inorganic oxide is too high, the elasticity is not sufficient and consequently the impact resistance is lowered. The optimum mixing ratio is determined according to the entire floor composition and the construction conditions, and can be adjusted within the range described above.

In the step (3) of the method for producing a binder composition of the present invention, the pH and the mixing ratio of the organic water-soluble polymer and the water-soluble sol-state inorganic oxide are adjusted so that the organic-inorganic hybrid binder composition of the present invention has a neutral pH value 7.0 ± 0.5) is advantageous in terms of long-term storage stability of the composition and the like.

The organic-inorganic hybrid binder composition of the present invention can be used in combination with flooring raw materials to be used in flooring construction, and also as a flooring coating agent for coating the surface of flooring applied.

The organic-inorganic hybrid binder composition of the present invention can be easily mixed with all kinds of concrete mortar composition. The mixing ratio of the inorganic hybrid binder composition can be appropriately adjusted according to the kind of the compound to be mixed and the use of the blend. For example, , The content of the organic hybrid binder may be generally from 1 to 60% by weight, preferably from 10 to 40% by weight, more preferably from 10 to 30% by weight, based on the total weight of the composition, Is suitably from 10 to 20% by weight.

When the organic binder hybrid composition of the present invention is blended with a floor material such as concrete mortar, conventional additives may be blended together. The kind of such additives is not particularly limited, and any additives conventionally used in the art All available. Examples of the additives include a thickener, a water repellent, a fluidizing agent, a defoaming agent, a dispersant, and a hardening accelerator. The thickener facilitates the construction of the flooring by controlling the viscosity of the flooring composition. Particularly, it has an advantage of improving the workability by preventing the separation of each constituent component in addition to the thickening effect of the bottom material, securing the water retention and securing the working time, as well as imparting lubrication, finish and cohesion. When the thickener is used in an amount of more than 5% by weight, the viscosity of the thickener is increased and the workability is decreased. When the content of the thickener is less than 1% by weight, the viscosity is lowered, And the layer separation occurs, which is not preferable. As the water repellent agent, it is necessary to solve the fire risk of existing oil-based water repellent agent, the regulations of the Ministry of Environment according to the air quality management law of metropolitan area, and to improve the durability of the building with excellent air permeability and penetration density, emulsion type moisture of the silane- It is preferable to use an acidic water repellent agent (aqueous repellent agent). The water repellent agent is preferably used in an amount of 3 to 10% by weight. When the water repellent agent is used in an amount less than 3% by weight, the water repellency is insufficient. When the water repellent agent is used in an amount exceeding 10% by weight, It is preferable that the fluidizing agent is used in an amount of 1 to 3% by weight. When the amount of the fluidizing agent is more than 3% by weight, the fluidity is increased and workability is good. However, There is a possibility that the sedimentation phenomenon may occur because the degree of phase mixture of organic components is low. The antifoaming agent is intended to inhibit the formation of bubbles in the finishing material composition. The bubbles cause the viscosity of the flooring composition to be lowered. In the case of forming a coating film, the adhesiveness is lowered and tints are generated on the surface of the film by bubbles, Is lowered and the strength is lowered, it is preferable to use it in the range of 0.1 to 2.0% by weight in order to suppress bubble generation. The dispersant is preferably used in the range of 0.1 to 2.0 wt.%. If the amount is less than the above range, the effect as a dispersant can not be exhibited. Even if it exceeds the above range, there is no further increase in effect.

The additives are added to maximize the effect of the organic / inorganic hybrid binder composition, which is the core of the present invention, and play an auxiliary role. When the binder composition of the present invention is mixed with the bottom material such as concrete mortar, To ensure uniformity of the composition and stability of the workability.

When the water-soluble organic or inorganic HiveReader binder composition of the present invention is mixed with a flooring material such as concrete flooring, it is necessary to (1) maximize the adhesion of the concrete floor to the first construction surface to improve the existing organic (urethane, epoxy, It is possible to improve problems such as peeling, deterioration, cracks, and long-term durability generated in the floor finish, 2) improvement of the denseness at the time of curing and curing of the flooring, and 3) The method of the present invention is advantageous in that the environmentally friendly method can be implemented by completely excluding the environmental harmful factors from the composition manufacturing process to the flooring construction since the composition is manufactured using the 100% water-based technique without using any organic solvent at all.

FIG. 1 is a schematic representation of a sol-gel reaction mechanism in the case of using SiO ₂ as the inorganic oxide used in the binder composition of the present invention, showing the stepwise chemical structure change process of the solubilization and gelation of silicon oxide.
FIG. 2 is a schematic representation of a strengthening mechanism of a floor (coating) material using the organic-inorganic hybrid binder composition of the present invention. The inorganic hybrid binder composition is prepared by mixing a mixture of cement and inorganic oxide (sand / silica) It is shown that a hybrid inorganic binder having high strength and high impact strength is obtained because there is mutual entanglement between the organic polymer chain having elasticity and the inorganic oxide chain having strong mechanical strength. In addition, it shows that the chemical bonding between the hydroxyl group present in the inorganic oxide by the gelling reaction and the concrete flooring material can exhibit a stronger mechanical strength. This mechanism also improves the adhesion to the primary concrete construction surface.
FIG. 3 is a graph showing the tensile behavior among the characteristics of the organic binder hybrid composition itself, showing well the complementary behavior between the organic polymer that imparts elasticity and the inorganic oxide that contributes to the improvement of strength.
4 is a graph showing Shore A hardness among characteristics of the organic binder hybrid composition itself.

The present invention can be more clearly understood by the following examples, but the following examples are intended to illustrate the present invention and the scope of the present invention is not limited by these examples.

Example  : Exhaust system hybrid  Preparation of binder composition and sample for property evaluation

Organic organic polymer and inorganic oxide sol were mixed in the composition shown in the following Table 1 to prepare organic hybrid binder compositions of pH 7.0. Each of the binder compositions thus prepared was dried in a Teflon mold at 60 DEG C for 24 hours and at 80 DEG C in a vacuum for 48 hours to prepare films as samples for evaluating physical properties. The thickness of the produced film was 1 mm.

Organic hybrid binder composition (% by weight) Organic polymer
(Solid content: 30% by weight) Inorganic oxide sol
(Solid content: 30% by weight) Example 1 90 10 Example 2 80 20 Example 3 70 30 Example 4 60 40 Example 5 50 50

The tensile behavior and hardness, which are typical physical properties, were evaluated for the samples for evaluating physical properties prepared as described above according to the following methods.

< Tensile behavior  >

Each of the film samples for evaluation of physical properties prepared by the organic hybrid binder compositions of Examples 1 to 5 was subjected to a tensile test at least five times and then compared with an average value. The evaluation results are shown in FIG.

<Hardness Measurement>

Each of the film samples for evaluating physical properties prepared by the organic hybrid binder compositions of Examples 1 to 5 was thickly overlaid by three or more layers to eliminate the influence of the bottom surface of the measurement. A (Shore A) type hardness meter, and their average values are compared and shown in FIG.

As shown in FIG. 4, it can be confirmed that the hardness is significantly improved as the content of the inorganic oxide increases.

Experimental Example  : Exhaust system hybrid  Preparation and Properties Evaluation of Flooring Materials Applied with Binder Composition

The organic binder hybrid composition prepared in Example 4 was compounded with a concrete raw material composition containing cement, silica sand and sand according to the composition shown in the following Table 2 to prepare a flooring composition, and then the chemical composition of the produced environmentally friendly flooring composition , And experiments for evaluating the physical properties were carried out as follows.

Flooring composition (% by weight) Portland cement Silica sand
(50/50) Absorber binder
Composition (Organic / Inorganic = 60/40) Control group 25 75 - Experimental Example 1 22 68 10 Experimental Example 2 20 60 20 Experimental Example 3 17 53 30

&Lt; Evaluation of chemical properties &

After the flooring material was applied using the flooring composition prepared by mixing together the concrete raw materials and the organic binder hybrid composition as described above, acid resistance (20% H ₂ SO ₄ , 72 hours), alkali resistance (20% NaOH, 72 hours), water resistance (H ₂ O, 72 hours) and vulcanization (100 hours exposure to ultraviolet rays).

Acid resistance Alkali resistance Water resistance Denudation Control group Good Good Good Good Experimental Example 1 Good Good Good Good Experimental Example 2 Good Good Good Good Experimental Example 3 Good Good Good Good

<Evaluation of physical properties>

Compressive strength and flexural strength were measured according to KS F-4042 after 28 days from the flooring composition using the flooring composition prepared by mixing together the concrete raw materials and the organic hybrid binder composition as described above. The results are shown in Table 4 below. &Lt; tb &gt; &lt; TABLE &gt;

Compressive strength (MPa) Flexural strength (Mpa) nonflammable Control group 70 25 Flame retardant grade 1 (fire retardant) Experimental Example 1 95 29 Flame retardant grade 1 (fire retardant) Experimental Example 2 110 35 Flame retardant grade 1 (fire retardant) Experimental Example 3 120 49 Flame retardant grade 1 (fire retardant)

From the results shown in Tables 3 and 4, when the water-soluble organic / inorganic hybrid binder composition of the present invention is applied to a flooring material such as concrete, the chemical and physical properties such as water resistance and chemical resistance, And the physical properties such as mechanical strength are further improved.

Claims (9)

delete delete delete delete delete (1) preparing an organic water-soluble liquid polymer,
(2) a step of hydrolyzing an inorganic oxide with a sol-gel method to produce an inorganic oxide in a water-soluble sol state, and
(3) preparing a water-soluble polymer-ceramic organic hybrid binder by mixing the organic water-soluble polymer obtained in the step (1) and the inorganic oxide in the water-soluble sol obtained in the step (2)
Wherein the organic-based water-soluble liquid polymer in the step (1) and the inorganic oxide in the water-soluble sol state in the step (2) are each adjusted to an acidic pH of from 1.5 to 3.0 or a basic condition of pH of 7.5 to 11.0 Wherein the hybrid binder composition is prepared by a method comprising the steps of:
delete delete delete

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