KR102039313B1 - The method for manufacturing and composition the same elastic paving material of eco-friendly water-soluble coating composition for surface enhancement of Cork Chips - Google Patents

Abstract

The present invention relates to an eco-friendly water-soluble coating liquid composition for surface modification of a cork chip, which can exhibit an effect of improving excellent adhesion, water resistance, tensile strength, workability, elongation, and the like of the cork chip which can be used as the elastic chip of an elastic floor packaging material when applying the coating to a natural material cork chips collected from a cork oak or an oriental oak. The eco-friendly water-soluble coating liquid composition comprises: a water-soluble mixture A liquid containing a urethane-modified water-soluble epoxy resin, a catalyst, and nanosilica sol; and a water-soluble mixed solution B liquid containing organosilane, modified aliphatic amine, a polymer emulsifier, and water as essential components.

Description

The method for manufacturing and composition the same elastic paving material of eco-friendly water-soluble coating composition for surface enhancement of Cork Chips}

The present invention relates to a composition for modifying the surface of the cork chip used as an elastic chip material of the elastic packaging material, more specifically, the adhesion, water resistance, tensile strength, workability of the cork chip, which is a natural material collected and crushed from oak or oyster oak The present invention relates to an environmentally friendly water-soluble coating liquid composition for cork chip surface modification, a modified cork chip for modifying elastic packaging materials, and an environmentally friendly cork chip usable for elastic packaging materials using the composition.

In places such as children's playgrounds, walks, walkways, bicycle paths, parks, etc., elastic flooring materials are provided to prevent slippage, shock absorption, and cushioning to prevent safety accidents of users.

Conventionally, an elastic floor packaging material was constructed by mixing waste tire chips or EPDM chips with urethane. For example, in Patent No. 10-1156499 (Construction method and structure of elastic floor materials for children's playgrounds, elastic rubber chips). And color rubber chips. In the patent, the elastic rubber chip is used as the elastic rubber chip having a particle size of 5 to 7 mm made of recycled rubber such as waste tire, and the colored rubber chip is a polyurethane rubber or ethylene propylene diene (EPDM) having excellent heat resistance, cold resistance and color stability. : Ethylene Propylene Diene Monomer) Made of rubber. In addition, polyurethane binders and thinners are used as binders for the elastic rubber chips and color rubber chips.

However, social and environmental problems continue to occur due to waste tire chips, which are essentially used in the construction of conventional elastic rubber chips, or harmful components contained in EPDM chips.

In order to solve this problem, there have been attempts to replace the natural cork chips.

Cork is a bark in which oyster oak or cork oak is aged and deposited and has a very low specific gravity and has a porous structure. Cork is used for bottle caps, car gaskets, wall panels, boards, fishing rod handles, etc. because of its excellent naturalness and impact resistance, and is expected to be used as an alternative to elastic rubber chips containing harmful ingredients.

For example, in Patent Publication No. 10-2012-0002773, a technique for elastic floor packaging material using cork is introduced. At one time, cork chips, ore particles, polyurethane adhesives, silane coupling agents, organic solvents, esters or hydrocarbon solvents. It is supposed to make a bottom packaging composition by putting into a sealed tank and stirring. However, a new environmental problem occurs due to the use of organic solvents, and a special tank capable of operating a closed tank, decompression, vacuum, etc. can be installed, so that the general construction is very difficult for general construction.

In addition, when the elastic floor packaging material is installed using cork chips, new problems such as chip detachment due to poor specific gravity and poor adhesion to the urethane binder, rot caused by water infiltration, and a marked drop in tensile strength or elongation are caused. The situation is appearing in various ways.

In order to improve this point, some reforming of the cork chip has been attempted. For example, Patent No. 10-871855 attempts to solve the above problems by using a urethane chip binder and calcium carbonate, but some problems such as specific gravity and tensile strength are considered to be solved, but dust generated by using calcium carbonate is generated. As the use of organic solvents that induce VOCs for the coating of urethane binders with high viscosity, air pollution is a problem, and time and cost difficulties due to several coatings of urethane binders can be a big problem. It will be very difficult to apply.

The present invention has been made in view of the above point, an object of the present invention is to solve the problems caused by replacing the existing elastic rubber chip with natural cork chip, that is, to modify the cork chip or construction, VOC and dust It solves problems such as poor compatibility due to mixing, adhesion, low specific gravity, and improves the water resistance, tensile strength, elongation, and properties. Eco-friendly water-soluble coating liquid composition for surface modification of cork chip, modified cork chip for modified elastic packing material, and eco-friendly cork chip for elastic packing material which can be easily installed by general contractor due to its ease of use It is to provide a manufacturing method.

In order to achieve the above object, the present inventors permeate or apply coatings to cork chips using various aqueous coating agents, oils, plasticizers, inorganic coating agents, etc. as various basic experiments, and after various curing tests, are repeated. As described above, the present invention has been completed, which is an environment-friendly water-soluble coating liquid composition for surface modification of cork chips, a cork chip for modified elastic packaging material, and an eco-friendly cork chip manufacturing method using the same.

Environment-friendly water-soluble coating liquid composition for surface modification of the cork chip of the present invention is a "water-soluble A" liquid containing a urethane-modified water-soluble epoxy resin, a plasticizer, a nano silica sol, and a catalyst, an organosilane, polyoxyethylene glycol diamine, a polymer emulsifier And it is characterized by consisting of "water-soluble B liquid" containing water.

Of the water-soluble A liquid used in the present invention, the urethane-modified water-soluble epoxy resin serves as a main component to increase the adhesion of the cork chip, and also serves to complement the elongation of the cork chip. This component primarily reacts with a plasticizer, which is another component of the water-soluble A liquid, to form a skeleton of a polymer resin that can increase elongation, restoring force, and the like.

The plasticizer supplements the brittleness of the epoxy resin and reduces the hardness. The plasticizer may be an environmentally friendly plasticizer such as a naphthenic plasticizer, a nonphthalate plasticizer and an acrylic plasticizer.

In addition, most of the nano-silica sol is composed of inorganic components, the external functional group mainly consists of hydroxyl groups or silanol groups, and the elastic floor packaging material when reacting with the urethane component in part plays a role of increasing the heat resistance and weather resistance.

Of the water-soluble B liquid used in the present invention, the organosilane penetrates deep into the surface of the cork chip and reacts with moisture to form silanol groups, and when heated, reacts with the urethane-modified water-soluble epoxy resin to increase the specific gravity of the cork chip. The silanol groups increase the reactivity with the urethane binder to form a dense polymer network having a thermosetting structure on the surface.

Polymeric emulsifiers are environmentally friendly emulsifiers and serve to ensure that the water-soluble B solution is well mixed and stabilized with each other.

The modified aliphatic polyamine is well mixed with the emulsifier and water to cause a hardenable reaction with the oxirane ring in the water-soluble A liquid resin component to increase adhesion and tensile strength.

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The water-soluble B liquid is high-speed by using 34.0 to 46.0 parts by weight of water, 2.5 to 7.5 parts by weight of eco-friendly polymer emulsifier, 7.0 to 13.0 parts by weight of polyoxyethylene glycol diamine, and 36.0 to 54.0 parts by weight of organosilane, based on 100 parts by weight of the water-soluble B solution. It is prepared by dispersing at high temperature for about 2 hours with dissolva.

The water-soluble A liquid and the water-soluble B liquid may be a dispersing agent, an antifoaming agent, a stabilizer, a leveling agent, a gas absorbent, a moisture absorbent, a tackifier, a catalyst, a humectant, a thickener, and a rheology, which are used in the usual water-soluble coating materials, in addition to the above components. (rheology) Control agents, preservatives, cryoprotectants, virus inhibitors, pH adjusters, rust inhibitors, ultraviolet absorbers, antioxidants, emulsifiers and the like can be added.

On the other hand, the present invention discloses a method for producing a cork chip showing the effect of improving the adhesion, water resistance, tensile strength, workability, elongation, etc. using the environment-friendly water-soluble coating liquid composition for surface modification of the cork chip, Method for producing a cork chip is a water-soluble A solution prepared above after drying the cork chip of 2 to 3 times the weight of the aqueous solution A, B mixture solution at 50 ~ 80 ℃ 20 ~ 30 minutes in a mixer capable of temperature control and mixer After mixing the B solution and then uniformly mixed for 20 to 30 minutes at 100 ~ 110 ℃ to completely remove the moisture at 76 ~ 380 mmHg pressure to produce a modified cork chip.

When constructing an elastic floor packaging material using the cork chip, which is actually coated with an eco-friendly water-soluble coating liquid composition for surface modification of the cork chip of the present invention, it does not generate VOC and dust in the entire process of manufacturing and constructing the cork chip. In addition, it greatly improves the properties of miscibility, water resistance, tensile strength and elongation due to low mixing, adhesiveness and low specific gravity, which are problems in the use of cork chips, and can be easily installed by general contractors. It is economical and can be distributed in the field, so it provides convenient construction property to the contractor, and contributes to the environment by generating little VOC in the environment, and economically reduces the cost of construction. Bring the possible effect.

1 is a photo of a cork chip and a general cork chip modified by the present invention
Figure 2 is a cork chip modified by the present invention and a general cork chip photo
3 is a photograph of a modified cork chip 3a, a general cork chip 3b, and an EPDM chip 3c based on Example 6. FIG.

The composition which comprises the above-mentioned water-soluble A, B liquid is explained concretely and in detail.

The water-soluble A solution is prepared by dispersing the above-described raw materials at room temperature in a high-speed dissolver in turn for 1 hour and then preparing the water-soluble A solution.

The urethane-modified water-soluble epoxy resin in the water-soluble A liquid is partially modified with a water-soluble isocyanate resin and a polyether polyol in an epoxy resin in which the chemical structure is solubilized, and reacts with the active hydrogen contained in the water-soluble B solution to cork chip adhesion. In addition to acting as a major component to increase the pressure, the urethane adhesive used in the construction of the elastic floor packaging material and a hardenable chemical functional group (silanol group) are formed on the surface, forming a strong and dense polymer network of thermosetting structure on the surface to elongation and tension It also plays a role in improving water resistance.

Scheme 1: Process overview and chemical structure of urethane modified epoxy resin

Urethane-modified water-soluble epoxy resins are readily available on the market. For example, there are polyferon products, and are classified into EHB-4600U, EHB-4700U, EHB-4800U, EHB-4900U, etc. according to the solid content. Two or more types may be used in combination.

The plasticizer supplements the brittleness of the coated surface and increases the elongation. The available types are all non-phthalate-based, and are the naphthenic plasticizers such as ESOL N-15, ESOL N-50 and ESOL N-100. Aekyung Emulsifier NEO-T, NEO-T3, LG Chem BL-100, GL-300, DOTP and the like can be used, but may be used alone or in combination of two or more.

Nano-silica sol is composed mostly of inorganic components, and is a hydrosol that is stably dispersed in a state that solid silica particles do not precipitate or agglomerate. The functional group as a chemical component that exhibits heat resistance, abrasion resistance, and anti-slip effect is mainly used. It is composed of hydroxyl group or silanol group and plays a role of improving heat resistance, weather resistance, and wear resistance by reacting with urethane component during construction of elastic floor packaging material.

Scheme 2: curing reaction of silane or nanosilica sol with urethane adhesive

Nanosilicazol can be used as YGS-30, YGS-40, YGS-4040, YGS-4080, Y-Samtech's SS-SOL 30SG, SS-SOL 30E, SS-SOL 30F, SS-SOL 30A, SS-SOL 20AM, SS-SOL 100, etc. can be used, and one or two or more types can be used.

As the organic metal catalyst, zirconium octate, dibutyl tin oxide, bismuth octate, silver octate, aluminum talcite, and the like can be used, and tertiary amine, imidazole and the like can also be used.

Aqueous B solution is prepared by high-speed dispersion for 2 hours at room temperature in a high-speed dissolver.

Among the water-soluble B liquids, water is preferably used in an amount of 34.0 to 46.0 parts by weight based on 100 parts by weight of the water-soluble B liquid. When the amount thereof is less than 36.0, the viscosity is high. , Corrosion chip surface penetration may not occur sufficiently. If the content exceeds 46.0, a large amount of water may cause a delay in drying and curing.

Eco-friendly polymer emulsifiers serve to ensure that the water-soluble B liquid is well mixed and stable with each other. As the anionic emulsifier, one or more combinations of an alkylbenzenesulfonate, an olefin sulfonate, an alkyl sulfate, an alkyl ether sulfate and a sodium alkanesulfonate-based emulsifier are used, and an alkylbenzene sulfonate-based KH-103 is used. desirable. In addition, raw materials having similar functions may be used in combination of one or more types, and are not limited to specific types.

It is preferable to use 2.5 to 7.5 parts by weight with respect to 100 parts by weight of the water-soluble B solution, and when the amount is less than 2.5, the emulsifying micelle of the water-soluble B solution may not be sufficiently formed, which may cause aggregation due to poor solution storage ability. . When the content exceeds 7.5 it causes a problem that the water resistance is lowered.

For emulsion stability, non-ionic emulsifiers such as polyethylene glycol derivatives, polyhydric alcohol derivatives, and the like may be used, and MAXEMUL 9107, which is an environmentally friendly polymer emulsifier, is preferable. In addition, one or more kinds of raw materials having a similar function may be used, and an emulsifier containing no VOC and no harmful components is not limited to a specific kind.

Of the water-soluble B liquid used in the present invention, the organosilane penetrates deep into the surface of the cork chip and reacts with moisture to form silanol groups, and when heated, reacts with the urethane-modified water-soluble epoxy resin to increase the specific gravity of the cork chip. The silanol groups increase the reactivity with the urethane binder to form a dense polymer network having a thermosetting structure on the surface.

The organosilane is preferably used 36.0 ~ 54.0 parts by weight based on 100 parts by weight of water-soluble B liquid, and when the amount of use is 36.0 million, the reaction density with the urethane adhesive used in the construction of the elastic packaging material is inferior, thereby improving adhesion and water resistance. When the fall significantly, and the content exceeds 54.0, the curing ratio with the urethane adhesive is not matched, which may lead to poor curing, cloudiness.

Examples of the organosilane include vinyltrimethoxysilane, methyltriethoxysilane, vinylmethyldimethoxysilane, methyltriisopropoxysilane, methyltriacetoxysilane, aminopropyltrimethoxysilane, and aminopropyltrie. Methoxysilane, fluoropropyltriethoxysilane, aminopropylmethyldimethoxysilane, β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-mercetopropyltrimethoxysilane, β- (aminoethyl) -γ -Aminopropylmethyldimethoxysilane, glycidoxy propyl triethoxysilane, etc. can be used 1 type or in combination or 2 or more types. It is preferable to use glycidoxy propyl triethoxy silane, methyltriacetoxy silane, aminopropyl trimethoxy silane, methyl triethoxy silane, etc. which are easy to apply to a water solubility. Specific examples include TSL-8325, TSL-8330, TSL-8350, TSL-8355, TSL-8380, TSL-8330KEM-128, KEM-172-50, KEM-019-50, and the like. Products from other companies (KCC, DOW CORNING, etc.) that have characteristics can also be used.

Among the water-soluble B liquids, polyoxyethylene glycol diamine forms a chemical structure that increases the adhesion and tensile strength of the surface of the cork chip by causing a curable reaction with the oxirane ring in the water-soluble A liquid resin component, and is used for the construction of the elastic floor packing material. It is cured with a urethane adhesive to form a dense hardening network.

Scheme 3: curing reaction of polyamine and urethane-modified epoxy resin

Polyoxyethylene glycol diamines that can be used include JEFAMINE ED600, JEFFAMINE ED900, JEFFAMINE ED2003, JEFAMINE M600, JEFFAMINE M1000, JEFFAMINE M2005, BCA-WB001, BCA-WB002, BCA-WB004, BCA-WB004, BCA-WB00 , BCA-WB006, etc. can be used, and raw materials having similar functions can be used in combination of one or more kinds.

It is preferable to use 7.0 to 13.0 parts by weight of polyoxyethylene glycol diamine, and when the amount thereof is less than 7.0, the functional group reacting with the oxirane ring of the liquid A may be insufficient, resulting in poor curing density and poor curing. When the content exceeds 13.0, there are many polyamines or polyamide chromophores, and yellowing phenomenon comes quickly when constructing the elastic packaging material.

An overview of the multi-curing cis and chemical reaction of the eco-friendly water-soluble coating liquid composition for surface modification of the cork chip can be expressed as follows.

Hereinafter, the present invention will be further described based on examples through various experiments, but the following examples are provided to illustrate the present invention, and the scope of the present invention is not limited thereto.

Cork applied to the following examples were used to purchase the product of the company of Korea Cork manufactured by shredding process with a shredder. Its shape is irregular, its thickness is 2 ~ 4mm, specific gravity is about 0.05 ~ 0.3, and it is a domestic cork chip that is harmless to human body as an eco-friendly natural material without heavy metals and harmful substances detected.

Preparation of Modified Cork Chips

The process for producing a modified cork chip is a water-soluble A liquid prepared in Example 6 after drying the cork, which is twice the weight of the water-soluble A liquid and B liquid, at 80 ° C. for 20 minutes in a mixer capable of temperature control and a mixer. After mixing the B solution and uniformly mixed for 20 minutes at 100 ~ 110 ℃ and completely removed the moisture at 380 mmHg pressure to produce a modified cork chip.

Elastic Packaging Specimen Manufacturing

The mechanical strength values, ie tensile strength (MPa) and elongation (%), were measured in 8.1 by the KS F 3888-2, and the physical properties were measured. The ratio of urethane adhesive and modified cork was 2: 1 (weight ratio). To prepare a specimen (Fig. 1).

Examples and comparative examples of the coating liquid composition of the present invention and a comparative test of the elastic floor packaging material made of cork chips using the same were performed as shown in Table 1.

Comparative test results according to urethane adhesive content division Compounding ratio (cork: adhesive)
(Weight) Tensile Strength (MPa) Elongation
(%) Modified Cork (Example 6) 1: 1.5 0.603 25.4 1: 2.0 1.033 32.9 Uncoated cork 1: 1.5 0.303 23.1 1: 2.0 0.601 27.5

The physical property test in the above table used the following method.

Test Methods

 -Viscosity measurement: The viscosity of the product was measured using a viscometer from FUNGI LAB.

-Drying property: When water-soluble A and B liquids were mixed with cork and used in Preparation Example 1, the degree of dry contact was measured and expressed as good, normal or bad.

-Tensile strength: After fabrication of the specimen according to KS F 3888-2 8.11 (Fig. 1) was tested by a universal testing machine (AND, 5KN).

-Elongation rate: After the specimen preparation according to KS F 3888-2 8.11 (Fig. 1) was tested by a universal testing machine (AND, 5KN).

-Lower limit height: The lower limit height was tested according to Safety Certification Standard Annex 2 (Children's Play Equipment) [Ministry of Trade, Industry and Energy Notice No. 2016-0094].

-Water resistance test: As shown in Fig. 2, after mixing the unmodified cork and the modified cork with urethane adhesive and installing it in a plastic container, infiltrating water, blocking the surface with a chalet, the state of the cork elastic packaging material after 7 days The corrugated brown impurity state was expressed as good and dissolution at the bottom of the elastic packaging material.

-Coating surface appearance: The appearance of the coating surface was visually identified by the surface of the cork when mixing the normal cork and the water-soluble A, B solution prepared in the above example was divided into transparent, translucent, HAZY, Figure 3 is in Example 6 above Based on the modified cork 3a, normal cork 3b, EPDM chip 3c.

As described above, the surface-modified cork chip according to the present invention has various problems that may occur in construction in the cork chip elastic floor packaging material that is currently commercially available, that is, miscibility due to low mixing, adhesion, low specific gravity, Excellent performance of water resistance, tensile strength and elongation can be improved, convenient construction properties for workers, and environmentally friendly, with little VOC generated. In terms of economics, when manufacturing and constructing the surface-modified cork chip with the composition of the present invention, the total material cost was calculated to be reduced to about 20 to 30%. Appeared to have.

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Claims (4)

As an eco-friendly water-soluble coating liquid composition for surface modification of cork chips containing water-soluble A liquid and water-soluble B liquid
The water-soluble A liquid contains a urethane-modified water-soluble epoxy resin, a plasticizer, nano silica sol and a catalyst,
The water-soluble B liquid is an organosilane, polyoxyethylene glycol diamine, a polymer emulsifier, and an environment-friendly water-soluble coating liquid composition for surface modification of the cork chip, characterized in that it comprises water. delete Surface-modified cork chip for elastic flooring prepared by mixing the coating liquid composition of claim 1 and the cork chip. The coating liquid composition of claim 1 and the cork chips of 2 to 3 times the weight of the coating liquid composition into a mixer capable of mixing and then uniformly kneading, pouring the dough solution on a drying stage where vibration occurs and applying heat to dry and harden Method for producing a modified cork chip.

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