KR102212337B1 - 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 is excellent in adhesion, water resistance, tensile strength, workability, elongation, etc. of cork chips that can be used as elastic chips for elastic floor packaging when coating on natural cork chips collected and crushed from cork oak or oyster oak. Provides an eco-friendly water-soluble coating composition for modifying the surface of cork chips that can exhibit an enhancing effect, and as essential components, a water-soluble mixture A solution containing a urethane-modified water-soluble epoxy resin, a catalyst, and nano silica sol, and an organosilane, modified It is characterized in that it is composed of an aqueous mixed solution B solution containing an aliphatic amine, a polymer emulsifier, and water.

Description

The method for manufacturing and composition the same elastic paving material of eco-friendly water-soluble coating composition for surface enhancement, which is an eco-friendly water-soluble coating composition for surface modification of cork chips, and a modified cork chip for elastic packaging material. of Cork Chips}

The present invention relates to a composition for surface modification of cork chips used as an elastic chip material for elastic packaging materials, and in more detail, adhesion, water resistance, tensile strength, and workability of cork chips, a natural material collected and pulverized from oak or oyster oak. , An eco-friendly water-soluble coating composition for modifying the surface of cork chips that can show an effect of remarkably improving elongation, etc., a modified cork chip for elastic packaging material, and a method of manufacturing an eco-friendly cork chip that can be used for an elastic packaging material using the composition.

In places such as children's playgrounds, walking paths, walking paths, bicycle paths, parks, etc., elastic flooring materials that provide anti-slip, shock absorption and cushioning power are installed to prevent safety accidents of users.

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

However, there is a situation in which social and environmental problems continue to occur due to harmful components contained in the waste tire chip, which is an elastic chip that is essentially used in the construction of the conventional elastic rubber chip as described above, or the EPDM chip.

In order to solve this problem, there have been attempts to replace and use cork chips, which are natural materials.

Cork is a bark accumulated by aging of oyster oak or cork oak, and has a very low specific gravity and is light and has a porous structure. Cork is used as bottle caps, car gaskets, wall panels, boards, and fishing rod handles because of its excellent naturalness and impact resistance, and is expected to be used as a substitute for elastic rubber chips containing harmful ingredients.

For example, Korean Patent Publication No. 10-2012-0002773 introduces a technology for elastic floor coverings using cork. At once, cork chips, ore particles, polyurethane adhesives, silane coupling agents, organic solvents such as esters or hydrocarbon-based solvents Is put in an airtight tank and stirred to make a floor packaging composition. However, a new environmental problem occurs due to the use of organic solvents, and it is very difficult for a general contractor to construct universally because it can be constructed only when there is a special facility capable of operating a sealed tank and decompression, vacuum, etc.

In addition, when the elastic floor packaging material is constructed using cork chips, new problems such as detachment of the chip due to poor adhesion to the urethane binder due to the light specific gravity, decay due to the penetration of water, remarkable decrease in tensile strength or elongation, etc. It is present in various ways.

In order to improve this point, some attempts have been made to modify the cork chip. For example, Patent No. 10-871855 tried to solve the above problems by using a urethane chip binder and calcium carbonate, but it is determined that some problems such as specific gravity and tensile strength have been solved, but dust generated due to the use of calcium carbonate , Air pollution is a problem due to the use of organic solvents that cause VOC for coating of urethane binders with high viscosity, and time and cost difficulties due to several coatings of urethane binders are inevitably presented as a real problem in the construction site of elastic packaging materials. It will be said that it is very difficult to apply.

The present invention has been devised in view of the above points, and an object of the present invention is to solve various problems that occur when replacing the existing elastic rubber chip with natural cork chips, that is, VOCs and dust that may occur during construction or It does not occur, but solves problems such as lowering of miscibility due to low mixing, adhesion, and specific gravity, which are problems in the construction and use of cork chips, and excellently improves the physical properties of water resistance, tensile strength, and elongation. Because of its ease of use, it can be easily installed by general contractors, and it is economical and can be applied to actual sites. Eco-friendly water-soluble coating composition for surface modification of cork chips, modified cork chips for elastic packaging materials, and eco-friendly cork chips available for elastic packaging materials. It is to provide a method of manufacturing.

In order to achieve the above object, the inventors of the present invention conducted experiments in which various water-based coatings, oils, plasticizers, inorganic coatings, etc. were used as various basic experiments to penetrate or apply coatings, and various hardening experiments. As described above, the present invention, which is an eco-friendly water-soluble coating composition for surface modification of cork chips, cork chips for modified elastic packaging materials, and an eco-friendly cork chip manufacturing method using the same, has been achieved.

The eco-friendly water-soluble coating composition for surface modification of cork chips of the present invention includes a urethane-modified water-soluble epoxy resin, plasticizer, nano silica sol, and a "water-soluble A" liquid containing a catalyst, organosilane, polyoxyethylene glycoldiamine, and polymer emulsifier , And characterized in that it consists of a "water-soluble B liquid" containing water.

Of the aqueous solution A 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 at the same time supplements the elongation of the cork chip. This component primarily reacts with a plasticizer, another component of the aqueous solution A, to form a skeleton of a polymer resin that can increase elongation and resilience.

Plasticizers complement the brittleness of epoxide resins and reduce hardness, and environmentally friendly plasticizers such as naphthenic plasticizers, nonphthalate plasticizers, and acrylic plasticizers are used.

In addition, nanosilicasols are mostly composed of inorganic components, and their external functional groups are mainly composed of hydroxyl groups or silanol groups, and play a role in enhancing heat resistance and weather resistance by partially reacting with urethane components when constructing elastic flooring materials.

In the aqueous B solution used in the present invention, organosilane penetrates deep into the surface of the cork chip and reacts with moisture to form a silanol group and reacts with the urethane-modified water-soluble epoxy resin when heat is applied to increase the specific gravity of the cork chip. , The silanol group increases the reactivity with the urethane binder to form a dense polymer network with a thermosetting structure on the surface.

Polymer emulsifiers are eco-friendly emulsifiers and play a role in allowing water-soluble B solutions to be well mixed and stabilized.

The modified aliphatic polyamine is well mixed with the emulsifier and water to cause a curable reaction with the oxysilane ring in the aqueous solution A resin component, thereby increasing adhesion and tensile strength.

Urethane-modified water-soluble epoxy resin is 70.0 to 86.2 parts by weight, plasticizer is 10.1 to 23.7 parts by weight, nano silica sol is 3.5 to 6.5 parts by weight, and catalyst is 0.2 to 1.4 parts by weight per 100 parts by weight of aqueous A solution. It is prepared by dispersing for about 1 hour at room temperature.

Water-soluble B liquid is high-speed 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 glycoldiamine, and 36.0 to 54.0 parts by weight of organosilane based on 100 parts by weight of aqueous B solution. It is prepared by dispersing at room temperature for about 2 hours at high speed as a dissolve bar.

In addition to the above components, the water-soluble liquid A and water-soluble liquid B include dispersants, antifoaming agents, stabilizers, leveling agents, gas absorbers, moisture absorbers, tackifiers, catalysts, wetting agents, thickeners, rheology agents used in ordinary water-soluble coating materials as needed. (rheology) Control agents, preservatives, anti-freeze agents, anti-virus agents, pH adjusters, rust inhibitors, ultraviolet absorbers, antioxidants and emulsifiers can be added.

On the other hand, the present invention discloses a method of manufacturing a cork chip that exhibits excellent effects of improving adhesion, water resistance, tensile strength, workability, elongation, etc. by using the eco-friendly water-soluble coating composition for surface modification of cork chips. The manufacturing method of the prepared cork chips is to dry the cork chips of 2 to 3 times the weight of the aqueous solution A and B mixture in a mixer capable of temperature control and mixer at 50 to 80 ℃ for 20 to 30 minutes, and then the aqueous A solution prepared above. After mixing and B liquid, the mixture is uniformly mixed at 100 to 110°C for 20 to 30 minutes, and then moisture is completely removed at a pressure of 76 to 380 mmHg to prepare a modified cork chip.

If the elastic floor packaging material is constructed using the cork chip in which the eco-friendly water-soluble coating composition for surface modification of the cork chip of the present invention is actually coated on the cork chip, VOC and dust are not generated in the entire process of the cork chip manufacturing process and the construction process. Due to low specific gravity, mixing, adhesion, and low specific gravity, which are problems in the construction and use of calligraphy and cork chips, the properties of miscibility, water resistance, tensile strength, and elongation are excellently improved, and because of the ease of construction, general contractors can easily construct them. In addition, it is excellent in economics and can be distributed to the actual site, providing convenient constructability to the contractor, and contributing to the environment by not generating VOCs environmentally. Economically, it is possible to construct economical elastic packaging materials by reducing the construction cost. Brings possible effects.

1 is a photograph of a cork chip and a general cork chip modified by the present invention
Figure 2 is a photograph of a cork chip and a general cork chip modified by the present invention
3 is a photograph of a modified cork chip 3a, a general cork chip 3b, and an EPDM chip 3c according to the sixth embodiment.

A detailed and detailed description will be given of the composition constituting the above water-soluble A and B solutions.

The aqueous solution A is prepared by sequentially inserting the above-described ingredients in a high-speed dissolver at room temperature and then dispersing for 1 hour to prepare an aqueous solution A.

Urethane-modified water-soluble epoxy resin in aqueous solution A is partially modified with water-soluble isocyanate resin and polyether polyol in an epoxy resin whose chemical structure is water-soluble, and reacts with active hydrogen contained in aqueous solution B to adhere to cork chips. It acts as a main component to increase the value and at the same time contains a urethane adhesive used in the construction of elastic flooring materials and a chemical functional group (silanol group) capable of curing, forming a strong and dense polymer network with a thermosetting structure on the surface. , 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 products from Polyferon, and are classified into EHB-4600U, EHB-4700U, EHB-4800U, EHB-4900U, etc., depending on the solid content, and are divided into It is okay to mix and use two or more types. It is preferable to use 70.0 to 86.2 parts by weight of the total 100 parts by weight of the aqueous solution A, and if the amount is less than 70.0, there is a problem that the adhesiveness and elongation decrease, and if the content exceeds 86.2, the curability This can be bad.

Plasticizers complement the brittleness of the coated surface and increase the elongation. All of the available types are non-phthalate-based naphthenic plasticizers such as ESOL N-15, ESOL N-50, ESOL N-100, etc. In addition, Aekyung Petrochemical's NEO-T, NEO-T3, LG Chem's BL-100, GL-300, DOTP, etc. can be used, but it may be used singly or in combination of two or more. It is preferable to use 10.1 to 23.7 parts by weight based on the total 100 parts by weight of the aqueous solution A, and if the amount is less than 10.0, there is a problem that the elongation decreases, and when the content exceeds 23.7, dryness is poor. Or, it may cause a problem of poor curing.

Nano silica sol is mostly composed of inorganic substances, and is a hydrosol stably dispersed in a state where solid silica particles do not precipitate or aggregate. The functional group as a chemical component exhibiting heat resistance, abrasion resistance, and anti-slip effect is mainly It consists of a hydroxyl group or a silanol group, and plays a role in improving heat resistance, weather resistance, and abrasion resistance by partially reacting with the urethane component when constructing the elastic floor packaging material.

Scheme 2: Curing reaction of silane or nanosilicasol and urethane adhesive

The types that can be used as nano silica sols include YGS-30, YGS-40, YGS-4040, YGS-4080 of Young Il Hwaseong, SS-SOL 30SG, SS-SOL 30E, SS-SOL 30F, SS-SOL 30A of Schemtech, SS-SOL 20AM, SS-SOL 100, etc. can be used, and it is safe to use single or in combination of two or more. It is preferable to use 3.5 to 6.5 parts by weight based on the total 100 parts by weight of the aqueous solution A. If the amount is less than 3.5, there is no improvement in heat resistance or abrasion resistance, and if the content exceeds 6.5, after curing It may cause problems such as cloudiness and poor drying.

As an organometallic catalyst, zirconium octate, dibutyltin oxide, bismuth octate, silver octate, aluminum talcite, etc. can be used as an organometallic catalyst, and tertiary amines, imidazole, and the like can also be used. It is preferable to use 0.2 to 1.4 parts by weight with respect to the total 100 parts by weight of the water-soluble A solution, and if the amount is less than 0.2, the curability may be poor, and if the content exceeds 1.4, the hardness after curing is high and the elongation rate Have to drop.

The aqueous B solution is prepared by dispersing at high speed for 2 hours at room temperature in a high speed dissolve bar.

It is preferable to use 34.0 to 46.0 parts by weight of water based on 100 parts by weight of water-soluble B liquid, and if the amount is less than 36.0, the viscosity is high, so when mixing the water-soluble coating liquid mixed with water-soluble A and B with cork chips. , There may be a problem that the surface penetration of the cork chip does not occur sufficiently. When the content exceeds 46.0, the amount of water is large, which may cause delay in drying and hardening.

Eco-friendly polymer emulsifiers play a role in allowing water-soluble B solutions to be well mixed and stabilized. As an anionic emulsifier, it is recommended to use a combination of one or more emulsifiers of alkylbenzenesulfonate, olefin sulfonate, alkyl sulfate, alkyl ether sulfate, sodium alkanesulfonate, and use of alkylbenzenesulfonate-based KH-103. desirable. In addition, raw materials having similar functions may be used in combination of one or more, and a specific type is not limited.

It is preferable to use 2.5 to 7.5 parts by weight of the emulsifier based on 100 parts by weight of the aqueous B solution, and if the amount is less than 2.5, the emulsified micelles of the aqueous B solution are not sufficiently formed, and agglomeration may occur due to poor solution storage. . When the content exceeds 7.5, the water resistance is deteriorated.

For emulsification stability, non-ionic emulsifiers such as polyethylene glycol derivatives and polyhydric alcohol derivatives can be used, and MAXEMUL 9107, an eco-friendly high molecular emulsifier, is preferred. In addition, more than one type of raw material having a similar function may be used in combination, and an emulsifier that does not contain VOC and does not contain harmful components does not limit a specific type.

In the aqueous B solution used in the present invention, organosilane penetrates deep into the surface of the cork chip and reacts with moisture to form a silanol group and reacts with the urethane-modified water-soluble epoxy resin when heat is applied to increase the specific gravity of the cork chip. , The silanol group increases the reactivity with the urethane binder to form a dense polymer network with a thermosetting structure on the surface.

It is preferable to use 36.0 to 54.0 parts by weight of organosilane based on 100 parts by weight of aqueous B solution, and when the amount is 36,000, the reaction density with the urethane adhesive used when constructing the elastic packaging material decreases, improving adhesion and water resistance. When the content is significantly lowered and the content exceeds 54.0, the curing ratio with the urethane adhesive does not match, which may lead to poor curing and clouding.

As an organosilane, it is possible to use vinyl trimethoxysilane, methyltriethoxysilane, vinylmethyldimethoxysilane, methyltriisopropoxysilane, methyltriacetoxysilane, aminopropyltrimethoxysilane, aminopropyltrie. Toxisilane, fluoropropyltriethoxysilane, aminopropylmethyldimethoxysilane, β(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, β-(aminoethyl)-γ -Aminopropylmethyldimethoxysilane and glycidoxypropyltriethoxysilane can be used alone or in combination of two or more. Among these, it is preferable to use glycidoxypropyltriethoxysilane, methyltriacetoxysilane, aminopropyltrimethoxysilane, methyltriethoxysilane, etc., which are easy to apply to water-soluble. Specific examples include Tongyang Silicon's TSL-8325, TSL-8330, TSL-8350, TSL-8355, TSL-8380, TSL-8330KEM-128, KEM-172-50, KEM-019-50, etc. Products of other companies (KCC, DOW CORNING, etc.) with characteristics can also be used.

Among water-soluble liquid B, polyoxyethylene glycoldiamine forms a chemical structure that increases the adhesion and tensile strength of the surface of cork chips by causing a curable reaction with oxysilane ring in the resin component of water-soluble liquid A, and is used when constructing elastic flooring materials. It cures with urethane adhesive to form a dense curing network.

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

Available polyoxyethylene glycol diamines include Huntsman's JEFAMINE ED600, JEFFAMINE ED900, JEFFAMINE ED2003, JEFAMINE M600, JEFFAMINE M1000, JEFFAMINE M2005, BRENNTAG's BCA-WB001, BCA-WB002, BCA-WB003, BCA-WB004, BCA-WB004 , BCA-WB006, etc. can be used, and in addition, raw materials with similar functions can be used in combination of one or more.

Polyoxyethylene glycol diamine is preferably used in an amount of 7.0 to 13.0 parts by weight, and if the amount is less than 7.0, the functional group reacting with the oxirane ring in Solution A is insufficient, resulting in a decrease in curing density and poor curing. When the content exceeds 13.0, there are many polyamines or polyamide chromophores, so yellowing occurs quickly during the construction of elastic packaging materials.

An overview of the multi-curing sheath and the chemical reaction of the eco-friendly water-soluble coating composition for surface modification of cork chips described above can be shown as follows.

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

Cork applied to the following examples was used by purchasing a product manufactured by Daehan Cork Co., which was manufactured by crushing with a crusher. Its particle shape is irregular, its thickness is 2 ~ 4mm, specific gravity is about 0.05 ~ 0.3, and it is an eco-friendly natural material that does not detect heavy metals and harmful substances. It is a domestic cork chip that is harmless to the human body.

Preparation of modified cork chips

The manufacturing process of the modified cork chip is an aqueous solution A prepared in Example 6 below after drying twice the weight of the mixture of aqueous A and B solution in a mixer capable of temperature control and mixing for 20 minutes at 80°C. After mixing and B liquid, the mixture was uniformly mixed at 100 ~ 110 ℃ for 20 minutes, and then the moisture was completely removed at a pressure of 380 mmHg to prepare a modified cork chip.

Manufacture of elastic packaging material specimen

The mechanical strength values, that is, tensile strength (MPa) and elongation (%), were prepared by measuring the specimen and physical properties values according to 8.11 in KS F 3888-2, and the mixing ratio of the urethane adhesive and the modified cork was 2:1 (weight ratio). To prepare a specimen (Fig. 1)

Comparative tests of the examples and comparative examples of the coating liquid composition of the present invention and the elastic floor packaging material made of cork chips using the same were carried out as shown in Table 1.

Comparative test result according to urethane adhesive content division Mixing ratio (cork: adhesive)
(Weight ratio) 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 made by FUNGI LAB.

-Drying: When water-soluble liquids A and B were mixed with cork and then carried out according to the method of Preparation Example 1, the degree of dryness to the touch was measured and marked as good, normal, or bad.

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

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

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

-Water resistance test: As shown in Fig. 2, after mixing the unmodified cork and the modified cork with urethane adhesive, placing it in a plastic container, infiltrating water, and blocking the surface with a chalet, 7 days after the state of the cork elastic packaging material, that is, The brown impurity state peculiar to cork on the underside of the elastic packaging material was expressed as good and elution.

-Appearance of the coated surface: The surface of the cork was visually checked when the general cork was mixed with the water-soluble A, B liquid prepared in the above example, and the surface of the cork was visually divided into transparent, translucent, and HAZY, and FIG. 3 is shown in Example 6 above. This is a photo of the modified cork (3a), general cork (3b), and EPDM chip (3c) based on it.

As described above, the surface-modified cork chip according to the present invention has a number of problems that can occur during construction in the currently commercially available cork chip elastic floor packaging material, namely, the miscibility due to the low density of the cork chip, Water resistance, tensile strength, and elongation properties are excellently improved, and it provides convenient construction to workers, and environmentally, it generates almost no VOCs, thus contributing to the environment. In terms of economics, it is calculated that the total material cost is reduced by around 20 to 30% when the surface-modified cork chip is manufactured and constructed with the composition of the present invention.It is excellent in economical efficiency and can be actually distributed to industrial sites. Appeared to have.

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Claims (3)

As an eco-friendly water-soluble coating liquid composition for surface modification of cork chips containing water-soluble A liquid and water-soluble liquid B
The aqueous solution A contains a urethane-modified water-soluble epoxy resin, a plasticizer, a nano silica sol and a catalyst, and the aqueous solution B contains an organosilane, polyoxyethylene glycoldiamine, a polymer emulsifier, and water. As an eco-friendly water-soluble coating liquid composition for surface modification of chips,
The aqueous solution A contains 70 to 86.2 parts by weight of a urethane-modified water-soluble epoxy resin, 10.1 to 23.7 parts by weight of a plasticizer, 3.5 to 6.5 parts by weight of nano silica sol, and 0.2 to 1.4 parts by weight of a catalyst based on 100 parts by weight of the aqueous A solution,
The aqueous B solution contains 34.0 to 46.0 parts by weight of water, 2.5 to 7.5 parts by weight of a polymer emulsifier, 7.0 to 13.0 parts by weight of polyoxyethylene glycoldiamine, and 36.0 to 54.0 parts by weight of organosilane based on 100 parts by weight of the aqueous B solution. Eco-friendly water-soluble coating composition for surface modification of cork chips, characterized in that. Surface-modified cork chip for an elastic flooring material prepared by mixing the coating liquid composition of claim 1 and the cork chip. The coating liquid composition of item 1 and the cork chips of 2 to 3 times the weight of the coating liquid composition are put into a kneader capable of a mixer, then kneaded evenly, poured on a drying table where vibration occurs, and then dried and cured by applying heat. Method for producing a modified cork chip according to.

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