KR101509725B1 - Integrated soft polyurethane wall with improved workability and a preparation method thereof - Google Patents

Abstract

The present invention relates to integrated soft polyurethane walls in sports facilities and children′s playgrounds which are used for shock mitigation. The present invention comprises: a step of forming an integrated soft polyurethane layer which includes 5-15 parts by weight of SAN (Styrene Acrylonitrile) polymer with respect to 100 parts by weight of soft polyurethane containing 50-60 wt% of isocyanate and 40-50 wt% of polyol; and a step of laminating a high-speed hardening polyurethane layer on the integrated soft polyurethane layer. The high-speed hardening polyurethane layer is produced by combining urea prepolymer containing 10-20 wt% of Free NCO and urea hardener containing 40-70 wt% of polyol, 15-45 wt% of amino compound, 1-10 wt% of chain lengthener, and 0.1-5 wt% of bismuth compound. The integrated soft polyurethane wall is eco-friendly, because it does not contain heavy metals and toxic substances in comparison with the existing polyurethane materials, and is easy to use and stable because it allows high-speed hardening in comparison with liquid urethane. In addition, the integrated soft polyurethane wall consists entirely of equal materials and thus has superior adhesive strength, and is evenly attached to curved walls as well because of its high elasticity and elongation.

Description

TECHNICAL FIELD [0001] The present invention relates to an integrated soft polyurethane wall material having improved workability and an improved method of manufacturing the wall material.

TECHNICAL FIELD The present invention relates to a safety fence and a wall for a sports facility and a children's playground. More particularly, the present invention is environmentally friendly, , An all-in-one flexible polyurethane based wall material excellent in adhesive force as a whole, and a manufacturing method thereof.

In sports facilities such as children's amusement facilities, indoor gymnasium, baseball field, etc., safety must be ensured. Therefore, shock absorbing walls are installed on walls of playgrounds and sports facilities to absorb shocks and prevent injuries.

One of the most commonly used methods for conventional shock absorbing walls is to put polyethylene (poly ethilene) or urethane plate sponge in a tarpaulin bag and make it into a pad of a certain size, and then use a glue A method in which a plate-like sponge is adhered to the wall by an adhesive, and then the rubber sheet is fixed on the sponge by an adhesive agent, and then wrapped. At this time, when the sponge is drenched with water, it should be prevented from leaking because it may fall down from the wall due to its considerable weight.

Accordingly, in Patent Document No. 0011426, a shock absorbing panel for shock absorption has been proposed in which a drainage ventilation layer having a plurality of projections is provided for rainwater treatment on the cement wall surface, and a plurality of cushion layers made of polyethylene and polyurethane And the rubber sheet layer was applied to the surface layer to cover the drainage ventilation layer and the multi-cushion layer. However, these walls are difficult to survive for more than two years due to tearing of the tarpaulin envelope due to severe impact, discoloration due to ultraviolet rays, oxidation or embrittlement.

In case of rubber sheet, EPDM (ethylene propylene-diene terpolymer) material is generally used. When it is applied to an outdoor ball park such as a ball park, the double bond part of EPDM is broken by ultraviolet rays, It is brittle to lose its function as a shock-absorbing wall, and the appearance of a sheet joint is not good. Also, the greater the number of joints of the rubber sheet, the greater the risk of water leakage, and thus the width of the rubber sheet is widened as much as possible. However, if the width of the cushion is widened, it is not a problem if the cushion wall is straight, but if the wall is curved, the curved surface can not come out naturally.

On the other hand, in the construction of the shock absorbing wall, it is also possible to apply the polyurethane foam used as the conventional shock absorption absorbing flooring material to the wall surface by high pressure spraying. Conventional polyurethane materials use a pigment composed of a heavy metal reaction promoter and an organic compound, and contain a harmful substance as a system using volatile organic solvents. Accordingly, in the process for producing a flexible polyurethane foam of Patent Publication No. 0596990, a lead compound and 4,4'-methylene bis ortho-chloroaniline (hereinafter referred to as "MOCA" Compounds as curing accelerators have been proposed, but these tin compound-based curing accelerators are disadvantageous in that the curing rate at room temperature is slow and the use of pomegranate as an environmental hormone is regulated recently There is a problem.

Open Patent Publication No. 0011426 (published on Jan. 29, 2005) Patent Publication No. 0596990 (published on October 6, 2001)

The present invention relates to an integral flexible polyurethane based wall material having improved workability and a manufacturing method thereof, and more particularly, to a wall material for shock absorption which is applied to a wall of a children's play facility and a sports facility to absorb shock and prevent injury .

In order to solve the problems of the prior art, it is an object of the present invention to provide a shock absorbing wall material that is environmentally friendly, easy to install and stable, has excellent adhesion, and can be installed not only on a flat wall but also on a curved wall .

In order to solve the problems of the prior art described above and to achieve the object of the present invention, the integral flexible polyurethane based wall material improved in workability proposed by the present invention is a soft polyurethane wall material comprising a) softener comprising 50 to 60% by weight of isocyanate and 40 to 50% Preparing a flexible polyurethane layer mixed with 5 to 15 parts by weight of SAN (styrene acrylonitrile) polymer based on 100 parts by weight of polyurethane; b) a urea prepolymer having a free NCO content of 10 to 20% by weight, 40 to 70% by weight of a polyol, 15 to 45% by weight of an amine compound, 1 to 10% by weight of a chain extender and 0.1 to 10% by weight of a bismuth compound ≪ / RTI > to 5% by weight of a curing agent; C) from 30 to 50% by weight of water, from 1 to 10% by weight of a surfactant, from 20 to 40% by weight of butyl acrylate, from 10 to 30% by weight of methyl methacrylate on the super-cured polyurea layer formed in step b) Wherein the soft polyurethane layer has a density of 80 to 120 kg / m < 3 >, wherein the soft polyurethane layer has a density of 1 to 10 wt% Wherein the hardened polyurea layer has a density of 500 to 1,000 kg / m < 3 >, and the soft polyurethane layer and the super-hardened polyurea layer in steps a) and b) are laminated by a spray method, molding block are preferably fabricated and laminated.
Further, the rim block may include a step of preparing a raw material of a liquid monomer or a prepolymer; Supplying the raw material to a mold and filling the mixture; Polymerizing and curing the filled material in a mold; And producting the cured raw material after desizing it.
In another embodiment of the present invention, there is an integral flexible polyurethane based wall material produced by such a method.

delete

delete

delete

A method for manufacturing a monolithic flexible polyurethane wall material having improved workability according to the present invention comprises the steps of applying a primer to the wall surface of the primer to help adhere the polyurethane wall material to the surface of the primer and then forming a flexible polyurethane layer and a super- It has an excellent impact relaxation effect by construction.

In addition, it is eco-friendly in composition that does not contain heavy metals and harmful substances compared with existing polyurethane materials, and can be quick-cured compared to conventional liquid urethane, so that it is easy to construct, and quick and stable construction is possible. On the other hand, since the wall laminate structure is constructed using the same series of materials, the adhesive force is excellent, and the elasticity and elongation are good, and even if the wall laminate structure is installed on a curved wall, it can be naturally attached without lifting.

1 is a cross-sectional view showing an integral flexible polyurethane wall material of a sports facility and a children's play facility according to the present invention.
2 is a graph showing an acceleration trajectory with respect to time.
Fig. 3 shows a test apparatus for measuring the limit falling height.
4 is a graph showing a typical curve of a collision injury value (HIC) according to a descent height.

Hereinafter, the technical features of the present invention will be described in detail with reference to embodiments and drawings. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents. shall.

The integral flexible polyurethane based wall material of the present invention having improved workability comprises the steps of: a) smoothing the surface of a conventional concrete wall or removing foreign matter; b) applying the primer to the concrete surface by one or more methods selected from brushes, rollers, and spray; c) applying an integral flexible polyurethane layer over the primer; And d) constructing a super-hardened polyurea layer on the integral flexible polyurethane layer.

The integral flexible polyurethane layer comprises a flexible polyurethane comprising from 50 to 60% by weight of isocyanate and from 40 to 50% by weight of polyol; And SAN (Styrene Acrylonitrile) polymer. The soft polyurethane is produced by chemically reacting two substances, a polyol and an isocyanate. The properties of the flexible polyurethane and the properties of the flexible polyurethane The curing rate is determined. In general, the higher the ratio of isocyanate, the faster the reaction rate and the higher the density of the product flexible polyurethane. In particular, when the content of isocyanate is 50% by weight or less, the strength of the soft polyurethane is weakened and the shock absorption is not easy. When the content is 60% by weight or more, the soft polyurethane hardens. The polyol may be polypropylene glycol or polyether glycol, and the isocyanate may be toluene diisocyanate (TDI) or methylene diisocyanate (MDI) But is not limited thereto.

Further, the SAN polymer functions to control the elasticity and hardness of the flexible polyurethane, and when the polyurethane contains 5 to 15 parts by weight of the SAN polymer relative to 100 parts by weight of the flexible polyurethane, the desired impact strength can be obtained.

The super-property cured polyurea layer comprises a urea prepolymer having a free NCO (residual NCO) content of 10 to 20 wt% and a urea curing agent in a volume ratio of 1: 0.5 to 1.5, wherein the volume ratio of the urea prepolymer to the urea curing agent is within the above range , There is an excellent effect on excellent film stretchability, mechanical strength improvement, waterproofing and moisture proofing. At this time, the urea prepolymer may be prepared by reacting a diol having a number average molecular weight of 2,000 to 3,000 g / mol and an isocyanate compound having a number average molecular weight of 100 to 500 g / mol in a reactor at 70 to 90 ° C for 3 to 5 hours have. It is preferable that the urea curing agent comprises a polyol, an amine compound, a chain extender and a bismuth compound, and the polyol is contained in an amount of 40 to 70 wt% in the urea curing agent. When the content is within the above range, The effect of improving the rate is obtained. At this time, examples of the polyol include polypropylene glycol and polyether glycol, but are not limited thereto.

The amine compound may be at least one selected from the group consisting of polyetheramine, diethyltoluene, and polypropylene diamine, and may be used in an amount of 15 to 45% by weight in the urea curing agent . When the content of the amine compound is within the above range, the mechanical strength is improved.

The chain extenders improve the mechanical strength of the cured product through molecular structure extension, and include 4,4'-Methylene bis Ortho-Chloroaniline (MOCA), 1,3-butylene But are not limited to, glycols such as 1,3-butylene glycols, 1,4-butadienes, trimethylol propane, 1,4-butadiol, and triethylenediamines . At this time, the content of the chain extender is preferably 1 to 10% by weight in the urea curing agent. If the content of the chain extender is less than 1% by weight, the hardness properties and the reaction efficiency of the final cured product are inferior. When the content of the chain extender is more than 10% by weight, the final viscosity of the composition is increased.

On the other hand, the bismuth compound has a characteristic of a Group 13 specific gravity metal series, and is environmentally friendly and accelerates product curing, and is preferably contained in an amount of 0.1 to 5% by weight in the urea curing agent. When the content of the bismuth compound is within the above range, there is a synergistic effect such as ensuring workability and increasing the expansion / contraction ratio, mechanical strength, shortening of curing time, etc. with the control of the reaction rate. The bismuth compound may be at least one selected from the group consisting of bismuth octoate, bismuth naphthenate, bismuth propionate, bismuth maleate, bismuth neotecanoid, and bismuth neopentanoide. no.

The density of the integral flexible polyurethane based wall material should be adjusted according to the purpose. When the soft polyurethane and the hardened polyurea density are less than 80 kg / m 3 and 500 kg / m 3, respectively, durability and the floor material of the stadium are insufficient, And when it exceeds 120 kg / m 3 and 1000 kg / m 3 respectively, there is a problem that the hardness is high and the flexibility is low because of low elasticity.

The acrylic coating layer may further comprise 30 to 50% by weight of water, 1 to 10% by weight of a surfactant, 20 to 20% by weight of butyl acrylate, To 40 wt%, methyl methacrylate 10 to 30 wt%, methacrylic acid 1 to 10 wt%, and acrylic acid 0.1 to 5 wt%.

The acrylic coating agent acts not only as a waterproof agent but also to protect the polyurethane flooring material. The acrylic coating agent is applied at a rate of 0.1 to 10 L / m ^{2. When} the coating ratio is less than 0.1 L / m ² , If it does not appear and exceeds 10 l / m ² , cracks are generated.

On the other hand, in the method of applying the integral soft polyurethane layer and the super-hardened polyurea layer in steps c) and d), a laminated structure is formed by spraying or a reaction injection molding (RIM) block is manufactured and laminated . Preparing a raw material for a monomer or a prepolymer in a liquid block by a block made by a polymer processing method in which the rim block is formed simultaneously with the polymerization of the monomer to the polymer in the mold; Supplying the raw material to a mold and filling the mixture; Polymerizing and curing the filled material in a mold; And producting the cured raw material after desizing it.

Hereinafter, an integral flexible polyurethane wall material having improved workability of the present invention and a manufacturing method thereof will be described with reference to specific examples. It should be understood, however, that these embodiments are provided for the purpose of illustration only and are not to be construed as limiting the scope of the present invention. Accordingly, various equivalents and modifications may be made thereto at the time of filing of the present invention .

Three kinds of test specimens of Comparative Example 1 and Experimental Examples 1 and 2 were prepared in order to confirm the impact reduction effect of the integrally molded flexible polyurethane wall material having improved workability.

First, Comparative Example 1 is a concrete wall material without any construction, and Experimental Example 1 is a flexible polyurethane based wall material in which a flexible polyurethane layer is applied to Comparative Example 1. More specifically, after the surface of the concrete wall material was leveled, the urethane resin primer was sufficiently applied by spraying. When the primer was dried, an integral flexible polyurethane layer containing 10 parts by weight of a SAN polymer was laminated on the surface of 100 parts by weight of a flexible polyurethane comprising 60% by weight of toluene diisocyanate and 40% by weight of polypropylene glycol by spraying.

In Experimental Example 2, a super-property cured polyurea layer was applied by the spray method in Experimental Example 1 above. More specifically, the surface of the monolithic flexible polyurethane layer of Experimental Example 1 was coated with a urea prepolymer having a free NCO content of 10% by weight and a polypropylene glycol of 65% by weight, polyethyramine of 25% by weight, triethylenediamine of 5.5% 8 wt% of urea curing agent were mixed at the same volume ratio and sprayed.

The performance certifications of the shock-absorbing wall materials of Experimental Examples 1 and 2 prepared in Example 1 are shown in Safety Administration Notice No. 2013-15 and the Pro Baseball Field Fence Protection Pad Basic Instruction (KBO Professional Baseball Field Fence Protection Pad Basic Instruction KISS T0005) It was evaluated according to the proposed test method.

According to the test method described above, when the head impact load (HIC) value of the impact force applied to the head is less than 1,000, it is assumed that the hemispherical head model is dropped on the floor at different heights, And the critical falling height Hc is calculated from the collision injury value for each falling height.

As shown in FIG. 3, the test apparatus includes a test body 10, a head model 20, an output device 30, and an accelerometer 40. The head model 20 was an aluminum hemispherical launch vehicle having a diameter of 160 mm and a weight of 4.6 kg, and an accelerometer 40 was attached thereto.

The collision injury is calculated using the following equation (1) for the total time interval (between t _start and t _end ) of the time / acceleration curve obtained at a sample frequency of 10 kHz. The limit fall height was calculated to be a value corresponding to the collision injury value = 1,000 as shown in FIG. 4 using a regression curve obtained from the relationship between the collision injury value per falling height and the corresponding fall height.

(1)

(One)

An acceleration represented by the formula (1) in a head model 20 is the acceleration of gravity (G) is received, t is a number of seconds of time is expressed in ms between t1, t2 is t _start and t _end t It means some two intermediate values. In this case, t _start is the time at which the impact starts when the acceleration of the head model is 0 or more, and t _end is the time at which the impact ends when the acceleration of the head model is 0 or less for the first time. However, this procedure is only valid for impact results that last more than 3 ms, ie, (t _end - t _start ) ≥ 3 ms.

  In order to test the safety of the impact-attenuating wall material of the present invention, the limit lowering height at the point of impact damage of 1,000 in Comparative Example 1 in which no work was performed by the above test method was obtained. The collision injury values of Experimental Examples 1 and 2 at the lowering height of Comparative Example 1 were obtained using Table 1.

division Type of wall constructed Collision Injury (HIC) Comparative Example 1 - 1000 Standard: 40 or less Experimental Example 1 Polyurethane layer 43 Experimental Example 2 Polyurethane layer + polyurea layer 36

According to the results shown in Table 1, the impact injury value of Experimental Example 1 in which only the polyurethane layer was applied was 43, and the impact injury value of Experimental Example 2 in which the polyurea layer was applied to the surface of the polyurethane layer of the present invention was 36. According to the Basic Guideline of Professional Baseball Field Fence Protection Pad (KISS T0005 Basic Instruction for KBO Professional Baseball Stadium Fence Protection Pad), the safety standard of impact injuries was less than 40,

The present invention is not limited to the above-described specific embodiment and description, and various changes and modifications may be made by those skilled in the art without departing from the scope of the present invention as claimed in the claims. And such modifications are within the scope of protection of the present invention.

10: Test body
20: Head model
30: Output device
40: Accelerometer

Claims (8)

a) preparing a flexible polyurethane layer mixed with 5 to 15 parts by weight of a SAN (styrene acrylonitrile) polymer based on 100 parts by weight of a flexible polyurethane containing 50 to 60% by weight of an isocyanate and 40 to 50% by weight of a polyol;
b) on said flexible polyurethane layer,
A urea prepolymer having a free NCO content of 10 to 20% by weight;
A step of laminating a super-hardened polyurea layer comprising 40 to 70% by weight of a polyol, 15 to 45% by weight of an amine compound, 1 to 10% by weight of a chain extension and 0.1 to 5% by weight of a bismuth compound ; And
c) 30 to 50% by weight of water, 1 to 10% by weight of surfactant, 20 to 40% by weight of butylacrylate, 10 to 30% by weight of methyl methacrylate on the super-cured polyurea layer formed in step b) % Of acrylic acid, 1 to 10 wt% of methacrylic acid, and 0.1 to 5 wt% of acrylic acid,
The density of the flexible polyurethane layer is 80 to 120 kg / m 3, the density of the super-nature cured polyurea layer is 500 to 1,000 kg / m 3,
Wherein the flexible polyurethane layer and the super-cured polyurea layer in steps a) and b) are laminated by a spraying method, or a reaction injection molding (RIM) block is produced and laminated. A method of manufacturing a wall material. delete delete delete delete delete The method according to claim 1,
The rim block comprises:
Preparing a raw material of a liquid monomer or prepolymer;
Supplying the raw material to a mold and filling the mixture;
Polymerizing and curing the filled material in a mold; And
And removing the cured raw material from the mold and then commercializing the cured raw material. An integral flexible polyurethane based wall material produced by the method according to any one of claims 1 to 7.

Images