KR20060012187A - The packing method oh urethane - elasticity with the reforming urethane binder for elasticity - packing use - Google Patents

Abstract

The present invention uses a urethane prepolymer having 1) an isocyanate group at the terminal and having an equivalent ratio (NCO / OH) of hydroxyl groups in the polyether or polyester polyol in the range of 2-20, the curing agent being 2) an active hydrogen compound. The amount (equivalent ratio) of active hydrogen compounds composed of polyamines and / or polyols is 0.05-5% by weight relative to the total amount of active hydrogen compounds and 3) hardeners in which the ratio of NCO / H (active hydrogen) is in the range of 0.5-3.0. The modified polyurethane binder using a catalyst composed of amines, sulfur, and organometallic compounds (tin, lead) in the range of to produce a modified polyurethane binder and use it as a binder of the urethane elastic rubber chip used in the urethane elastic packaging to improve the durability and strength of the elastic packaging material It is possible to improve and control the curing rate.

Polyurethanes, Elastic Packaging, Rubber Chips, Urethane Prepolymers, Curing Agents, Polyols, Polyisocyanates

Description

URTHING PACKING METHOD OH URETHANE-ELASTICITY WITH THE REFORMING URETHANE BINDER FOR ELASTICITY-PACKING USE}

 The present invention relates to a urethane elastic packaging method using an urethane prepolymer having an isocyanate group at its molecular end and a curing agent to prepare a modified urethane binder for elastic packaging containing an active hydrogen compound, sulfur and an organometallic compound catalyst. More specifically, 1) urethane prepolymers having an isocyanate group at the terminal and having an equivalent ratio (NCO / OH) of hydroxyl groups in the polyether or polyester polyol in the range 2-20, and 2) active hydrogen compounds are polyamines and / or It is composed of polyol and the amount of active hydrogen compound (equivalent ratio) is 0.05-5% by weight relative to the total amount of hardener and 3) hardener, which is an active hydrogen compound in the ratio of NCO / H (active hydrogen) in the range of 0.5-3.0. Improved durability and strength of elastic packaging materials by producing modified polyurethane binders using catalysts composed of amines, sulfur and organometallic compounds (tin, lead) in the range and using them as binders for urethane elastic rubber chips used in urethane elastic packaging. And modified urethane binder for elastic packaging which can control curing rate It relates to a packaging method.

 Recently, various types of resins have been packaged in sports facilities such as golf courses, swimming walkways, tennis courts, track and field stadiums, school campuses, trails, and park facilities. Among them, packaging with urethane resin is widely used because of its easy construction and excellent wear resistance, flatness, and plastering properties.

However, in general, urethane resins are expensive, and in Korea, waste tires are pulverized into chips, mixed with urethane resin elastomers at an appropriate ratio, and cured with a binder to be used for urethane elastic packaging. As a binder used here, a lot of moisture-curable urethane binders are conventionally used. After mixing rubber chips and binders sufficiently, they are poured into molds or laid at the construction site, and then compacted using trowels or rags. It is a process that waits for 24 hours to naturally harden by moisture. As the moisture-curable urethane binder used herein, urethane prepolymers having isocyanate groups at the molecular ends obtained by reacting excess isocyanates with polyols are generally used. As polyols, polyether polyols are used. Diphenylmethane diisocyanate (MDI) type is widely used in terms of cost and workability.

However, the conventional moisture-curable polyurethane binder is hard to be cured by moisture in the air, so that hardening takes a long time, so it is difficult to harden in a short time on a road with heavy traffic and it is difficult to control the curing speed. In addition, there is a method of adding water or using a catalyst to increase the curing rate, but most of the foaming occurs due to a rapid reaction with water, thereby reducing the strength of the cured elastic packaging material.

  On the other hand, the moisture-curable polyurethane binder is mixed together as an adhesive for rubber chips, and then constructed by flattening the surface with a trowel or a heat roller. However, this compaction is intended to smooth the surface and finish the edges so that the binder bonds the rubber chips. Due to the weak force, the rubber chip is easily detached from the surface, and in particular, where spikes such as golf courses and tracks are used, many problems appear due to the detachment of the elastic rubber chip. Therefore, in order to improve the durability, strength, etc. of the elastic packaging material and to control the curing rate, it is necessary to modify the polyurethane binder.

When the elastic packaging material is used by using the polyurethane binder of the present invention as a binder of an elastic rubber chip, the curing time is significantly increased by the action of the curing agent, and the curing time is controlled by controlling the content of the polyamine, polyol, catalyst, etc. contained in the curing agent. It is possible to control the adverse effects such as foaming and to control the elasticity of the binder and the elastic rubber chip due to the use of a curing agent to manufacture a modified urethane binder for elastic packaging that can improve the physical properties such as durability and strength of the packaging material It is to provide a urethane elastic packaging method using the same.

Technical means for achieving the above object uses a urethane prepolymer having an isocyanate group at the molecular end as a subject and a modified polyurethane binder containing an active hydrogen compound and sulfur and an organometallic compound catalyst as a curing agent. That is, the present invention uses a urethane prepolymer having 1) an isocyanate group at the terminal and having an equivalent ratio (NCO / OH) of hydroxyl groups in the polyether or polyester polyol in the range of 2-20. 3) The total amount of the active hydrogen compound (equivalent ratio) of the hydrogen compound is composed of polyamines and / or polyols, and the total amount of the active hydrogen compound having the ratio of NCO / H (active hydrogen) is in the range of 0.5-3.0 and 3) the total amount of the curing agent. It is made by producing a modified polyurethane binder using a catalyst composed of amines, sulfur and organometallic compounds (tin, lead) used in the range of 5% by weight and using it as a binder of a urethane elastic rubber chip used for urethane elastic packaging.

Here, polyurethane elastic pavement can be carried out on most of the base such as asphalt concrete, concrete, mortar, and after the base treatment of the base, apply a suitable primer of urethane, epoxy-based, if the base is asphalt concrete primer Solvents should not invade asphalt concrete.

As a polyurethane binder, it consists of a urethane prepolymer and a hardening | curing agent which have an isocyanate group in a molecule terminal. The urethane prepolymer having an isocyanate group at the terminal of the molecule may be prepared by heating the organic polyisocyanate and the polyol for 1 to 5 hours at 80-100 degrees Celsius in nitrogen gas according to a generally known urethane production method.

 Further, the polyurethane binder is composed of a main ingredient mainly composed of a urethane prepolymer having an isocyanate group at the terminal prepared above, and a curing agent containing a specific ratio of active hydrogen compound, sulfur, and a catalyst. : 3-3: 1 Mixing at a free ratio to the desired curing speed, which requires rapid curing using sprayer or air compressor for anti-slip processing of road paving binders or foundation surfaces requiring sufficient curing time. Hard binder can be manufactured. In addition, by mixing the elastic rubber chip in various ratios within the range of 5-500 parts by weight with respect to 100 parts by weight of the polyurethane binder, it is possible to perform elastic packaging for the purpose ranging from urethane flooring to hard, semi-rigid, elastic packaging. .

Organic polyisocyanates as raw materials for producing urethane prepolymers having isocyanate groups at the terminals include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and mixtures of these isomers (TDI), and crude tolylene diisocyanate , Metaphenylene diisocyanate, diphenylmethane diisocyanate (MDI), polymethylenepolyphenyl polyisocyanate (crude MDI), hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and the like. Use individually or in mixture of 2 or more types.

As a polyol as a raw material for producing a urethane prepolymer having an isocyanate group at its terminal, various polyether polyols, polyester polyols, polybutadiene polyols, polytetramethylene ether glycol, and the like can be used, but propylene oxide or propylene oxide and ethylene for water, propylene glycol, etc. Particularly preferred are polyoxyalkylene glycols, glycerine, trimethylolpropane, and the like, and polyoxyalkylene triols added with propylene oxide and ethylene oxide. Moreover, a low molecular glycol can also be used together. Examples of low molecular glycols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, and the like. These polyols may be used alone or in combination of two or more, and the average molecular weight of the polyol is preferably in the range of about 75-10,000.

In addition, the urethane prepolymer may be prepared by heating the organic polyisocyanate and the polyol as described above in 1 to 5 hours at 80-100 degrees Celsius in nitrogen gas according to a generally known urethane production method. The equivalent ratio (NCO / OH) of the isocyanate group in the urethane prepolymer thus prepared and the hydroxyl group in the polyether or polyester polyol is usually 2-20, and the free isocyanate group in the urethane prepolymer occupies about 1-15% by weight.

The curing agent consists of polyamines and / or polyols as active hydrogen compounds, and polyamines include ethylene diamine, tetramethylenediamine, hexamethylenediamine, para-phenylene diamine, 3,3'-dichloro 4,4'-diaminodiphenylmethane , 3,3'-dimethyl-4,4'-diaminodiphenylmethane and the like are used. As the polyol, polyether polyols, polyester polyols, polymer polyols and the like which are well known are used. As for the usage-amount (equivalent ratio) of an active hydrogen compound, it is preferable that the ratio of NCO / H (active hydrogen) exists in the range of 0.5-3.0.

As the catalyst used in the curing agent, amines and sulfur and organometallic compounds (tin, lead) which are generally known are commonly used. Specific examples thereof include tin octoate, dibutyl tin dilaurate, lead octoate, and lead naphthenate. Use at least two kinds of mixture. The amount of the catalyst used is preferably 0.05-5% by weight based on the total amount of the curing agent.

As the inorganic filler, calcium carbonate, talc, clay, carbon black, silicic anhydride (white carbon), zeolite and titanium dioxide are preferable. Such fillers may be used alone or in combination of two, and the amount thereof is preferably 1-50% by weight based on the total amount of the curing agent.

As other preparations, plasticizers, organic solvents, pigments and the like are used. Plasticizers include dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl adiphthalate (DOA), tricresyl phosphate (TCP), and chlorinated paraffin.The organic solvents used as diluents can be appropriately adjusted according to their needs. It is mixed with a urethane binder and an elastic chip, and a nonpolar solvent such as toluene is mainly used, but various kinds of general organic solvents can be used within a range that does not erode primers applied to the base. Examples of the pigment for colored packaging include organic pigments such as inorganic pigments such as chromium oxide and red iron oxide, phthalocyanine pigments and azo pigments.

As the elastic rubber chip, a foamed polyurethane chip or colored polyurethane chip may be mainly used. However, in view of cost saving, a rubber chip obtained by crushing a diene-based synthetic rubber or waste tire may be mixed with a polyurethane chip at a predetermined ratio. The average particle diameter of a rubber chip can be selected and used according to a use in the range of 0.5-10 mm. If the average particle diameter of the rubber chip is 0.5 mm or less, the friction resistance and the wear resistance are inferior, and if it exceeds 10 mm, it is easily detached from the surface. In addition, an inorganic filler may be mixed with the rubber chip, and the mixing ratio may be used in the range of 5-500 parts by weight based on 100 parts by weight of the total weight of the main material and the curing agent. If it is less than 5 parts by weight, the friction resistance is inferior, and if it exceeds 500 parts by weight, desorption of the rubber chip from the surface is not good. The shape of the rubber chip may be any shape such as circular, square, and plate.

In addition, in the case of general packaging, the mixing time of the rubber chip is designed to have sufficient pot life by adjusting the blending amount of the curing agent, and then, when mixing the main ingredient and the curing agent, the rubber chip is mixed together and the trowel in the pot life. Alternatively, it can be applied to the adherend by using regi, and in case of performing anti-slip processing on the surface, adjust the mixing ratio of the curing agent and design the mixing ratio with the short-hard binder with short pot life. The mixture is mixed in a batch, and the mixed liquid is blown out at a high pressure using a sprayer, applied in a mixed state on the adherend, and rapidly cured, thereby giving the surface a concave-convex state, thereby performing a surface anti-slip processing with increased friction resistance.

In the elastic packaging material of the present invention, the blending ratio is 5-500 parts by weight of the above various kinds of rubber tips with respect to 100 parts by weight of the polyurethane binder, and if necessary, aggregates such as silica sand, stone powder, barium sulfate, talc, Inorganic fillers such as mica, clay, calcium carbonate and ground resins, and organic solvents such as benzene, toluene and urethane thinner can be mixed in a proportion as a diluent.As a preparation, a plasticizer, an antifoaming agent, a coloring pigment, a hydrolysis inhibitor , Leveling agents and the like can be blended.

The above-mentioned compounding ingredients are blended at a construction site, kneaded by a general method, laid on a base coated with a primer, and then installed in a range of 5-500 parts by weight with respect to 100 parts by weight of a polyurethane binder. By adjusting the ratio at various ratios, it is possible to carry out polyurethane pavement for various purposes, ranging from construction of urethane flooring in basketball courts to elastic pavement of hard, semi-rigid, and trails.

An example of the elastic packaging method of this invention is introduced. First, clean the base surface of asphalt concrete, concrete, mortar, etc. with a vacuum cleaner or an air compressor, and fill the cracks or cracks on the surface with mortar or putter and put a tape to prevent the primer from getting around. Apply enough primer for asphalt or concrete onto the surface of the foundation with a roller, dry for 2-3 hours and begin laying elastic material. Next, various types of rubber chips such as urethane rubber chips, synthetic rubber chips, waste tire rubber chips, and colored color chips are appropriately selected according to the cost saving aspect and color rendering purpose, and the rotary chips are appropriately selected. The urethane prepolymer, the curing agent, and the inorganic filler, the diluent, the pigment, the plasticizer, the antifoaming agent, and the like are mixed in a predetermined ratio, and then stirred sufficiently to obtain a mixed solution for elastic packaging. Lay the mixture on the base surface, make it a certain thickness (usually 5-15mm) with a rake, and then press it evenly with an electric heat roller to compact it, clean up rough or curved surfaces with a thermal trowel, It's a good idea to work with laying snow or horizontal stripes.

Hereinafter, the present invention will be described in detail with reference to the following examples.

Example 1

Preparation of Urethane Prepolymer, Subject

440 parts by weight of polyoxypropylene diol having an average molecular weight of 3,000, 450 parts by weight of polyoxypropylene triol having an average molecular weight of 6,000, and 130 parts by weight of 2,4-tolylene diisocyanate were mixed uniformly, followed by 80 degrees Celsius under a nitrogen stream. The reaction was carried out for 2 hours and 4 hours at 100 degrees Celsius to obtain a urethane prepolymer having an NCO content of 3.2% by weight and a viscosity of 7,000 cps / 25 degrees Celsius.

Example 2

Preparation of Curing Agent

8 parts by weight of 3,3'-dichloro 4,4'-diaminodiphenylmethane, 24 parts by weight of polyoxypropylene diol having an average molecular weight of 4,000, 20 parts by weight of polyoxypropylene triol having an average molecular weight of 6,000, dioctyl phthalate 7 weight part, 40 weight part of calcium carbonate, 3 weight part of lead octylates (25% of lead content) which are a catalyst, 0.01 weight part of sulfur, and 5 weight part of red iron oxides which are inorganic pigments were added, it knead | mixed uniformly, and the hardening | curing agent was obtained.

Example 3

Urethane Elastic Packaging

100 parts by weight of the main urethane prepolymer and 100 parts by weight of the curing agent were mechanically mixed for about 10 minutes using a stirring device equipped with a rotary vane to prepare a polyurethane binder. 600 parts by weight of the rubber chip mixed at a blending ratio of 1 was added to a stirrer, and the mixture was stirred and mixed uniformly for 5 minutes. This elastic packaging mixture was placed on the surface of the urethane primer-treated base material, and the thickness was 8 mm with a rake, followed by compaction with an electric heat roller, and the surface was smoothly finished using a resin to complete the urethane elastic packaging material.

When the elastic packaging material is constructed using the polyurethane binder of the present invention as a binder of the elastic rubber chip, the curing speed is significantly increased by the action of the curing agent, and the content of the polyamine, polyol, sulfur, catalyst, etc. contained in the curing agent is controlled. Hardening time can be adjusted, adverse effects such as foaming can be suppressed, and the use of a curing agent increases the bonding strength between the binder and the elastic rubber chip, thereby improving physical properties such as durability and strength of the packaging material.

While the invention has been shown and described with respect to particular embodiments, it will be appreciated that the invention can be varied and modified without departing from the spirit or scope of the invention as set forth in the claims below. It will be appreciated that those skilled in the art can easily know.

Claims (9)

(1) Urethane prepolymers and curing agents having an isocyanate group at the end and having an equivalent ratio (NCO / OH) of hydroxyl groups in the polyether or polyester polyol in the range 2-20, (2) active hydrogen compounds are polyamines and And / or polyol and the amount of active hydrogen compound used (equivalent ratio) is 0.05-5% by weight relative to the total amount of active hydrogen compound and (3) curing agent in the ratio of NCO / H (active hydrogen) in the range of 0.5-3.0. Elastic packaging using modified urethane binder for elastic packaging, which manufactures a modified polyurethane binder using a catalyst composed of amines, sulfur, and organometallic compounds used in the range, and uses it as a binder of a urethane elastic rubber chip used for urethane elastic packaging. Way. The non-slip processing of the foundation surface by laying on a general road or spraying a sprayer by mixing the polyurethane prepolymer and the curing agent at a free ratio within a range of 1: 3-3: 1 to a desired curing speed. Or elastic packaging method using a modified urethane binder for elastic packaging, characterized in that the surface irregularities imparting processing is possible. The modified urethane binder for elastic packaging according to claim 1, wherein the modified urethane binder for elastic packaging is used for hard, semi-rigid and elastic packaging of the urethane flooring material by mixing at a ratio of 5-500 parts by weight of the elastic rubber chip with respect to 100 parts by weight of the polyurethane binder. Elastic packaging method used. The organic polyisocyanate as a raw material for producing a urethane prepolymer having an isocyanate group at its terminal is 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and a mixture of these isomers (TDI), Crude tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate (MDI), polymethylenepolyphenyl polyisocyanate (crude MDI), hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate An elastic packaging method using a modified urethane binder for elastic packaging, characterized in that any one or a mixture of two or more. The polyol as a raw material for producing a urethane prepolymer having an isocyanate group at its terminal is various polyether polyols, polyester polyols, polybutadiene polyols, polytetramethylene ether glycol and the like, and propylene oxide or the like. Polyoxyalkylene glycol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene with propylene oxide or propylene oxide and ethylene oxide added to polyoxyalkylene glycol, glycerine, trimethylolpropane added with propylene oxide and ethylene oxide Modified for elastic packaging, which is used alone or in combination of two or more of glycol, tripropylene glycol, 1,3-butylene glycol, and 2,3-butylene glycol, and has an average molecular weight of about 75-10,000. Urethane Vine Elastic packing method using more  The urethane prepolymer is prepared by heating an organic polyisocyanate and a polyol in nitrogen gas at 80-100 degrees Celsius for 1 to 5 hours, and an equivalent ratio of isocyanate groups in the urethane prepolymer and hydroxyl groups in the polyether or polyester polyol. (NCO / OH) is 2-20, the free packing isocyanate group contained in the urethane prepolymer is 1-15% by weight, characterized in that the elastic packaging method using a modified urethane binder for elastic packaging. The method of claim 1 wherein the curing agent is composed of polyamines and / or polyols as active hydrogen compounds and the polyamines are ethylene diamine, tetramethylenediamine, hexamethylenediamine, para-phenylene diamine, 3,3'-dichloro 4,4 ' Any one or two or more of -diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane is used, and the polyol is any one of polyether polyol, polyester polyol or polymer polyol. Or use two or more kinds alone. The amount of the active hydrogen compound (equivalent ratio) is an elastic packaging method using a modified urethane binder for elastic packaging, characterized in that the ratio of NCO / H (active hydrogen) is in the range of 0.5-3.0.   The catalyst used in the curing agent is amines, sulfur, tin octoate, dibutyl tin dilaurate, lead octoate, lead naphthenate alone or in combination of two or more, the amount of the catalyst used is a curing agent Elastic packaging method using a modified urethane binder for elastic packaging, characterized in that 0.05 to 5% by weight based on the total amount of. The rubber chip according to claim 3, wherein the elastic rubber chip is a foamed polyurethane chip, colored polyurethane chips, rubber chips obtained by crushing diene-based synthetic rubber or waste tires, polyurethane chips, and the average particle diameter of the rubber chips is 0.5-10. Elastic packaging method using a modified urethane binder for elastic packaging, characterized in that the range of mm.