KR100910732B1 - Polyurethane binder composition with pro-enviromental property and polyurethane binder chip prepared by the same and polyurethane paving material prepared by the same - Google Patents

Abstract

An environment-friendly polyurethane binder composition is provided to control pot life and to be useful as packing materials such as bicycle path, children`s playground, playground court and track due to excellent various physical properties. An environment-friendly polyurethane binder composition comprises 100.0 parts by weight of a urethane prepolymer base material containing 3.5~6.5% free NCO; and 100~300 parts by weight of a polyol hardener. The polyol hardener comprises inorganic filler and pigment. A bismuth compound is added based on 100.0 parts by weight of the polyol hardener so that the metal conversion amount of the bismuth compound become 0.1~3.0 parts by weight.

Description

Eco-friendly polyurethane binder composition, polyurethane binder chip and polyurethane packaging material produced by the same {Polyurethane binder composition with pro-enviromental property and polyurethane binder chip prepared by the same and polyurethane paving material prepared by the same}

The present invention relates to an environment-friendly polyurethane binder composition, a polyurethane binder chip and a polyurethane packaging material produced therein, and more specifically, do not contain environmental hormone-induced heavy metals, which are environmentally friendly, easy to adjust pot life, and various physical performances. It relates to an excellent environmentally friendly polyurethane binder composition, polyurethane binder chips and polyurethane packaging materials produced therefrom.

As is well known, polyurethane is a generic term for polymer polyols having a reactive hydroxyl group (hydroxyl group) and polymer materials obtained by urethane reaction with these reactive polyols and isocyanates. Polyurethane is a synthetic coating elastomer that is relatively inexpensive and easy to install while exhibiting acid resistance, alkali resistance, oil resistance, abrasion resistance, low temperature characteristics, excellent tensile strength and elastic shock absorption performance. At the time, the world's first 3M company introduced the so-called artificial urethane elastic track under the name "Tartan track".

Increasing ride times due to the development of mechanization, automation, and transportation due to the development of modern scientific civilization has led modern people to increase the incidence of modern diseases due to lack of physical activity, which in turn has increased their interest in well-being and thus maintaining a healthy life. The number of people participating in leisure-sports activities such as sports, in-line skating and cycling is increasing rapidly. However, since the road environment is composed of concrete and asphalt, the lack of elasticity of these roads impacts the knees or ankles during long-time leisure-sport activities. Therefore, the use of polyurethane with excellent elasticity and workability is expanding.

Such an elastic polyurethane package is manufactured using a polyurethane chip and a polyurethane binder as shown in FIGS. 1 and 2, and in Korea, with the establishment of the Korea Composite Elastic Packaging Industry Association in 2003, As part of the school sports facilities expansion support policy, it is currently intensively expanding and operating a large budget for the installation of sports flooring in schools at various schools with the support of the National Sports Promotion Foundation.

Recently, as part of the resource recycling and resource recycling policy, the use of recycled polyurethane chips, waste tire recycle chips, etc. instead of polyurethane chips emphasizes the so-called resource recycling aspects. Although many reports have been reported, carcinogenic PAHs (lead polynuclear aromatic hydrocarbons) and lead are released several times more than the standard in these replacement chips and some newly manufactured urethane chips. Situation.

As a management standard for composite elastic packaging materials consisting of polyurethane elastic chips or elastic rubber chips and polyurethane binders, the Sports Flooring Performance and Quality Standards (KISS) of the National Institute of Sports Science and the National Institute of Technology and Standards It is regulated by "Construction Coating Film Waterproofing Material Specification (KS F 3211)" and International Shock Absorption Rate (FIFA 05 / 05-01) standard of the International Amateur Athletic Federation (IAAF).

In addition, in order to minimize the adverse effects of these floorings on the human body by heavy metals, the heavy metal content of the urethane elastic packaging material is regulated according to KS R 1301, US EPA 3060A, KS M 3719.

Therefore, the composite elastic packing material has the physical performance satisfying KISS, KS F3211, FIFA 05 / 05-01, but the Pb by KS R 1301, US EPA 3060A, KS M3719 is below 90mg / kg, Cd is below 75mg / kg, Cr Heavier metals such as silver below 60 mg / kg and Hg below 25 mg / kg must be met.

In particular, the standards on the regulation of heavy metal content are regulated by the Resource Recycling and Resource Recycling Policy in the situation that is strictly operated in accordance with the Children's Toys Test Act (KSG ISO 8124-3) to manage the safety of children's playground application. Waste tire chips, recycled polyurethane chips, and some newly manufactured urethane chips, which are used as part of rubber chips, have been irradiated with dozens of times more heavy metals, causing social controversy and the same result in flooring using some new urethane binders. Investigation reports have recently been published.

In preparing such a conventional polyurethane chip and polyurethane binder, according to the Republic of Korea Patent No. 0425027, Republic of Korea Patent No. 0465231, etc., the number average molecular weight of 1,000 ~ 6,000 two diol (diol) and three tree Urethane prepolymer (Urethane) prepared to react the equivalent ratio of triol mixed polyol with isocyanate such as toluene diisocyanate or methylene diisocyanate at 1.0: 1 ~ 1.5 to free NCO (%) content Prepolymer) and particle size by mixing amines with inorganic fillers such as calcium carbonate and talc, colorants and chain extenders to a mixed polyol of diol and triol with two reactors with a number average molecular weight of 1,000 to 6,000 The curing agent was adjusted to a ratio that meets the desired physical performance and a lead compound (Pb-Octoates) or tin compound (Tin-compound) was added as a curing accelerator. Sikimeuroseo to prepare the urethane cross-linking reaction

The hardening accelerator which is widely used in the conventional urethane chip and binder manufacturing method like this conventional patent technology is mainly lead compounds (Pb-Octoates, Pb-Naphthanates).

These lead compound curing accelerators have been used for many years since lead compounds have been used as curing accelerators for a long time since they are easily urethane-reacted, even at room temperature, to give excellent physical performance by urethane reaction. have. However, the fact that these lead compounds themselves are the target of heavy metal regulation at the time when the regulations on the regulation of heavy metal contents have been strengthened is not preferable.

In addition, in the case of tin compounds, efficacy as a curing accelerator is lower than that of lead (Pb) compounds, and tin compounds have recently been designated as environmental hormones, and their use is currently restricted.

Meanwhile, Korean Patent No. 0492370 discloses 4,4'-methylene bisorthochloroaniline (4,4'-Methylene bis Ortho) as a lead (Pb) -compound and a chain extender in the production of environmental hormone-induced heavy metal-free polyurethane. -Chloro Aniline: A technique in which a tin compound is used as a curing accelerator without using "MOCA"). These tin compound type curing accelerators have a slow normal temperature curing rate.

Therefore, although the patent regulates the curing rate at room temperature by specifying the type of polyol, it is not preferable because tin has recently been regulated as an environmental hormone agent as well as there is a problem in developing the curing rate at room temperature. .

In addition, Korean Patent No. 0586037 discloses diethyltoluenediamine, polypropylenediamine, isophoronediamine, which has a high reaction rate instead of MOCA as a chain extender without using heavy metals such as lead (Pb) compounds or tin (compound) compounds. By using amines such as diphenylmethanediamine to increase the reaction rate of the main urethane prepolymer and the curing agent polyol, it is a technology for producing urethane chips and binders free of environmental hormone-induced heavy metals without curing accelerators. However, this preparation method requires the use of extremely limited amines, and at the same time the temperature of the reaction is greatly affected by the reaction rate. Therefore, in domestic field conditions with four distinct seasons, it is difficult to control the reaction time according to the addition of these amines, especially in summer, and it is very difficult to control the pot life in the field.There is no curing accelerator, so the curing reaction rate of the prepolymer and the polyol curing agent This becomes low and stable physical performance of the cured product is critical, which is not preferable in practical terms.

Therefore, in the composite elastic urethane flooring system, it is easy to control the pot life during the construction, and the physical performance of the obtained cured polyurethane conforms to the standard, and the composition of the practical composite elastic packaging material containing no environmental hormone-induced heavy metals containing no heavy metals. Development is urgently needed.

An object of the present invention is to provide an environment-friendly polyurethane binder composition that is environmentally friendly and easy to adjust the pot life, and excellent in various physical properties when producing a cured product, so as to solve the conventional problems, do not contain heavy metals that are environmental hormone regulatory substances. .

Another object of the present invention is to provide a polyurethane binder chip and packaging material made of the environmentally friendly polyurethane binder composition.

In order to achieve the above problems, in the present invention, an eco-friendly polyurethane binder composition is prepared using a non-carcinogenic bismuth-compound curing accelerator.

In addition, in the present invention, the polyurethane binder chip and the polyurethane packaging material are manufactured using the eco-friendly polyurethane binder composition.

The eco-friendly polyurethane binder composition according to the present invention does not contain heavy metals, which are environmental hormone regulating substances, and is environmentally friendly and easy to adjust the pot life, and excellent in various physical properties when preparing cured products.

Therefore, the present invention is useful for paving materials such as bicycle paths, children's playgrounds, playground courts and tracks, trails and the like.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The eco-friendly polyurethane binder composition of the present invention includes (ii) a bismuth containing 100 parts by weight of a polyurethane prepolymer having a free NCO content of 3.5 to 6.5%, (ii) an inorganic filler and a pigment, and 100 parts by weight of a polyol curing agent. It is characterized in that 100 to 300 parts by weight of a polyol curing agent added with a bismuth compound are mixed so that the metal equivalent of the compound is 0.1 to 3.0 parts by weight.

The urethane prepolymer is prepared by adding toluene diisocyanate in an equivalence ratio of 1: 1.0 to 1.5 with respect to a mixed polyol of diol having a number average molecular weight of 2000 to 3000 and a triol having a number average molecular weight of 3000 to 500. The reaction is carried out until free NCO (%) = 5.0 ± 1.5%, and if necessary, chain extender 1,3-butylene glycol (1,3-Butylene Glycol) or tri methylol propane The reaction may be carried out by addition reaction to produce a cooled extraction.

The polyol curing agent has a composition in which a mixed polyol, an inorganic filler, a pigment and a bismuth compound are mixed.

Specifically, the polyol curing agent is 30 to 40 weight of mixed polyol of (i) Triol having a number average molecular weight of 3,000 to 5,000 and Diol having a number average molecular weight of 3,000 to 5,000 with respect to 100 parts by weight of the polyol curing agent. Part (ii) 40 to 60 parts by weight of the inorganic filler and 10 to 30 parts by weight of (i) coloring are mixed, and (i) metal conversion amount of the bismuth compound is 0.1 to 3.0 parts by weight based on 100 parts by weight of the polyol curing agent. A bismuth compound is added and mixed so that it may be added.

The bismuth compound is a bismuth carboxylate prepared by reacting with a bismuth organic acid, and specifically, the bismuth compound is a bismuth octonate, a bismuth naphthenate, a bismuth propionate, a bismuth maleate, and a bismuth neo Tekanoids or bismuth neopentanoids.

Eco-friendly polyurethane binder composition according to the invention is easy to adjust the pot life 30 ~ 70 minutes.

When the metal equivalent of the bismuth compound of the present invention is less than 0.1 part by weight relative to 100 parts by weight of the polyol curing agent, the reaction rate is slow, the tensile strength of the resulting cured product is 245 ± 5 N / cm 2 or less, and the Shore A hardness is 60 ± 5. It is not preferred to be less than, and exceeding 3.0 parts by weight is not preferable because it is difficult to control the pot life in the range of 50 ± 20 minutes.

The eco-friendly polyurethane binder composition of the present invention is blended in a composition ratio of 100 to 300 parts by weight of a polyol curing agent based on 100 parts by weight of a urethane prepolymer so that the pot life is 50 ± 20 minutes depending on the field conditions and the temperature change. If the polyol curing agent is less than 100 parts by weight, it is not preferable to become a rigid urethane elastomer having a Shore A hardness of 65 or more, and if it exceeds 300 parts by weight, it is not preferable because it becomes a soft urethane having a hardness of 55 or less.

The composition and composition ratio of the urethane prepolymer and the composition and composition ratio of the polyol curing agent, which are the subjects of the present invention, are not particularly limited as long as the composite elastic urethane cured body meets various specifications, but the curing accelerator of the present invention is a bismuth compound and the amount of the polyol curing agent is used. Addition of 0.1 to 3.0 parts by weight of the metal equivalent to 100 parts by weight is the main core of the present invention.

Bismuth of the present invention is a non-carcinogenic and non-carcinogenic non-metallic substance unlike the "Lead" of Group 14, and is a metal belonging to Group 15 as reported in US EPA. The carboxyl salt is a polyurethane curing accelerator, and has been reported in the academic field as having a room temperature curing rate much faster than that of the lead carboxyl salt.

According to a recent research paper of Polyurethane Industries, polyurethane curing speed of 24% bismuth compound curing agent is about 3.5 times faster than 24% lead compound curing agent. Such a bismuth compound curing agent is a new expensive water-soluble urethane reaction catalyst mainly used for water dispersion reaction of polyurethane using water as a solvent, and the application of the composite urethane elastomer as a curing catalyst as in the present invention is It was not done at all.

Accordingly, the present inventors have made use of the bismuth compound, which has been used as a catalyst for exclusively water-dispersed urethane, on the contrary, the effect of the urethane prepolymer on the urethane prepolymer main body and the polyol curing agent as a curing accelerator, and these bismuths. After many years of research on the changes in the physical performance of hardened products obtained by the action of compounds, composite elasticity of non-metallic materials with non-carcinogenic, non-carcinogenic, non-carcinogenic eco-friendliness and physical performances can be met. Urethane chips and binders could be provided.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

However, the present invention is not limited only to the following examples.

Example 1

First, while purging nitrogen in a clean reactor, 300 g of Korean polyol PP-2000 having a number average molecular weight of 2,000 and 400 g of Korean polyol GP-3000 having a number average molecular weight of 3000 and 70 g of dioctylphthalate were added and heated to 80-90 ° C. while homogeneously mixing. The water content of the contents is set to 500 ppm or less, and then the temperature of the reaction is cooled to 30 ° C. Thereafter, 210 g of toluene diisocyanate is slowly added dropwise while paying attention to the exothermic reaction. The urethane reaction is performed while the temperature of the contents is raised to 80 ° C. and the same temperature is maintained. Reactant samples were taken while maintaining the same temperature and analyzed by FT-IR (Frequer Infrared Spectrometer) to measure the size of the 2284 cm ^-1 peak (Free NCO). At%, the reaction was terminated, and after cooling, purging with nitrogen was carried out to prepare a urethane prepolymer main body having a viscosity of 6250 cps and a Gardner color of 1.5.

Next, 80g of polyol GP-4000 with number average molecular weight 4000, 30g of dioctylphthalate, 18g of 4,4'-methylene bisorthochloroaniline, and polyol PP with number average molecular weight 3000 while purging nitrogen in a clean reactor. After adding -3000 320g, the temperature of the contents was raised to 110 ℃, 500g of calcium carbonate and 40g of iron oxide were added to increase the stirring speed, and maintained until the particle size of the contents was 10-20. 7 g of Shepherd) Bismuth # 1376 was added thereto, followed by homogeneous mixing, cooling and purging with nitrogen purge to prepare a polyol curing agent having a viscosity of 7200 cps.

Next, 400 g of the urethane prepolymer prepared as described above and 800 g of the polyol curing agent prepared as described above were homogeneously mixed to prepare an eco-friendly polyurethane binder composition.

The polyurethane binder composition prepared for physical performance evaluation prepared a sample according to KF F 3211 and then cured by standard curing (168 hours curing at 20 ℃, RH 65%) to prepare a binder sample.

In addition, the polyurethane binder composition prepared as described above was put into a mold and cured at room temperature by sheeting to a thickness of 20 mm, and then further cured at 70 ° C. for 4 to 8 hours, and then cut into a chip grinder to be a polyurethane binder chip. Was prepared.

In addition, the binder sample prepared above was further cured at 70 ° C. for 6 hours to prepare a chip sample.

Comparative Example 1

Polyurethane binder composition was the same as in Example 1, except that 21 parts by weight of 24% lead-compound curing agent (Pb-Octoates) was mixed instead of Bismuth 1376 (manufactured by Shepard) of Example 1 to prepare a polyol curing agent. And binder sample Polyurethane binder chips were produced, respectively.

Comparative Example 2

Instead of mixing Bismuth 1376 (manufactured by Shepard) of Example 1 (without curing accelerator) and 18 g of 4,4'-methylene bisorthochloroaniline of Example 1 in preparing the polyol curing agent A polyurethane binder composition and a binder sample polyurethane binder chips were prepared in the same manner as in Example 1, except that 9 g of dimethyl thio toluene diamine was mixed.

The pot life of the polyurethane binder composition prepared in Example 1 and Comparative Examples 1 and 2 was evaluated to evaluate the ease of field application. Pot life evaluations were performed using the Brook Field Viscometer RV- type for each polyurethane binder composition to simulate the pot life temperature of the constant temperature bath to simulate pot life at 15 ° C, 25 ° C and 32 ° C. The viscosity was measured while maintaining the temperature equilibrium by dipping the viscosity measuring cup by keeping the same as.

The evaluation criteria of pot life evaluated the time when the viscosity reaches 100,000 cps as pot life.

The evaluation results of the pot life evaluated by the above method were as shown in Table 1.

                                                           (Unit: cps) division 15 ℃ viscosity change 25 ℃ viscosity change 32 ℃ viscosity change Example 1 Comparative Example 1 Comparative Example 2 Example 1 Comparative Example 1 Comparative Example 2 Example 1 Comparative Example 1 Comparative Example 2 0 min 8,420 8,420 8,420 6,900 6,900 6,900 5,080 5,080 5,080 10 minutes 13,553 12,764 15,492 12,287 11,560 13,579 11,580 10,499 14,329 20 minutes 21,815 19,348 28,503 21,879 19,366 26,723 26,399 21,700 40,419 30 minutes 35,114 29,330 52,442 38,959 32,444 52,590 60,178 44,849 114,013 40 minutes 56,521 44,461 96,487 69,375 54,354 103,495 137,182 92,695 321,601 50 minutes 90,977 67,398 177,525 123,535 91,060 203,674 312,721 191,581 907,153 60 minutes 146,439 102,167 326,624 219,977 152,554 400,824 712,879 395,959 Measurement Over

As can be seen from the results of the pot life evaluation of Table 1, the pot life of Example 1 and Comparative Example 1 of the present invention is distributed in the required pot life specification 50 ± 20 minutes in the domestic air temperature range of 15 ° C to 32 ° C. However, it was found that the pot life is shorter than the specification in the high temperature range (@ 32 ° C.) without the curing accelerator as in Comparative Example 2, which is inappropriate to realize stable field construction. Could.

The results of the physical performance evaluation of the binder sample and chip sample of Example 1 and the binder samples of Comparative Examples 1 and 2 at 25 ° C satisfying the pot life are summarized as follows.

division Example 1 Comparative Example 1 Comparative Example 2 Standard value Binder sample Chip sample Binder sample Binder sample Hardness 58 62 64 51 Shore A, 60 ± 5 The tensile strength 280 292 286 240 N / ㎠, 245.2 min Tear strength 151 164 172 129 N / cm, 147.1 min. Elongation 1700 1450 480 520 %, 450 min. Pb Not detected Not detected 178 Not detected mg / Kg, 90 max. CD Not detected Not detected Not detected Not detected mg / Kg, 75 max. Cr Not detected Not detected Not detected Not detected mg / Kg, 60 max. Hg Not detected Not detected Not detected Not detected mg / Kg, 25 max.

Comprehensive evaluation of the above test result is as follows.

In Example 1 of the present invention, the pot life was in the range of 50 ± 20 minutes in the air temperature of 15 ° C. to 32 ° C., no heavy metal was detected, the physical properties satisfied the standard range, and the elongation was excellent.

Comparative Example 1 has a pot life within the range of 50 ± 20 minutes in the air temperature 15 ℃ ~ 32 ℃, the physical properties satisfy the specification range, there was a problem that the lead content exceeds the specification range.

In Comparative Example 2, the physical properties satisfy the specification range and heavy metals were not detected, but there was a problem in that pot life was insufficient in the high temperature region (32 ° C.) of the atmospheric temperature.

1 and 2 are cross-sectional schematic diagrams of the composite elastic package.

* Description of the protection of the main parts of the drawing

1: concrete layer or ascon layer 2: primer

3,4: soft urethane layer 5: semi-hard urethane layer in which polyurethane chips are wrapped

6: elastic layer consisting of polyurethane chips or rubber chips

7: polyurethane top cord layer.

Claims (9)

(Iii) Based on 100 parts by weight of a urethane prepolymer having a content of 3.5 to 6.5% of free NCO, (ii) an inorganic filler and a pigment, and a metal equivalent of the bismuth compound is 0.1 to 3.0% by weight based on 100 parts by weight of a polyol curing agent. Eco-friendly polyurethane binder composition, characterized in that 100 to 300 parts by weight of a polyol curing agent to which a bismuth compound is added so as to be added. delete The eco-friendly polyurethane binder composition according to claim 1, wherein 40 to 60 parts by weight of the inorganic filler is mixed with 100 parts by weight of the polyol curing agent. The eco-friendly polyurethane binder composition according to claim 1, wherein 10 to 30 parts by weight of the colorant is mixed with 100 parts by weight of the polyol curing agent. The eco-friendly polyurethane binder composition according to claim 1, wherein the bismuth compound is a bismuth carboxyl salt prepared by reacting with a bismuth organic acid. The eco-friendly polyurethane binder composition according to claim 1, wherein the pot life of the eco-friendly polyurethane binder composition is 30 to 70 minutes. The bismuth compound is bismuth octonate, bismuth naphthenate, bismuth propionate, bismuth maleate, bismuth neothecanoid, and bismuth neopentanoid. Eco-friendly polyurethane binder composition. Eco-friendly polyurethane chip made of the eco-friendly polyurethane binder composition of claim 1. Eco-friendly polyurethane packaging material made of the eco-friendly polyurethane binder composition of claim 1.

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