KR102157018B1 - Polyurethane composition, and eco-friendly polyurethane packaging material produced therefrom - Google Patents

Abstract

The present invention relates to a polyurethane composition comprising: a base material part comprising a urethane prepolymer having an isocyanate group (NCO) content of 3.5 to 6.5%; and a curing agent part including polyol, inorganic filler, pigment, bismuth 2-ethylhexanoate, bismuth propionate and heavy naphtha, and to an eco-friendly polyurethane packaging material produced therefrom.

Description

Polyurethane composition, and eco-friendly polyurethane packaging material produced therefrom}

The present invention relates to a polyurethane composition and an eco-friendly polyurethane packaging material prepared therefrom.

Polyurethane is a generic term for a polymer material obtained by urethane reaction between a polymer polyol having a reactive hydroxyl group and a polyisocyanate compound.

Such a urethane reaction is carried out in the presence of a catalyst, a blowing agent, a surfactant, a flame retardant, a crosslinking agent, and the like, if necessary.

In particular, in the production of polyurethane, various amine compounds or metal compounds are used alone or as catalysts for combination.

Among the catalysts, amine catalysts are widely used, and as the amine catalysts, for example, triethylenediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, bis(2 -Dimethylaminoethyl) ether, N,N,N',N",N"-pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N,N-dimethylethanolamine, etc. have.

However, when a polyurethane coating film is formed using the amine-based catalyst, the basic physical properties of the coating film are deteriorated, and there is a problem of causing headache and nausea due to excessive odor generated from the amine-based compound.

In addition, organometallic compounds such as organotin compounds and organic lead compounds are often used as the metal compounds, but the productivity, moldability, and physical properties of polyurethane are deteriorated, and heavy metals contained in the metal compounds remain, causing toxicity. There was a problem.

Therefore, it is eco-friendly because it does not contain heavy metals, which are environmentally regulated substances, does not cause excessive odor, does not cause headaches, nausea, etc., it is easy to control pot life, and it is possible to improve the physical properties of the polyurethane coating film to be manufactured. There is a need to develop a composition.

Korean Patent Publication No. 10-1123558 is proposed as a similar prior document for this.

Republic of Korea Patent Publication No. 10-1123558 (2012.02.27)

In order to solve the above problems, the present invention is environmentally friendly because it does not contain heavy metals, which are environmentally regulated substances, does not generate excessive odor, does not cause headaches, nausea, etc., and it is easy to control pot life, and manufacture It is an object of the present invention to provide a polyurethane composition capable of improving the physical properties of a polyurethane coating film.

In addition, it is made of the polyurethane composition for the purpose of providing an eco-friendly polyurethane packaging material having excellent mechanical strength and elongation properties.

One aspect of the present invention for achieving the above object is a main part comprising a urethane prepolymer having an isocyanate group (NCO) content of 3.5 to 6.5%; And a curing agent part including polyol, inorganic filler, pigment, bismuth (2-ethylhexanoate), bismuth propionate and heavy naphtha; it relates to a polyurethane composition comprising.

In the above aspect, the molar ratio of the bismuth (2-ethylhexanoate)/bismuth propionate (M ₁ /M ₂ ) may be 2 to 10.

In the above aspect, the content of bismuth (Bi) in the polyurethane composition may be 0.05 to 1 part by weight based on 100 parts by weight of the polyol.

In the above aspect, the polyol may be a mixture of a polyether-based diol having a number average molecular weight of 3,000 to 5,000 g/mol, and a polyether-based triol having a number average molecular weight of 3,000 to 5,000 g/mol.

In the above aspect, the inorganic filler and the pigment may be surface-modified with a silane-based compound independently of each other.

In addition, another aspect of the present invention is a main part comprising a urethane prepolymer having an isocyanate group (NCO) content of 3.5 to 6.5%; And polyol, inorganic filler, pigment, bismuth (2-ethylhexanoate), bismuth propionate, and a curing agent portion comprising a heavy naphtha; Regarding an eco-friendly polyurethane packaging material, characterized in that made of a polyurethane composition comprising will be.

As the polyurethane composition according to the present invention uses a mixture of bismuth (2-ethylhexanoate) and bismuth propionate as a catalyst, the urethane reaction is performed even when an amine-based catalyst, an organotin-based, or an organic lead-based catalyst is not used. It can play an effective catalyst role, it is easy to control pot life, and has the advantage of improving the physical properties of the product when manufacturing a polyurethane packaging material.

In addition, since it is eco-friendly because it does not contain heavy metals, which are environmentally regulated substances, and does not use an amine-based catalyst, it does not generate excessive odors, so it can prevent problems such as headaches and nausea, and prevent excessive air bubbles. I can.

In addition, when preparing polyurethane by mixing a curing agent part including polyol, inorganic filler, pigment, bismuth (2-ethylhexanoate), bismuth propionate, and heavy naphtha with a main material, the mechanical strength and elongation rate can be effectively improved. I can be good.

Hereinafter, the polyurethane composition according to the present invention and the eco-friendly polyurethane packaging material prepared therefrom will be described in detail. The drawings introduced below are provided as examples so that the spirit of the present invention can be sufficiently conveyed to those skilled in the art. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention. At this time, unless there are other definitions in the technical terms and scientific terms used, they have the meanings commonly understood by those of ordinary skill in the technical field to which this invention belongs, and the gist of the present invention in the following description and accompanying drawings Descriptions of known functions and configurations that may be unnecessarily obscure will be omitted.

The present invention relates to a polyurethane composition, specifically, a main portion comprising a urethane prepolymer having an isocyanate group (NCO) content of 3.5 to 6.5%; And a curing agent part including polyol, inorganic filler, pigment, bismuth (2-ethylhexanoate), bismuth propionate and heavy naphtha; it relates to a polyurethane composition comprising.

As such, the polyurethane composition according to the present invention uses a mixture of bismuth (2-ethylhexanoate) and bismuth propionate as a catalyst, and thus, urethane without using an amine-based catalyst, an organic tin-based, or an organic lead-based catalyst, etc. It can play an effective catalyst role during the reaction, it is easy to control pot life, and has the advantage of improving the physical properties of the product when manufacturing a polyurethane packaging material.

In addition, since it is eco-friendly because it does not contain heavy metals, which are environmentally regulated substances, and does not use an amine-based catalyst, it does not generate excessive odors, so it can prevent problems such as headaches and nausea, and prevent excessive air bubbles. I can.

In addition, when preparing polyurethane by mixing a curing agent part including polyol, inorganic filler, pigment, bismuth (2-ethylhexanoate), bismuth propionate, and heavy naphtha with a main material, the mechanical strength and elongation rate can be effectively improved. I can be good.

As a specific example, the tensile strength of the polyurethane packaging material made of the polyurethane composition of the present invention may be 2.5 to 5.0 MPa, elongation may be 1000 to 2000%, and hardness may be 55 to 60 Hs.

Hereinafter, each component of the polyurethane composition according to the present invention will be described in more detail.

First, the subject part according to the present invention will be described.

The main part according to an embodiment of the present invention may include a urethane prepolymer having an isocyanate group (NCO) content of 3.5 to 6.5%, and specifically, the urethane prepolymer has a number average molecular weight of 2,000 to 3,000 g/mol and a number of diols. It may be prepared by reacting a mixed polyol of triol having an average molecular weight of 3,000 to 5,000 g/mol and an aromatic diisocyanate-based compound.

In particular, in order to prepare a urethane prepolymer having an isocyanate group (NCO) content of 3.5 to 6.5%, it is important to react a mixed polyol and an aromatic diisocyanate compound in an appropriate ratio. Specifically, the mixed polyol: equivalent ratio of the aromatic diisocyanate compound May be 1: 1.0 to 1.5. In such a range of equivalent ratio, a urethane prepolymer having a free NCO content of 3.5 to 6.5% can be easily prepared, and if necessary, a chain extender such as 1,3-butylene glycol or trimethylol propane is added to react to cool and extract. Urethane prepolymers can be prepared.

At this time, the content of the isocyanate group (NCO) is unreacted during the reaction of the mixed polyol and the aromatic diisocyanate-based compound, and may mean the content of the isocyanate group (NCO) located at the terminal of the urethane prepolymer.

Meanwhile, the aromatic diisocyanate-based compound may be used without particular limitation as long as it is commonly used in the art, and as a specific example, any selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate. There may be one or two or more, and preferably the use of toluene diisocyanate may be effective in achieving the desired mechanical strength and elongation.

Next, the curing agent unit according to the present invention will be described.

As described above, the curing agent unit according to an example of the present invention may include polyol, inorganic filler, pigment, bismuth (2-ethylhexanoate), bismuth propionate, and heavy naphtha.

In this way, as a mixture of bismuth (2-ethylhexanoate) and bismuth propionate is used as a catalyst, it can play an effective catalyst role in urethane reaction even without using an amine-based catalyst, an organotin-based catalyst, or an organic lead-based catalyst. In addition, it is easy to adjust the pot life, and it can improve the physical properties of the product when manufacturing the polyurethane packaging material. In addition, since it is eco-friendly because it does not contain heavy metals, which are environmentally regulated substances, and does not use an amine-based catalyst, it does not generate excessive odors, so it can prevent problems such as headaches and nausea, and prevent excessive air bubbles. I can.

For this purpose, it is desirable to properly control the mixing ratio between the two components. If there is too much bismuth (2-ethylhexanoate), it is easy to control the pot life, but the physical properties of the cured product may be relatively poor, and bismuth propionate If too much is too much, the curing reaction rate is lowered, resulting in poor work efficiency when applied in the field, as well as relatively poor physical properties of the cured product.

In a preferred example, the molar ratio of the bismuth (2-ethylhexanoate)/bismuth propionate (M ₁ /M ₂ ) may be 2 to 10, more preferably 3 to 7, most preferably 4 to 5 days I can. Even at a temperature of 15 to 35° C. in this range, the pot life (time for the viscosity of the polyurethane composition to reach 100,000 cps in the present invention) can be adjusted to 30 to 70 minutes, and more specifically, to be adjusted to 40 to 60 minutes. I can. On the other hand, when the molar ratio (M ₁ /M ₂ ) is less than 2, the curing reaction may proceed too slowly, resulting in poor work efficiency, and when the molar ratio (M ₁ /M ₂ ) exceeds 10, the physical properties of the cured product will be relatively lowered. I can.

In an example of the present invention, the content of bismuth (Bi) in the curing agent part may be 0.05 to 1 parts by weight, preferably 0.1 to 0.5, and most preferably 0.13 to 0.2 parts by weight, based on 100 parts by weight of the polyol. If the content of bismuth relative to 100 parts by weight of polyol is less than 0.05 parts by weight, the curing speed is too slow, and if it exceeds 1 part by weight, the curing speed is too fast. In both cases, the work efficiency may be degraded, and the physical properties of the cured product also satisfy the standard value. It can be difficult. In this case, the content of bismuth may mean the weight occupied by the bismuth metal (Bi), not the total weight of bismuth (2-ethylhexanoate) and bismuth propionate.

In an example of the present invention, the heavy naphtha is a mixture of hydrocarbons having 6 to 12 carbon atoms distilled in the range of 100 to 220°C when refining crude oil, and may have been subjected to hydrodesulfurization. have. Such heavy naphtha prevents the bismuth (2-ethylhexanoate) and bismuth propionate catalyst from reacting with air or moisture so that the catalytic activity can be effectively maintained for a long time, while itself does not interfere with the urethane reaction. It may not reduce the physical properties of the cured product.

Meanwhile, the polyol according to an example of the present invention may be used without particular limitation as long as it is commonly used in the art. In particular, the polyol suitable for the present invention may be a polyether-based polyol, and more specifically, the number average molecular weight 3,000 to 5,000 g/mol polyether-based diol; And a polyether triol having a number average molecular weight of 3,000 to 5,000 g/mol. By mixing a polyether-based diol and a polyether-based triol satisfying the above molecular weight range, physical properties of the product may be further improved when manufacturing a urethane packaging material.

More preferably, it is good to properly adjust the content of the polyether-based diol and the polyether-based triol, and the weight ratio of the polyether-based diol/polyether-based triol may be 2 to 8, and more preferably 3 to May be 5. In this range, when manufacturing a urethane packaging material, the mechanical strength and elongation improvement effect may be particularly excellent.

The inorganic filler according to an example of the present invention may be used without particular limitation as long as it is commonly used in the art, and for example, any selected from the group consisting of calcium carbonate, barium sulfate, silicon dioxide, calcium oxide, talc, etc. It may be one or more than one.

More preferably, the inorganic filler may be surface-modified with a silane-based compound. By using an inorganic filler surface-modified with a silane-based compound, the miscibility with the polyol and the urethane prepolymer mixed later can be improved. As the isocyanate group and the mercapto group react, the inorganic filler in the polyurethane is firmly bound to the mechanical product. It is good that the strength can be further improved. The inorganic filler surface-modified with such a silane compound was added 10 to 20 parts by weight, preferably 10 to 20 parts by weight of a pigment based on 100 parts by weight of the silane compound, and stirred for 5 to 60 minutes at a speed of 50 to 150 rpm. It may be dried.

At this time, the silane-based compound may be a mercapto group-containing silane-based compound, and as a preferred embodiment, (mercaptomethyl)methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxy It may be any one or a mixture of two or more selected from the group consisting of silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriphenoxysilane, and 11-mercaptoundecyltrimethoxysilane.

The pigment according to an example of the present invention may be used without particular limitation as long as it is commonly used in the art, and for example, iron oxide, iron hydroxide, chromium oxide, barium sulfate, barium carbonate, titanium oxide, titanium dioxide, manganese dioxide, dioxide It may be any one or two or more selected from the group consisting of titanium, zirconium silicate, carbon black, sodium aluminosilicate, etc., and the color selection accordingly may be a reddish brown pigment such as iron oxide red, iron oxide yellow, chromium oxide yellow, or iron hydroxide. As a yellow pigment, a green pigment such as iron oxide green or chromium oxide green, a white pigment such as titanium oxide, an ultra-blue pigment such as sodium aluminosilicate, etc., a pigment commonly marketed in this field may be selected.

More preferably, the pigment may be surface-modified with a silane-based compound. By using a pigment surface-modified with a silane-based compound, the miscibility with the polyol and the urethane prepolymer mixed later can be improved.As the isocyanate group and the mercapto group react, the pigment in the polyurethane is firmly bound to improve the mechanical strength of the product. It is good to be able to improve it further. The pigment surface-modified with such a silane-based compound was added 10-20 parts by weight, preferably 10-20 parts by weight, based on 100 parts by weight of the silane-based compound, and stirred at a speed of 50 to 150 rpm for 5 to 60 minutes, and then dried. It may have been.

At this time, the silane-based compound may be a mercapto group-containing silane-based compound, and as a preferred embodiment, (mercaptomethyl)methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxy It may be any one or a mixture of two or more selected from the group consisting of silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriphenoxysilane, and 11-mercaptoundecyltrimethoxysilane.

In addition, the curing agent part may include 80 to 200 parts by weight of an inorganic filler and 1 to 50 parts by weight of a pigment based on 100 parts by weight of the polyol. More preferably, it may include 100 to 150 parts by weight of an inorganic filler and 5 to 30 parts by weight of a pigment based on 100 parts by weight of the polyol. The physical properties of the polyurethane packaging material manufactured in this range may be the most excellent.

In addition, the curing agent unit according to an example of the present invention may further include a latent heat material.

As described above, it is possible to prepare a polyurethane packaging material by mixing the main material and the curing agent part, and the polyurethane packaging material can be used as a flooring material such as a track of a stadium or a multipurpose stadium.

In particular, in the case of playground tracks, as polyurethane packaging is installed outdoors, shrinkage or expansion occurs due to external temperature changes, and this can easily cause cracks in the packaging material or between the packaging material and the boundary of the floor layer. By further including ash, it is possible to prevent damage by reducing the degree of shrinkage and expansion of the packaging material by storing surrounding heat by itself and releasing heat when necessary.

As a specific example, the latent heat material may be an inorganic latent heat material, an organic latent heat material, or a mixture thereof, and the inorganic latent heat material may be LiClO ₃ ·3H2O, CaCl ₂ ·6H2O or a mixture thereof, and the organic latent heat material is n-tetra It may be any one or two or more selected from the group consisting of decane, n-hexadecane and n-ocadecan.

Such a latent heat material may be added to the curing agent part, and may be added in an amount of 1 to 15 parts by weight based on 100 parts by weight of the polyol, and more preferably in an amount of 3 to 10 parts by weight. In such a range, the latent heat effect may be excellent and other physical properties of the packaging material may not be deteriorated.

Preferably, it is good to properly mix and use an inorganic latent heat material and an organic latent heat material, and as a preferred example, the weight ratio of the inorganic latent heat material: the organic latent heat material may be 30:70 to 70:30, and more preferably 40: It may be from 60 to 50:50. When the inorganic latent heat material and the organic latent heat material are mixed and used in the above range, excellent latent heat effect can be ensured for a long time, and the packaging material can be prevented from being easily cracked by physical impact. In addition, unlike conventional packaging materials that generate cracks due to shrinkage due to low temperatures in winter, there is an advantage in that cracks can be effectively prevented by mitigating shrinkage of the packaging material through latent heat performance.

Meanwhile, in an example of the present invention, the curing agent part may be mixed in an amount of 50 to 400 parts by weight based on 100 parts by weight of the main part, more preferably 150 to 250 parts by weight. In this range, it is possible to easily manufacture a polyurethane packaging material having excellent mechanical strength and elongation.

Hereinafter, the polyurethane composition according to the present invention and the eco-friendly polyurethane packaging material prepared therefrom will be described in more detail through examples. However, the following examples are only one reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Further, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. The terms used in the description herein are merely to effectively describe specific embodiments and are not intended to limit the invention. In addition, the unit of the additive not specifically described in the specification may be a weight %.

[Production Example 1]

A catalyst mixture was prepared by mixing 22.5 g of bismuth (2-ethylhexanoate), 2.5 g of bismuth propionate, and 75 g of heavy naphtha (hydrodesulfurized).

[Production Examples 2 to 7, and Comparative Preparation Examples 1 to 2]

As shown in Table 1 below, the molar ratio of bismuth (2-ethylhexanoate)/bismuth propionate (M ₁ /M ₂ ) and the content of bismuth in the catalyst mixture (% by weight) were determined by varying the amount of each component added. All processes other than those adjusted were performed in the same manner as in Preparation Example 1.

Heavy
Naphtha (g) Bi-ethylhexanoate Bi-propionate M _One /M ₂
Molar ratio Bi content
(weight%) Addition amount (g) Confiscation (M _One , mmol) Addition amount (g) Confiscation (M ₂ , mmol) Manufacturing Example 1 75.0 22.5 35.23 2.5 7.93 4.4 9.02 Manufacturing Example 2 77.8 17.0 26.62 5.2 16.49 1.6 9.01 Manufacturing Example 3 75.4 21.7 33.98 2.9 9.20 3.7 9.02 Manufacturing Example 4 74.2 24.1 37.74 1.7 5.39 7.0 9.01 Manufacturing Example 5 73.7 25.1 39.30 1.2 3.81 10.3 9.01 Manufacturing Example 6 125 22.5 35.23 2.5 7.93 4.4 6.01 Manufacturing Example 7 50 22.5 35.23 2.5 7.93 4.4 12.03 Comparative Production Example 1 72.5 27.5 43.06 - - - 9.00 Comparative Production Example 2 86.4 - - 13.6 43.13 - 9.01

[Examples 1 to 7, and Comparative Examples 1 to 2]

First, while purging nitrogen in a clean reactor, 300 g of polypropylene diol having a number average molecular weight (Mn) of 2,000 g/mol, 400 g of polyglycerol having a number average molecular weight of 3,000 g/mol, and 70 g of dioctylphthalate were added and homogeneously mixed. After heating to a temperature range of 80 to 90°C so that the moisture content of the contents was 500 ppm or less, the temperature of the reaction product was cooled to 30°C. Then, 210 g of toluene diisocyanate was slowly added dropwise while paying attention to the exothermic reaction. The temperature of the contents was raised to 80°C, and the urethane reaction was carried out while maintaining the same temperature. While maintaining the same temperature, a sample of the reactant was taken, analyzed by FT-IR (Frier Infrared Spectrometer), and the size of the 2284 cm ^-1 peak (Free NCO) was measured, and the Free NCO (%) was 5.1 according to the calibration formula verified in advance. %, the reaction was terminated, and nitrogen was purged while cooling and then taken out to prepare a urethane prepolymer base material having a viscosity of 6,250 cps and a Gardner color of 1.5.

Next, 80 g of polyglycerol (PG) having a number average molecular weight of 4,000 g/mol, 30 g of dioctylphthalate, 18 g of 4,4'-methylenebisorthochloroaniline, and polypropylene having a number average molecular weight of 3,000 g/mol After adding 320 g of diol (PPD) to raise the temperature of the contents to 110°C, add 500 g of calcium carbonate and 40 g of iron oxide, and increase the stirring speed to maintain the contents until the particle size of the contents is 10-20. If the particle size is in accordance with the standard, 6.8 g of the catalyst mixtures each prepared in Preparation Examples 1 to 7, and Comparative Preparation Examples 1 to 2 were added and mixed homogeneously, followed by cooling with nitrogen purging to prepare a polyol curing agent having a viscosity of 7200 cps. did.

At this time, the calcium carbonate was added to 15 parts by weight of calcium carbonate based on 100 parts by weight of 3-mercaptopropyltrimethoxysilane, stirred for 10 minutes at a speed of 100 rpm, and then dried and surface-modified, and the iron oxide was also 3 -15 parts by weight of iron oxide was added to 100 parts by weight of mercaptopropyltrimethoxysilane, stirred for 10 minutes at a speed of 100 rpm, and then dried to add surface-modified ones.

Next, a polyurethane binder composition was prepared by homogeneously mixing 400 g of the prepared urethane prepolymer base material and 800 g of a polyol curing agent. The polyurethane binder composition was prepared as a sample according to KF F 3211 and then subjected to standard curing (cured for 168 hours at 20° C., RH 65%) to prepare a binder sample.

[Physical property evaluation]

Physical properties and pot life were evaluated according to the method described below, and the results are shown in Table 2 below.

1) Tensile strength (MPa): The tensile strength of the binder sample was measured according to the KS F 3211 standard using a universal testing machine (5965, INSTRON Inc.).

2) Elongation (%): The elongation at break of the binder sample was measured according to the KS F 3211 standard using a universal testing machine (5965, INSTRON Inc.).

3) Hardness (Hs): The hardness of the binder sample was measured using a Shore A Type hardness tester.

4) Pot life (minutes): Pot life was evaluated to confirm the ease of application of the polyurethane binder composition to the field. Pot life evaluation is for each polyurethane binder composition, Brook Field Viscometer RV-type to simulate the pot life at ambient temperatures of 15 ℃, 25 ℃ and 32 ℃, the temperature of the constant temperature water bath to ambient temperature. The viscosity was measured while maintaining the temperature equilibrium state by immersing the viscosity measuring cup while maintaining the same as. At this time, the evaluation criterion for pot life was measured for the time until the viscosity reached 100,000 cps.

The tensile strength
(㎫) Elongation
(%) Hardness
(Hs) Pot life (minutes) 15℃ 25℃ 32℃ Example 1 3.1 1720 64 53 48 43 Example 2 2.3 1060 56 71 58 50 Example 3 2.9 1560 59 59 52 47 Example 4 3.0 1670 63 52 45 41 Example 5 2.7 1130 60 51 45 39 Example 6 2.6 1210 57 72 63 54 Example 7 2.8 1480 60 49 44 38 Comparative Example 1 2.4 1130 61 46 41 37 Comparative Example 2 2.0 980 55 75 62 51

As described in Tables 1 and 2, the molar ratio of bismuth (2-ethylhexanoate)/bismuth propionate (M ₁ /M ₂ ) satisfies 2 to 10, and the content of bismuth in the catalyst mixture is 7 to When using the catalyst mixture of Preparation Examples 1, 3 and 4 satisfying 11% by weight, not only the properties of the prepared binder sample (cured product) are excellent, but also the pot life at a temperature of 15 to 35°C is measured within 40 to 60 minutes. Therefore, it was confirmed that the work efficiency was excellent when applied to the field.

On the other hand, the content of bismuth in the catalyst mixture satisfies 7 to 11% by weight, but when the catalyst mixtures of Preparation Examples 2 and 5 in which the molar ratio (M ₁ /M ₂ ) deviates from 2 to 10 were used, the physical properties of the prepared cured product Not only was it relatively lowered, but also the pot life was too short or too long. In addition, the molar ratio (M ₁ /M ₂ ) satisfies 2 to 10, but the content of bismuth in the catalyst mixture is out of 7 to 11% by weight, even when the catalyst mixtures of Preparation Examples 6 and 7 are used, the physical properties of the prepared cured product This was relatively lowered, and the pot life was also somewhat short or somewhat longer.

On the other hand, when using the catalyst mixture of Comparative Preparation Example 1 in which only bismuth (2-ethylhexanoate) was added, the pot life at 32°C was somewhat short, the physical properties of the cured product also decreased, and comparison with bismuth propionate alone was used. In the case of using the catalyst mixture of Preparation Example 2, the working efficiency was not good because the pot life at 15° C. was too long, and the physical properties of the cured product were also greatly degraded, which was the worst.

[Examples 8 to 11]

As shown in Table 3 below, all processes were performed in the same manner as in Example 1 except for varying the amount of each component added in the polyol curing agent.

Polyol (100 parts by weight conversion) Inorganic filler (part by weight) Pigment (parts by weight) Catalyst mixture
(Part by weight) PPD (diol) PG (triol) PPD/PG
Weight ratio Calcium carbonate Iron oxide Example 1 80 20 4 125 10 1.7 Example 8 50 50 One (Same as above) (Same as above) (Same as above) Example 9 85 15 5.67 (Same as above) (Same as above) (Same as above) Example 10 90 10 9 (Same as above) (Same as above) (Same as above) Example 11 80 20 4 125
(Surface unmodified) 10
(Surface unmodified) (Same as above)

The tensile strength
(㎫) Elongation
(%) Hardness
(Hs) Example 1 3.1 1720 64 Example 8 3.4 1090 66 Example 9 3.0 1750 61 Example 10 2.6 1790 56 Example 11 2.1 1240 63

As shown in Table 4, in the case of Examples 1 and 9 in which diol and triol were mixed at an appropriate weight ratio, the mechanical strength and elongation were very excellent, but in the case of Example 8 in which an excessive amount of triol was added, the elongation rate was It dropped significantly, and in the case of Example 10 in which an excessive amount of diol was added, there was a disadvantage of lowering the tensile strength and hardness.

In addition, in the case of Example 11 in which the inorganic filler and pigment were not surface-modified, both the tensile strength and the elongation were significantly decreased as the binding strength between the inorganic filler and the pigment and the polyurethane was not good compared to Example 1.

[Example 12]

All processes were carried out in the same manner as in Example 1, except that 12 g of LiClO ₃ ·3H2O and 18 g of n-hexadecane were further added to prepare a polyol curing agent.

Dimensional stability and dimensional stability were evaluated by the following method using the binder sample prepared through this. After repeating the operation of leaving the binder sample at room temperature at 40℃ for 3 days and in a freezer at -10℃ for 3 days, it was repeated 10 times. And morphological changes were observed.

Dimensional change rate (%) = (Length before change-Length after change)/Length before change × 100

As a result, it was confirmed that the dimensional change rate was less than 3%, so that there was little shrinkage and expansion, and no damage such as cracks occurred at all when observed with the naked eye.

Although the present invention has been described through the above-specified matters and limited embodiments, this is only provided to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, to which the present invention pertains. Those of ordinary skill in the field can make various modifications and variations from these descriptions.

Therefore, the spirit of the present invention is limited to the described embodiments and should not be defined, and all things that are equivalent or equivalent to the claims as well as the claims to be described later belong to the scope of the spirit of the present invention. .

Claims (6)

A main part comprising a urethane prepolymer having an isocyanate group (NCO) content of 3.5 to 6.5% by weight; And
A curing agent portion including polyol, inorganic filler, pigment, bismuth (2-ethylhexanoate), bismuth propionate, and heavy naphtha;
Polyurethane composition comprising a.
The method of claim 1,
The molar ratio of the bismuth (2-ethylhexanoate) / bismuth propionate (M ₁ /M ₂ ) is 2 to 10, polyurethane composition.
The method of claim 1,
The content of bismuth (Bi) in the curing agent part is 0.05 to 1 part by weight based on 100 parts by weight of polyol, a polyurethane composition.
The method of claim 1,
The polyol is a mixture of a polyether-based diol having a number average molecular weight of 3,000 to 5,000 g/mol, and a polyether-based triol having a number average molecular weight of 3,000 to 5,000 g/mol, a polyurethane composition.
The method of claim 1,
The inorganic filler and the pigment are each independently surface-modified with a silane-based compound, polyurethane composition.
A main part comprising a urethane prepolymer having an isocyanate group (NCO) content of 3.5 to 6.5% by weight; And
A curing agent portion including polyol, inorganic filler, pigment, bismuth (2-ethylhexanoate), bismuth propionate, and heavy naphtha;
Eco-friendly polyurethane packaging, characterized in that made of a polyurethane composition comprising a.