KR102299012B1 - Polyurethane foam composite for shock absorption comprising shear thickening fluid and method for preparing same - Google Patents

Abstract

The present invention relates to a matrix comprising a porous, polyurethane; And it is distributed in the matrix, and a domain comprising a shear thickening fluid; includes, wherein the shear thickening fluid will include glycol and silica, it relates to a polyurethane foam composite. The polyurethane foam composite of the present invention includes a shear thickening fluid, and the polyurethane and the shear thickening fluid are connected by a urethane bond, thereby having an excellent impact absorption performance.

Description

Polyurethane foam composite for shock absorption containing shear thickening fluid and manufacturing method thereof

The present invention relates to a polyurethane foam composite, and more particularly, to a polyurethane foam composite for shock absorption to which a shear thickening fluid is applied.

Shock absorbing materials absorb impact energy to reduce injuries to objects or bodies, and plastic foam materials are typically used in a variety of ways. The plastic foam material has a lot of small-sized pores inside, so it has excellent cushioning properties, and has the advantage of being relatively light and flexible. Polymer materials such as polyurethane, polystyrene, polypropylene, and polyethylene are mainly used for foaming products.

However, when the conventional plastic foam-type shock-absorbing material is deformed too easily, it cannot effectively block external impact, whereas if it is difficult to deform, the foam itself may become an impact object. In addition, when trying to increase the impact absorption effect of the plastic foam, the volume increases, and inconvenience occurs when using the plastic foam.

It is an object of the present invention to provide a polyurethane foam composite with improved shock absorption ability by connecting the shear thickening fluid with polyurethane and urethane bonds.

According to one aspect of the present invention, a porous matrix comprising a polyurethane; and a domain distributed in the matrix and including a shear thickening fluid, wherein the shear thickening fluid includes glycol and silica, a polyurethane foam composite is provided.

In addition, the domain and the matrix may be connected by a urethane bond represented by Structural Formula 1 below, and the urethane bond may connect the polyurethane of the matrix and the glycol of the shear thickening fluid.

[Structural Formula 1]

In addition, the polyurethane foam composite may include 1 to 30 parts by weight of the shear thickening fluid based on 100 parts by weight of the polyurethane.

In addition, the shear thickening fluid may include 5 to 30 parts by weight of the silica based on 100 parts by weight of the glycol.

In addition, the polyurethane may be prepared by condensation reaction of a polyol compound and an isocyanate compound.

In addition, the polyol compound may include at least one selected from the group consisting of polyether polyols and polyester polyols.

In addition, the polyether polyol includes at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polymethylene glycol, and polytetramethylene glycol, and the polyester polyol is ethylene glycol, diethylene glycol, dipropylene glycol , propanediol, butanediol, neopentyl glycol, pentanediol, and at least one selected from the group consisting of hexanediol, and succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, oxalic acid and naph It may include at least one selected from the group consisting of a esterification reaction of at least one selected from the group consisting of tylene dicarboxylic acid.

In addition, the isocyanate compound is 4,4'-diphenylmethane diisocyanate (MDI), carbodiimide-modified MDI, polymeric MDI, hexamethylene diisocyanate, hydrogenated MDI, 4,4'-dicyclohexylmethane Diisocyanate (H ₁₂ MDI), isophorone diisocyanate (IPDI), 1,4-cyclohexylmethane diisocyanate (CHDI), 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI) And it may include at least one selected from the group consisting of isophorone diisocyanate.

In addition, the glycol is ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, polyethylene glycol, poly-1,2-propylene glycol, poly-1,3-propylene glycol, the group consisting of polytetramethylene glycol It may include one or more selected from.

In addition, the number average molecular weight of the polyethylene glycol may be 100 to 4,000.

In addition, the silica may include at least one selected from the group consisting of fumed silica, spherical silica, and fused silica.

According to another aspect of the present invention, there is provided a shock-absorbing material comprising the polyurethane foam composite.

According to another aspect of the present invention, (a) preparing a shear thickening fluid comprising silica and glycol; (b) preparing a first mixture by mixing and stirring the polyol and the shear thickening fluid; And (c) mixing and stirring the isocyanate compound in the first mixture and reacting after injecting into a mold to prepare a polyurethane foam composite; is provided a method for producing a polyurethane foam composite comprising.

In addition, the shear thickening fluid may include 5 to 30 parts by weight of the silica based on 100 parts by weight of the glycol.

In addition, the polyurethane foam composite may include 1 to 30 parts by weight of the shear thickening fluid with respect to 100 parts by weight of the polyurethane foam composite.

In addition, the method for producing the polyurethane foam composite after the step (b), (b-1) further adding a catalyst to the first mixture and stirring; may further include.

In addition, the stirring of step (b) may be performed for 5 to 120 seconds, the stirring of step (c) may be performed for 2 to 60 seconds, and the stirring of step (b-1) may be performed for 5 to 100 seconds. .

In addition, the reaction of step (c) may be carried out in a mold at a temperature of 40 to 70 ℃.

In addition, the first mixture of step (c) may further include a blowing agent.

The polyurethane foam composite of the present invention includes a shear thickening fluid, and the polyurethane and the shear thickening fluid are connected by a urethane bond, thereby having an excellent impact absorption performance.

These drawings are for reference in describing an exemplary embodiment of the present invention, and the technical spirit of the present invention should not be construed as being limited to the accompanying drawings.
1 shows the change in viscosity according to the shear rate of the shear thickening fluid prepared according to Preparation Example 1. FIG.
Figure 2 shows a scanning electron microscope image of the polyurethane foam prepared according to Examples 1 to 4 and Comparative Example 1.
3a is an FT-IR spectrum of the polyurethane foam according to Example 3 and the shear thickening fluid according to Preparation Example 1, and FIG. 3b is an FT-IR spectrum of the polyurethane foam prepared according to Comparative Example 1.
Figure 4 shows the rear deformation of the polyurethane foam prepared according to Examples 1 to 4 and Comparative Example 1.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art to which the present invention pertains can easily carry out the present invention.

However, the following description is not intended to limit the present invention to specific embodiments, and when it is determined that a detailed description of a related known technology may obscure the gist of the present invention in describing the present invention, the detailed description thereof will be omitted. .

The terminology used herein is only used to describe specific embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate that a feature, number, step, operation, element, or combination thereof described in the specification exists, but is one or more other features or It should be understood that the existence or addition of numbers, steps, acts, elements, or combinations thereof, is not precluded in advance.

Also, terms including an ordinal number such as first, second, etc. to be used below may be used to describe various elements, but the elements are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.

In addition, when it is said that a component is "formed" or "stacked" on another component, it may be formed or laminated directly attached to the front surface or one surface on the surface of the other component. It should be understood that other components may be present in the .

In addition, as used herein, "matrix (matrix)" means a continuous phase comprising the polyurethane present between the pores and pores in the polyurethane foam composite of the present invention.

In addition, as used herein, the term “domain” refers to a non-continuous phase that exists in the matrix and includes a shear thickening fluid.

Hereinafter, the shear thickening fluid will be described before describing the polyurethane foam composite.

Shear Thickening Fluid (STF) is a type of non-Newtonian fluid. In a colloid-like suspension in which solid particles are dispersed in a liquid dispersion medium, the viscosity increases when shear stress or shear rate increases. It is a fluid that causes a reversible state change from liquid to solid due to its rapidly increasing rheological properties.

The shear thickening fluid is normally in a liquid state, but when a sudden impact is applied from the outside, the phase change occurs to a solid state and becomes hard.

Hereinafter, the polyurethane foam composite for shock absorption containing the shear thickening fluid of the present invention and a manufacturing method thereof will be described in detail. However, this is provided as an example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the claims to be described later.

The polyurethane foam composite of the present invention includes a polyurethane foam and a shear thickening fluid.

Specifically, the polyurethane foam composite is porous, a matrix comprising a polyurethane; and a domain distributed in the matrix and including a shear thickening fluid, wherein the shear thickening fluid includes glycol and silica.

In addition, the domain and the matrix may be connected by a urethane bond represented by Structural Formula 1 below, and the urethane bond may connect the polyurethane of the matrix and the glycol of the shear thickening fluid.

[Structural Formula 1]

In addition, the polyurethane foam composite may include 1 to 30 parts by weight of the shear thickening fluid based on 100 parts by weight of the polyurethane.

In addition, the shear thickening fluid may contain 5 to 30 parts by weight of the silica based on 100 parts by weight of the glycol, preferably 10 to 25 parts by weight, more preferably 12 to 20 parts by weight.

In addition, the polyurethane may be prepared by condensation reaction of a polyol compound and an isocyanate compound.

In addition, the polyol compound may include a polyether polyol and a polyester polyol.

In addition, the polyether polyol includes at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polymethylene glycol, and polytetramethylene glycol, and the polyester polyol is ethylene glycol, diethylene glycol, dipropylene glycol , propanediol, butanediol, neopentyl glycol, pentanediol, and at least one selected from the group consisting of hexanediol, and succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, oxalic acid and naph It may include at least one selected from the group consisting of a esterification reaction of at least one selected from the group consisting of tylene dicarboxylic acid.

In addition, the isocyanate compound is 4,4'-diphenylmethane diisocyanate (MDI), carbodiimide-modified MDI, polymeric MDI, hexamethylene diisocyanate, hydrogenated MDI, 4,4'-dicyclohexylmethane Diisocyanate (H ₁₂ MDI), isophorone diisocyanate (IPDI), 1,4-cyclohexylmethane diisocyanate (CHDI), 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI) And it may include at least one selected from the group consisting of isophorone diisocyanate, preferably 4,4'-diphenylmethane diisocyanate.

In addition, the polyurethane may have a weight average molecular weight of 10,000 to 2,000,000.

In addition, the glycol is ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, polyethylene glycol, poly-1,2-propylene glycol, poly-1,3-propylene glycol, the group consisting of polytetramethylene glycol It may include one or more selected from.

In addition, the number average molecular weight of the polyethylene glycol may be 100 to 4,000, preferably 100 to 1,000, more preferably 100 to 500, even more preferably 100 to 300. When the number average molecular weight of polyethylene glycol is less than 100, when the shear thickening phenomenon occurs, the viscosity increase is insufficient, and the effect of absorbing shock energy due to shear stress is insignificant. It is not preferable because it is difficult for thickening to occur.

In addition, the silica may include at least one selected from the group consisting of fumed silica, spherical silica, and fused silica.

The present invention provides a shock-absorbing material comprising the polyurethane foam composite.

Hereinafter, a method for manufacturing the polyurethane foam composite of the present invention will be described.

First, a shear thickening fluid containing silica and glycol is prepared (step a).

Next, the polyol and the shear thickening fluid are mixed and stirred to prepare a first mixture (step b).

Next, the isocyanate compound is mixed with the first mixture and stirred to prepare a polyurethane foam composite by injecting it into a mold and reacting (step c).

In addition, the shear thickening fluid may be prepared by mixing 5 to 30 parts by weight of the silica based on 100 parts by weight of the glycol, preferably 10 to 25 parts by weight, more preferably 12 to 20 parts by weight. .

In addition, the polyurethane foam composite may include 1 to 30 parts by weight of the shear thickening fluid, based on 100 parts by weight of the polyurethane foam composite.

In addition, the method for producing the polyurethane foam composite may further include a step (step b-1) of further adding and stirring a catalyst to the first mixture after step b.

In addition, in step b-1, the catalyst may include amines, preferably triethyleneamine, pentamethylethylenetriamine, dimethylcyclohexylamine, and tris(3-dimethylamino). ) may include at least one selected from propylhexahydrotriamine (tris(3-dimethylamin)propylhexahydroamine), and more preferably include triethyleneamine.

In addition, the stirring of step b may be performed for 5 to 120 seconds, preferably 10 to 90 seconds, more preferably 15 to 60 seconds, even more preferably 20 to 40 seconds. When the stirring time of step b is less than 5 seconds, it is not preferable because it is insufficient to disperse the shear thickening fluid in the polyol. It is not preferable because the effect of absorbing shock energy due to shear stress is insignificant due to insufficient rise.

In addition, the stirring in step c may be performed for 2 to 60 seconds, preferably 3 to 30 seconds, more preferably 5 to 20 seconds, even more preferably 7 to 15 seconds. If the stirring time of step c is less than 2 seconds, it is not preferable because it is insufficient to disperse the isocyanate compound in the first mixture, and if it is more than 60 seconds, the polyol of the shear thickening fluid is diffused to the outside of the shear thickening fluid It is not preferable because the effect of absorbing shock energy due to shear stress is insignificant due to insufficient rise.

In addition, the stirring of step c may be performed at 500 to 5000 rpm, preferably 800 to 4,000 rpm, even more preferably 1,000 to 3,000 rpm, even more preferably 1,500 to 2,000 rpm. When the stirring in step c is less than 500 rpm, it is not preferable because it is not sufficiently mixed with the isocyanate compound between the first mixtures, and when it is more than 5,000 rpm, it is not preferable because the domain shape of the shear thickening fluid may be destroyed.

In addition, the stirring of step b-1 may be performed for 5 to 100 seconds, preferably 5 to 70 seconds, more preferably 5 to 50 seconds, even more preferably 10 to 30 seconds. When the stirring time of step b-1 is less than 5 seconds, it is not preferable because it is insufficient to disperse the catalyst in the first mixture, and when it exceeds 100 seconds, it is not preferable because the process efficiency decreases.

In addition, the reaction of step c may be carried out in a mold at a temperature of 40 to 70 ℃. When the temperature of step c is less than 40° C., it is not preferable because the reaction between the isocyanate functional group and the polyol functional group does not occur because it is not preferable.

In addition, the first mixture of step c may further contain a blowing agent, preferably water, cyclopentane, isopentane, normalpentane, chlorofluorocarbon, It may include one or more selected from hydrochlorofluorocarbon (hydrochlorofluorocarbon) and hydrofluorocarbon (hydrofluorocarbon), and more preferably include water.

The polyurethane foam composite prepared by the above method can be used as a shock-absorbing material. When the polyurethane foam composite of the present invention receives an impact, the molecules combine to absorb the energy and become hard in an instant and contain a shear thickening fluid that effectively absorbs the impact energy.

[Example]

Hereinafter, a preferred embodiment of the present invention will be described. However, this is for illustrative purposes only, and the scope of the present invention is not limited thereto.

Preparation Example 1: Shear thickening fluid

85 parts by weight of polyethylene glycol having a number average molecular weight (M _{n ) of 200 was put into a three-neck flask, and fumed silica (SiO 2} content: 99.8wt%, specific surface area (BET): 200m ² / g, pH: 4) was added in 15 parts by weight and stirred at 50 rpm or less for 24 hours to prepare a uniform shear thickening fluid.

Polyurethane Foam Composite

Example One

65 parts by weight of a polyol obtained by mixing polyethylene glycol having a number average molecular weight (M _{n ) of 1,000 and polypropylene glycol having a number average molecular weight (M n} ) of 400 in a weight ratio of 70:30 and 5 weights of the shear thickening fluid prepared according to Preparation Example 1 A uniform primary mixture was prepared by putting the part in a stirrer and performing preliminary dispersion by stirring for 30 seconds using a homogenizer.

0.01 parts by weight of triethyleneamine as a catalyst was added to the primary mixture, 3 parts by weight of water as a foaming agent was added, and stirred for 20 seconds to prepare a uniform secondary mixture.

While stirring the secondary premix at 1500 rpm, 30 parts by weight of 4,4'-diphenylmethane diisocyanate (MDI) was added, followed by mixing for 10 seconds. The urethane polymerization reaction was started, and the creamy foaming solution was injected into the mold within 15 seconds, and mold-molded at a temperature of 50 to 60° C. for 30 minutes to prepare a polyurethane foam composite.

The density of the polymerized polyurethane was 0.1915 g/cm ³ , and the hardness was 78.6 (Shore Hardness tester, F type).

Example 2

A polyurethane foam composite was prepared in the same manner as in Example 1, except that 10 parts by weight of the shear thickening fluid was used instead of 5 parts by weight of the shear thickening fluid. The polymerized polyurethane had a density of 0.1949 g/cm ³ and a hardness of 73.6.

Example 3

A polyurethane foam composite was prepared in the same manner as in Example 1, except that 15 parts by weight of the shear thickening fluid was used instead of 5 parts by weight of the shear thickening fluid. The polymerized polyurethane had a density of 0.1844 g/cm ³ and a hardness of 70.3.

Example 4

A polyurethane foam composite was prepared in the same manner as in Example 1, except that 20 parts by weight of the shear thickening fluid was used instead of 5 parts by weight of the shear thickening fluid. The density of the polymerized polyurethane was 0.1851 g/cm ³ , and the hardness was 39.0.

Example 5

A polyurethane foam composite was prepared in the same manner as in Example 1, except that 29.25 parts by weight of MDI and 3.25 parts by weight of the shear thickening fluid were used instead of using 30 parts by weight of MDI and 5 parts by weight of the shear thickening fluid.

Example 6

A polyurethane foam composite was prepared in the same manner as in Example 1, except that 30.79 parts by weight of MDI and 3.42 parts by weight of the shear thickening fluid were used instead of using 30 parts by weight of MDI and 5 parts by weight of the shear thickening fluid.

comparative example One

A polyurethane foam was prepared in the same manner as in Example 1, except that the shear thickening fluid was not used instead of using 5 parts by weight of the shear thickening fluid. The polymerized polyurethane had a density of 0.1835 g/cm ³ and a hardness of 81.6.

comparative example 2

A polyurethane foam was prepared in the same manner as in Example 1, except that 29.25 parts by weight of MDI was used instead of 30 parts by weight of MDI and 5 parts by weight of the shear thickening fluid, and the shear thickening fluid was not used.

Table 1 below summarizes the proportions by weight of the polyurethane foam composites according to Examples 1 to 6 and Comparative Examples 1 and 2.

division polyol
(parts by weight) isocyanate
(parts by weight) Shear thickening fluid
(parts by weight) catalyst
(parts by weight) Example 1 65 30 5 0.01 Example 2 65 30 10 0.01 Example 3 65 30 15 0.01 Example 4 65 30 20 0.01 Example 5 65 29.25 3.25 0.01 Example 6 65 30.79 3.42 0.01 Comparative Example 1 65 30 0 0.01 Comparative Example 2 65 29.25 0 0.01

[Test Example]

test example One: of the shear thickening fluid Viscosity measurement

1 shows the change in viscosity according to the shear rate of the shear thickening fluid prepared according to Preparation Example 1. FIG. Specifically, in order to observe the rheological behavior of the shear thickening fluid prepared according to Preparation Example 1, the shear viscosity according to the normal shear rate was measured using a rheometer (Advanced Rheometric Expansion System, Rhemetic Scientific, USA). The measurement having a diameter of 50mm was used for the angle of 2 ° cone and the plate-like viscoelasticity test fixture (Cone & plate geometry) range of shear rates of data 0.1 to 1000s ^- was measured at ^1. According to FIG. 1, it can be confirmed that a shear thickening fluid, which is a type of non-Newtonian fluid, exhibiting a rheological characteristic in which the viscosity rapidly increases when the shear rate is increased was prepared.

test example 2: electron microscope image

Figure 2 shows an electron microscope image of the polyurethane foam composite prepared according to Examples 1 to 4 and Comparative Example 1. Specifically, prepared according to Examples 1 to 4 and Comparative Example 1 at x35, x2000, x5000, and x10000 magnifications using a scanning electron microscope (SEM) to check whether a complex between the polyurethane foam and the shear thickening fluid is formed Surface observation of the polyurethane foam composite was performed.

According to FIG. 2, it can be confirmed that pores are formed inside the polyurethane foam in the x35 magnification image, and as a result of magnifying the observation between the pores and the pores at x2000 magnification, in Examples 1 to 4, the circular shape that is not visible in Comparative Example 1 It can be confirmed that a white domain indicated by a dotted line exists.

Therefore, when preparing the polyurethane foam composite according to Examples 1 to 4, it can be confirmed that the shear thickening fluid is present inside the pores and the polyurethane foam support (matrix) between the pores.

In addition, the x5000 magnification image of Figure 2 is an enlarged photo of the polyurethane foam support in which the domain containing the support part of the foam indicated by the dotted lines of the rectangle and trapezoid shape and the shear thickening fluid indicated by the dotted lines of the circular shape in the x2500 magnification image is present. As a result, it can be confirmed once again that the shape of the polyurethane foam support and the shear thickening fluid domain are significantly different.

As a result, it can be confirmed that the polyurethane foam composite of the polyurethane foam and the shear thickening fluid was formed when prepared according to Examples 1 to 4.

Test Example 3: Confirmation of urethane bonding between shear thickening fluid and polyurethane foam

Figure 3a is the FT-IR spectrum of the polyurethane foam according to Example 3 and the shear thickening fluid according to Preparation Example 1, Figure 3b is the present invention synthesized by the FT-IR spectrum of the polyurethane foam prepared according to Comparative Example 1 The structure of the urethane foam composite was analyzed. Referring to FIG. 3a, in the spectrum of the polyurethane foam according to Example 3, it was observed that the transmittance was slightly decreased at the ^{3390cm -1} point showing the expansion and contraction peak of OH compared to the spectrum of the shear thickening fluid according to Preparation Example 1. to increase the transmittance at 1537cm ^-1 and 1241cm ^-1 were observed point represents the NH stretching peak of 1726cm ^-1 and a urethane group that represents the C = O stretching peak. Referring to FIG. 3B , it was observed that transmittance increased at ^{1724 cm −1} and 1533 cm ⁻¹ points, similar to Example 3 of FIG. 3A . This is because polyethylene glycol in the shear thickening fluid is a type of polyol that forms polyurethane foam, so when forming the polyurethane foam containing the shear thickening fluid, polyethylene glycol in the shear thickening fluid reacts with isocyanate to form a urethane bond. can

Therefore, when forming the polyurethane foam containing the shear thickening fluid, it can be seen that a urethane bond is formed between the shear thickening fluid and the polyurethane foam, and the shear thickening fluid is a support (matrix, wall) between the pores of the polyurethane foam. ), it can be seen that the effect of the shear thickening fluid is exhibited when a shear stress is generated against an external external force.

Test Example 4: Analysis of low-speed shock absorption capacity

4 shows the rear deformation of Examples 1 to 4 and Comparative Example 1 according to the low-speed impact test results, and Table 2 below summarizes the trauma depth and shock resistance according to the low-speed impact test results. is indicated by

division Low-speed shock absorption test Impact resistance test Impact depth (mm) Impact Depth (%) Shock Transmission (N) Example 1 42.95 0.6 - Example 2 41.64 3.6 - Example 3 35.88 16.9 - Example 4 57.09 -32.2 - Example 5 - - 1217 Example 6 - - 1268 Comparative Example 1 43.19 0 - Comparative Example 2 - - 1649

The polyurethane foam composites prepared according to Examples 1 to 4 and Comparative Example 1 were subjected to an external force using a low velocity impactor to measure the trauma depth of the rear surface of the polyurethane foam. Measurements were carried out after the deformation of the foam was made by making a shape with gypsum using an oasis foam that shows the impact as it is on the back side of the impact.

According to FIG. 4, the dispersion state and energy size of the impact energy can be visually confirmed from the shape of the rear deformation, and in the case of the polyurethane foam containing the shear thickening fluid, the external force spreads to the surface compared to the non-containing polyurethane foam. It can be seen that the length change in the direction is shortened.

Therefore, it can be seen that the external impact energy is partially absorbed in the polyurethane foam containing the shear thickening fluid and reduces the impact transmitted to the back of the specimen.

According to Table 2, the measured impact depth (mm) of the polyurethane foam composites prepared according to Examples 1 to 4 and Comparative Example 1 were 42.95, 41.64, 35.88, 57.09, 43.19, respectively, 0.6 compared to the composite without the shear thickening fluid %, 3.6%, 16.9%, and -32.2%.

Therefore, when the content of the shear thickening fluid in the polyurethane foam composite is 20 parts by weight, the content of the shear thickening fluid excessively reduces the support bonding of the polyurethane foam to form a flexible polyurethane foam. can be seen to increase.

test example 5: Measurement of the amount of shock transmission

To measure the amount of impact delivered, the impact resistance was measured by dropping a 2.5kg dumbbell and measuring the energy reaching the lower sensor when 5J of energy was applied, and it is described in Table 2.

Referring to Table 2, in order to apply the polyurethane foam composite as a shock-absorbing pad, the amount of impact transmission of Example 5 and Comparative Example 2 that did not use the shear thickening fluid was 1217N, respectively, in Example 5 using 3.25 parts by weight of the shear thickening fluid, It can be confirmed that it is 1649N. That is, it was found that the impact transfer amount of the polyurethane foam composite of Example 5 in which 3.25 parts by weight of the shear thickening fluid was used was significantly reduced compared to the polyurethane of Comparative Example 2 in which the shear thickening fluid was not used. At this time, the thickness of the polyurethane foam composite used in the experiment was 10mm.

The scope of the present invention is indicated by the following claims rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention. do.

Claims (19)

(a) preparing a shear thickening fluid containing silica and glycol;
(b) preparing a first mixture by mixing and stirring the polyol and the shear thickening fluid;
(b-1) further adding a catalyst and a blowing agent to the first mixture and stirring to prepare a second mixture; and
(c) mixing and stirring the isocyanate compound to the second mixture, injecting it into a mold, and reacting to prepare a polyurethane foam composite;
The stirring of step (b) is carried out for 5 to 120 seconds,
The stirring of step (c) is carried out for 2 to 60 seconds,
The stirring of step (b-1) is carried out for 5 to 100 seconds,
The stirring of step (c) is carried out at 500 to 5,000 rpm,
The polyurethane foam composite is
a porous matrix comprising polyurethane; and
Distributed in the matrix, the domain containing the shear thickening fluid; Containing,
The shear thickening fluid includes glycol and silica,
The domain and the matrix are connected by a urethane bond represented by Structural Formula 1 below,
The urethane bond is to connect the polyurethane of the matrix and the glycol of the shear thickening fluid, the method for producing a polyurethane foam composite:
[Structural Formula 1]

delete delete delete According to claim 1,
The method for producing a polyurethane foam composite, characterized in that the polyurethane is prepared by a condensation reaction of a polyol compound and an isocyanate compound. 6. The method of claim 5,
The polyol compound is a method for producing a polyurethane foam composite, characterized in that it comprises at least one selected from the group consisting of polyether polyol and polyester polyol. 7. The method of claim 6,
The polyether polyol contains at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polymethylene glycol, and polytetramethylene glycol,
The polyester polyol is at least one selected from the group consisting of ethylene glycol, diethylene glycol, dipropylene glycol, propanediol, butanediol, neopentyl glycol, pentanediol and hexanediol, succinic acid, and adipic acid, sebacic acid, azelaic acid , phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, oxalic acid and at least one selected from the group consisting of at least one selected from the group consisting of esterification reaction of at least one selected from the group consisting of naphthylene dicarboxylic acid Poly comprising Method for producing a urethane foam composite. 6. The method of claim 5,
The isocyanate compound is 4,4'-diphenylmethane diisocyanate (MDI), carbodiimide-modified MDI, polymeric MDI, hexamethylene diisocyanate, hydrogenated MDI, 4,4'-dicyclohexylmethane diisocyanate (H12MDI), isophorone diisocyanate (IPDI), 1,4-cyclohexylmethane diisocyanate (CHDI), 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI) and isophorone di A method for producing a polyurethane foam composite, comprising at least one selected from the group consisting of isocyanates. According to claim 1,
The glycol is selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, polyethylene glycol, poly-1,2-propylene glycol, poly-1,3-propylene recall, and polytetramethylene glycol. Method for producing a polyurethane foam composite comprising at least one. 10. The method of claim 9,
The method for producing a polyurethane foam composite, characterized in that the number average molecular weight of the polyethylene glycol is 100 to 4,000. According to claim 1,
The silica is a method of manufacturing a polyurethane foam composite, characterized in that it comprises at least one selected from the group consisting of fumed silica, spherical silica, and fused silica. delete delete According to claim 1,
The method for producing a polyurethane foam composite, characterized in that the shear thickening fluid comprises 5 to 30 parts by weight of the silica based on 100 parts by weight of the glycol. According to claim 1,
The polyurethane foam composite is a method of manufacturing a polyurethane foam composite, characterized in that it comprises 1 to 30 parts by weight of the shear thickening fluid with respect to 100 parts by weight of the polyurethane. delete delete According to claim 1,
Method for producing a polyurethane foam composite, characterized in that the reaction of step (c) is carried out at a temperature of 40 to 70 ℃ in a mold. delete

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