WO2020050638A1

WO2020050638A1 - Polyurethane foam composite for absorbing shock, containing shear thickening fluid, and preparation method therefor

Info

Publication number: WO2020050638A1
Application number: PCT/KR2019/011448
Authority: WO
Inventors: 유의상; 권미연; 이현경; 김주혜
Original assignee: 한국생산기술연구원
Priority date: 2018-09-06
Filing date: 2019-09-05
Publication date: 2020-03-12

Abstract

The present invention relates to a polyurethane foam composite containing a matrix which is porous and which comprises a polyurethane, and a domain distributed in the matrix, and containing a shear thickening fluid, wherein the shear thickening fluid contains glycol and silica. The polyurethane foam composite of the present invention contains a shear thickening fluid, and has a polyurethane and the shear thickening fluid, which are connected by urethane bond, and thus has excellent shock-absorbing performance.

Description

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

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.

The shock absorbing material absorbs impact energy to reduce injury to an object or body, and plastic foam materials are typically used in various ways. The plastic foam material has the advantage of being excellent in cushioning, relatively light and excellent in flexibility because it has many pores of a small size inside. Polymer materials such as polyurethane, polystyrene, polypropylene, and polyethylene are mainly used for foaming products, and among them, polyurethane and polystyrene foams having a relatively high density and rigid and rigid form are mainly used as shock absorbing materials.

However, the conventional plastic foam-type shock absorbing material does not effectively prevent external shock when deformed too easily, while the foam itself may become an impact object when deformation is difficult. In addition, when trying to increase the shock absorbing effect of the plastic foam, the volume becomes large, which causes inconvenience when using it.

An object of the present invention is to provide a polyurethane foam composite having improved shock absorption capacity by connecting a shear thickening fluid with a polyurethane and a urethane bond.

According to one aspect of the invention, the porous, the 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, and 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 relative to 100 parts by weight of the polyurethane.

In addition, the shear thickening fluid may include 5 to 30 parts by weight of the silica with respect to 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 hexanediol and at least one selected from the group consisting of 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 one or more selected from the group consisting of one or more selected from the group consisting of styrene dicarboxylic acid esterification reaction.

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 isophorone diisocyanate.

In addition, the glycol is a group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, polyethylene glycol, poly-1,2-propylene glycol, poly-1,3-propylene glycol and 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 one or more selected from the group consisting of fumed silica, spherical silica (spherical silica) and fused silica (fused silica).

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

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 the first mixture with an isocyanate compound, stirring it, injecting it into a mold, and reacting to prepare a polyurethane foam composite; a method for producing a polyurethane foam composite is provided.

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

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

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

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

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 a polyurethane and a shear thickening fluid are connected to each other by urethane bonding, thereby providing excellent shock absorption performance.

Since these drawings are for reference to explain exemplary embodiments of the present invention, the technical spirit of the present invention should not be construed as being limited to the accompanying drawings.

Figure 1 shows the viscosity change according to the shear rate (shear rate) of the shear thickening fluid prepared according to Preparation Example 1.

Figure 2 shows a scanning electron microscope image of the polyurethane foam prepared according to Examples 1 to 4 and Comparative Example 1.

Figure 3a is a FT-IR spectrum of the shear thickening fluid according to Preparation Example 1 and the polyurethane foam according to Example 3, Figure 3b is an FT-IR spectrum of the polyurethane foam prepared according to Comparative Example 1.

Figure 4 shows the back strain of the polyurethane foam prepared according to Examples 1 to 4 and Comparative Example 1.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement 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 known technologies related to the present invention may obscure the subject matter of the present invention, the detailed description will be omitted. .

The terms used herein are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, terms such as “include” or “have” are intended to indicate that a feature, number, step, operation, component, or combination thereof described in the specification exists, or that one or more other features or It should be understood that numbers, steps, operations, elements, or combinations thereof do not preclude the presence or addition possibilities of those in combination.

In addition, terms including ordinal numbers such as first and second to be used below may be used to describe various components, but the components are not limited by the terms. The terms are used only for the purpose of distinguishing one component from other components. For example, the first component may be referred to as a second component without departing from the scope of the present invention, and similarly, the second component may be referred to as a first component.

Also, when a component is said to be "formed" or "stacked" on another component, it may be formed or stacked directly attached to the front or one side of the surface of the other component, but may be intermediate. It should be understood that other components may exist in the.

Also, as used herein, “matrix” refers to a continuous phase comprising a polyurethane present between pores and pores in the polyurethane foam composite of the present invention.

Also, as used herein, “domain” means a non-continuous phase that exists inside the matrix and contains a shear thickening fluid.

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

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

Shear thickening fluid is usually in a liquid phase, and when a sudden impact is applied from the outside, a phase change to a solid phase occurs, and due to the property of being hardened, research into which fibers are impregnated and used as bulletproof or anti-vibration materials has been actively conducted.

Hereinafter, the polyurethane foam composite for shock absorption containing the shear thickening fluid of the present invention and a method of manufacturing the same will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of 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 polyurethane; And a domain distributed in the matrix and including a shear thickening fluid, wherein the shear thickening fluid comprises glycol and silica.

[Structural Formula 1]

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

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

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 one or more 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 number average molecular weight of the polyethylene glycol may be 100 to 4,000, preferably 100 to 1,000, more preferably 100 to 500, and even more preferably 100 to 300. When the number average molecular weight of polyethylene glycol is less than 100, it is not preferable because the viscosity increase is insufficient when the shear thickening phenomenon occurs, and the impact energy absorption effect by the shear stress becomes insignificant, and when it exceeds 4,000, the shear as the fluid disappears. It is not preferable because thickening is difficult to occur.

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 comprising silica and glycol is prepared (step a).

Next, a first mixture is prepared by mixing and stirring the polyol and the shear thickening fluid (step b).

Next, an isocyanate compound is mixed with the first mixture, stirred, injected into a mold, and reacted to prepare a polyurethane foam composite (step c).

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

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

In addition, the catalyst in step b-1 may include amines, preferably triethyleneamine, pentamethylethylenetriamine, dimethylcyclohexylamine and tris (3-dimethylamino) ) It may include one or more selected from the group consisting of propyl hexahydrotriamine (tris (3-dimethylamin) propylhexahydroamine), and more preferably may 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, and even more preferably 20 to 40 seconds. When the stirring time of step b is less than 5 seconds, it is not preferable because the shear thickening fluid is insufficient to disperse in the polyol, and when it exceeds 120 seconds, the polyol of the shear thickening fluid diffuses out of the shear thickening fluid and viscosity during shear thickening. It is not preferable because the effect of absorbing impact energy due to shear stress is insufficient due to insufficient rise.

In addition, the stirring of step c may be performed for 2 to 60 seconds, preferably 3 to 30 seconds, more preferably 5 to 20 seconds, and even more preferably 7 to 15 seconds. When the stirring time in step c is less than 2 seconds, it is not preferable because the isocyanate compound is insufficient to disperse in the first mixture, and when it exceeds 60 seconds, the polyol of the shear thickening fluid diffuses out of the shear thickening fluid and viscosity during shear thickening. It is not preferable because the effect of absorbing impact energy due to shear stress is insufficient due to insufficient rise.

In addition, the agitation 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, and 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 the first mixture is not sufficiently mixed with the isocyanate compound, and when it exceeds 5,000 rpm, the domain form of the shear thickening fluid may be destroyed, which is not preferable.

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 in step b-1 is less than 5 seconds, it is not preferable because the catalyst is insufficient to disperse in the first mixture, and when it exceeds 100 seconds, the process efficiency is poor, which is undesirable.

In addition, the reaction of step c may be performed at a temperature of 40 to 70 ° C in the mold. If 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 is difficult to occur, and when it exceeds 70 ° C, an excessively fast reaction is induced, and it is difficult to control the reaction.

In addition, the first mixture of step c may further include a blowing agent, preferably water, cyclopentane, isopentane, normalpentane, chlorofluorocarbon, It may include one or more selected from the group consisting of hydrochlorofluorocarbons and hydrofluorocarbons, and more preferably water.

The polyurethane foam composite produced by the above method can be used in shock absorbing materials. The polyurethane foam composite of the present invention, when shocked, combines molecules so as to absorb its energy and becomes hard in an instant, and includes a shear thickening fluid that effectively absorbs the shock energy, and thus can significantly improve the shock absorbing power of the shock absorbing material.

[Example]

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

Preparation Example 1: Shear thickening fluid

Fumed silica (SiO ₂ content: 99.8 wt%, specific surface area (BET): 200 m ² /) while adding 85 parts by weight of polyethylene glycol having a number average molecular weight (M _n ) 200 to the 3-neck flask and stirring the impeller's stirring speed to 60 rpm or less. g, pH: 4) 15 parts by weight was added and stirred for 24 hours at 50 rpm or less to prepare a uniform shear thickening fluid.

Polyurethane foam composite

Example 1

65 weight parts of 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 weight of shear thickening fluid prepared according to Preparation Example 1 The mixture was placed in a stirrer and stirred for 30 seconds using a homogenizer to prepare a uniform primary mixture.

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

30 parts by weight of 4,4'-diphenylmethane diisocyanate (MDI) was added while stirring the secondary premix at 1500 rpm, followed by mixing for 10 seconds. The urethane polymerization reaction 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 density of the polymerized polyurethane was 0.1949 g / cm ³ and the hardness was 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 density of the polymerized polyurethane was 0.1844 g / cm ³ and the hardness was 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 30 parts by weight of MDI and 5 parts by weight of shear thickening fluid were used instead of 29.25 parts by weight of MDI and 3.25 parts by weight of shear thickening fluid.

Example 6

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

Comparative example One

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

Comparative example 2

Polyurethane foam was prepared in the same manner as in Example 1, except that 30 parts by weight of MDI and 5 parts by weight of shear thickening fluid were used instead of 29.25 parts by weight of MDI and no shear thickening fluid was used.

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

구분division	폴리올(중량부)Polyol (parts by weight)	이소시아네이트(중량부)Isocyanate (parts by weight)	전단농화유체(중량부)Shear thickening fluid (parts by weight)	촉매(중량부)Catalyst (parts by weight)
실시예 1Example 1	6565	3030	55	0.010.01
실시예 2Example 2	6565	3030	1010	0.010.01
실시예 3Example 3	6565	3030	1515	0.010.01
실시예 4Example 4	6565	3030	2020	0.010.01
실시예 5Example 5	6565	29.2529.25	3.253.25	0.010.01
실시예 6Example 6	6565	30.7930.79	3.423.42	0.010.01
비교예 1Comparative Example 1	6565	3030	00	0.010.01
비교예 2Comparative Example 2	6565	29.2529.25	00	0.010.01

[Test Example]

Test Example 1: Shear thickening fluid viscosity measurement

Figure 1 shows the viscosity change according to the shear rate (shear rate) of the shear thickening fluid prepared according to Preparation Example 1. Specifically, in order to observe the rheological behavior of the shear thickening fluid prepared according to Preparation Example 1, 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 having a rheological characteristic in which the viscosity rapidly increases when the shear rate is increased, was prepared.

Test Example 2: electron microscope image

2 shows electron microscopic images of polyurethane foam composites prepared according to Examples 1 to 4 and Comparative Example 1. In detail, it was 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 confirm whether the complex of the polyurethane foam and the shear thickening fluid was formed. The surface observation of the polyurethane foam composite was performed.

According to FIG. 2, it can be seen that pores were formed inside the polyurethane foam in the x35 magnification image, and the magnification between the pores and the pores was observed at an x2000 magnification, and as a result, in Examples 1 to 4, the circular shape was not visible You can see that the white domain indicated by the 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 matrix of the polyurethane foam between the pores.

In addition, the x5000 magnification image of FIG. 2 enlarges a polyurethane foam support in which a domain including a support portion of a foam indicated by a dotted line in a triangle, square and trapezoid shape and a shear thickening fluid indicated by a dotted line in a circular shape in the x2000 magnification image In one photo, it can be confirmed that the shape of the support and the shear thickening fluid domain of the polyurethane foam are significantly different.

As a result of this, 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 bond between shear thickening fluid and polyurethane foam

Figure 3a is a shear thickening fluid according to Preparation Example 1 and FT-IR spectrum of the polyurethane foam according to Example 3, Figure 3b is the invention synthesized by FT-IR spectrum of the polyurethane foam prepared according to Comparative Example 1 The structure of the urethane foam composite was analyzed. Referring to Figure 3a, the spectrum of the polyurethane foam according to Example 3 was observed to slightly decrease the transmittance at the point of 3390cm ^-1 indicating the stretch 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 Figure 3b, similar to Example 3 of Figure 3a it was observed that the transmittance increased at 1724cm ^-1 and 1533cm ^-1 points. This is a kind of polyol in which the polyethylene glycol in the shear thickening fluid forms a polyurethane foam, so when forming the polyurethane foam containing the shear thickening fluid, the 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 also a support (matrix, wall) between the pores and the pores of the polyurethane foam. It can be seen that it exerts the effect of shear thickening fluid when it is present in combination with) and shear stress is generated against external force.

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

Figure 4 shows the back strain of Examples 1 to 4 and Comparative Example 1 according to the low-speed impact test results, Table 2 summarizes the impact depth (trauma depth) and the impact transmission (shock resistance) according to the low-speed impact test results Is shown.

구분division	저속 충격흡수 시험Low speed shock absorption test		충격저항시험Impact resistance test
구분division	충격 깊이(mm)Impact depth (mm)	충격 깊이(%)Impact depth (%)	충격 전달량(N)Impact transmission (N)
실시예 1Example 1	42.9542.95	0.60.6	--
실시예 2Example 2	41.6441.64	3.63.6	--
실시예 3Example 3	35.8835.88	16.916.9	--
실시예 4Example 4	57.0957.09	-32.2-32.2	--
실시예 5Example 5	--	--	12171217
실시예 6Example 6	--	--	12681268
비교예 1Comparative Example 1	43.1943.19	00	--
비교예 2Comparative Example 2	--	--	16491649

The polyurethane foam composites prepared according to Examples 1 to 4 and Comparative Example 1 were measured using a low velocity impactor to measure the trauma depth of the back surface of the polyurethane foam subjected to external force. The oasis foam, which shows the impact as it is on the back side where the impact was applied, was used to measure the deformation of the foam after floating it in plaster.

According to FIG. 4, the dispersion state and energy size of 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 polyurethane foam not included in the impact. You can see that the length change for the direction is short.

Therefore, it can be seen that the external impact energy is partially absorbed from the polyurethane foam containing the shear thickening fluid to reduce the impact transmitted to the back of the test piece.

According to Table 2, the measured impact depths (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, and 43.19, respectively, compared to 0.6 in the shear-free fluid-free composite. %, 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 bond of the polyurethane foam to form a soft polyurethane foam, thereby reducing the relative compressive hardness and impact depth. Can be seen as getting bigger.

Test Example 5: Measurement of impact transmission

The impact transmission was measured by measuring the energy reaching the sensor below when 5J of energy was applied by dropping a 2.5kg dumbbell, and the impact resistance was measured, and the results are shown in Table 2.

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

The scope of the present invention is indicated by the following claims rather than the above detailed description, and it should be interpreted that all changes or modified forms derived from the meaning and scope of the claims and equivalent concepts thereof are included in the scope of the present invention. do.

Claims

A porous, matrix comprising polyurethane; And

A domain distributed in the matrix and comprising a shear thickening fluid; Including,

The shear thickening fluid is to include glycol and silica,

Polyurethane foam composite.
The method of claim 1,

The domain and the matrix are connected by a urethane bond represented by Structural Formula 1 below,

Polyurethane foam composite, characterized in that the urethane bond connects the polyurethane of the matrix and the glycol of the shear thickening fluid.

[Structural Formula 1]
The method of claim 1,

Polyurethane foam composite, characterized in that the polyurethane foam composite comprises 1 to 30 parts by weight of the shear thickening fluid relative to 100 parts by weight of the polyurethane.
The method of claim 1,

Polyurethane foam composite, characterized in that the shear thickening fluid comprises 5 to 30 parts by weight of the silica relative to 100 parts by weight of the glycol.
The method of claim 1,

The polyurethane foam composite, characterized in that the polyurethane is prepared by condensation reaction of a polyol compound and an isocyanate compound.
The method of claim 5,

Polyurethane foam composite, characterized in that the polyol compound comprises at least one selected from the group consisting of polyether polyols and polyester polyols.
The method of claim 6,

The polyether polyol includes 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, adipic acid, sebacic acid, azelaic acid, Polyurethane characterized in that it comprises at least one selected from the group consisting of esterification reaction of at least one member selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, oxalic acid and naphthylenedicarboxylic acid. Foam composite.
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 (H 12 MDI), isophorone diisocyanate (IPDI), 1,4-cyclohexylmethane diisocyanate (CHDI), 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI) and iso A polyurethane foam composite comprising at least one member selected from the group consisting of foron diisocyanate.
The method of 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 glycol and polytetramethylene glycol. Polyurethane foam composite, characterized in that it comprises at least one.
The method of claim 9,

Polyurethane foam composite, characterized in that the number average molecular weight of the polyethylene glycol is 100 to 4,000.
The method of claim 1,

The silica is a fumed silica (fumed silica), spherical silica (spherical silica), and fused silica (fused silica) polyurethane foam composite characterized in that it comprises at least one member selected from the group consisting of.
Shock-absorbing material comprising the polyurethane foam composite according to claim 1.
(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) preparing an polyurethane foam composite by mixing an isocyanate compound in the first mixture, stirring it, injecting it into a mold, and reacting;

Method for producing a polyurethane foam composite comprising.
The method of claim 13,

Polyurethane foam composite, characterized in that the shear thickening fluid comprises 5 to 30 parts by weight of the silica relative to 100 parts by weight of the glycol.
The method of claim 13,

Method for producing a polyurethane foam composite, characterized in that the polyurethane foam composite comprises 1 to 30 parts by weight of the shear thickening fluid relative to 100 parts by weight of the polyurethane.
The method for manufacturing the polyurethane foam composite according to claim 13,

After the step (b), (b-1) adding a catalyst to the first mixture and stirring; further comprising a polyurethane foam composite manufacturing method comprising the.
The method of claim 16,

Stirring in step (b) is performed for 5 to 120 seconds,

Stirring in step (c) is carried out for 2 to 60 seconds,

Method of manufacturing a polyurethane foam composite, characterized in that the stirring of step (b-1) is performed for 5 to 100 seconds.
The method of claim 13,

Method of manufacturing a polyurethane foam composite, characterized in that the reaction of step (c) is carried out at a temperature of 40 to 70 ℃ in the mold.
The method of claim 13,

Method of manufacturing a polyurethane foam composite, characterized in that the first mixture of step (c) further comprises a blowing agent.