KR101978113B1 - Method for manufacturing polyurethane compression sponge with water-repellent surface and polyurethane compression sponge by manufactured thereof - Google Patents

Abstract

The present invention relates to a method of manufacturing a polyurethane compressed sponge with water-repellent surface and a polyurethane compressed sponge manufactured thereby. An objective of the present invention is to provide a method of manufacturing a polyurethane compressed sponge with water-repellent surface, which can improve water-repellent performance provided in the surface by having a uniform mechanical strength on the whole through pretreatment of a polyurethane sponge, and a polyurethane compressed sponge manufactured thereby. The method of the present invention comprises: a preparation step of preparing the polyurethane sponge; a compression step of thermal compressing the polyurethane sponge into the polyurethane compressed sponge by a compression processing device; an aging step of discharging gas generated during the thermal compressing process; and a surface treatment step of providing functionality in the surface of the polyurethane compressed sponge, wherein the surface treatment step coats a super water-repellent coating agent on the surface of the polyurethane compressed sponge to provide the polyurethane compressed sponge with a super water-repellent functionality. The surface treatment step comprises the steps of: preparing the super water-repellent coating agent; spraying the super water-repellent coating agent on the surface of the polyurethane compressed sponge to provide the super water-repellent coating agent in the surface of the polyurethane compressed sponge; and drying the polyurethane compressed sponge to remove a solvent contained in the super water-repellent coating agent.

Description

TECHNICAL FIELD The present invention relates to a method for producing a polyurethane compression sponge having a water-repellent surface and a polyurethane compression sponge produced thereby,

The present invention relates to a method for producing a polyurethane compression sponge having a water-repellent surface and a polyurethane compression sponge produced thereby, and more particularly, to a polyurethane compression sponge produced by pretreating a polyurethane sponge, To a polyurethane compression sponge having a water repellent surface which provides improved water repellency to the surface of the polyurethane compression sponge using a novel coating material and a polyurethane compression sponge produced thereby.

As the industry develops in recent years, much research has been done to improve the quality of industrial and architectural materials. Among these materials, polyurethane has excellent mechanical and physical properties and is widely used in a wide range of fields such as building materials, surface coating, artificial leather materials, automobile interior materials and medical materials.

Polyurethane, which was first developed in Germany, is produced by using isocyanate as hard segment and synthesizing it as urethane or urea bond in the repeating unit by reacting them with soft segment such as polyol or diamine.

These polyurethanes are widely used as coating agents, adhesives, fillers, etc. in general for fibers, leather, plastics, wood, concrete, glass and metal materials and have excellent abrasion resistance, tensile strength, flexibility, durability and toughness And the use range thereof is gradually increasing.

In order to further improve the application of polyurethane, there have been various studies for providing water repellency on the surface of polyurethane. On the other hand, there is a problem that the pores contained in the polyurethane that provides the elasticity of the polyurethane provide a uniform surface of the polyurethane, and thus the difference in quality per batch in imparting water repellency to the polyurethane surface Various studies have been conducted to solve this problem.

Precedent patent

Korean Patent Publication No. 10-2016-0081474 (Jul. 08, 2016)

An object of the present invention is to provide a method for producing a polyurethane compression sponge having a water repellent surface capable of improving water repellency performance provided on a surface by having a polyurethane sponge as a whole having uniform mechanical strength through a pretreatment, To provide a compressed sponge.

Another object of the present invention is to provide a method for producing a polyurethane compression sponge having a water-repellent surface capable of providing an improved water-repellent ability on the surface of a polyurethane compressed sponge using a novel coating agent and a method and a polyurethane- .

According to one aspect of the present invention, embodiments of the present invention provide a method of manufacturing a polyurethane compression sponge, comprising the steps of: preparing the polyurethane sponge; A pressing step of pressing the polyurethane sponge with a polyurethane compression sponge by means of a compression processing device; An aging step of discharging the gas generated during the thermocompression bonding; And a surface treatment step of imparting functionality to the surface of the polyurethane compression sponge, wherein in the surface treatment step, the surface of the polyurethane compression sponge is coated with a super water-repellent coating agent so that the polyurethane compression sponge is super- Wherein the surface treatment step comprises the steps of: preparing an super water repellent coating agent; Spraying the super-water-repellent coating agent onto the surface of the polyurethane compression sponge; And drying the polyurethane compressed sponge to remove a solvent contained in the super water-repellent coating agent. The present invention also provides a method for producing a polyurethane compressed sponge having a water-repellent surface.

The water-repellent coating agent is prepared by dispersing a silica airgel powder in methanol at room temperature. The silica airgel powder is prepared by adding methanol to methyltriethoxysilane at room temperature, adding oxalic acid solution thereto, stirring the mixture for 30 to 50 minutes The mixture was stirred at room temperature for 24 hours, added with ammonium hydroxide solution and stirred for 10 minutes to 20 minutes, then methanol was added, followed by stirring for 5 minutes to homogenize to prepare a mixture, 110 DEG C and a rotation speed of 5,000 to 15,000 rpm using a centrifugal rotary atomizer.

1 to 49 parts by weight of an additive is mixed with 100 parts by weight of a polyurethane raw material for foaming to prepare a polyurethane foam composition, the polyurethane foam composition is injected into a sheet-shaped mold to prepare a sheet-shaped polyurethane sponge, Shaped polyurethane sponge is inserted into a metal mold and subjected to primary compression molding, and the polyurethane sponge having been subjected to the primary compression molding is punched by using a punching plate having a plurality of metal fins protruding therefrom to punch the polyurethane sponge, A polyurethane sponge having a hole formed therein is impregnated in the polyurethane foam composition and then inserted into a mold to perform secondary compression molding and aging the polyurethane sponge having undergone the secondary compression molding at room temperature And the polyurethane raw material for foaming is made of isocyanate and polyol And, the additive may be made of a blowing agent, surfactants, catalysts and fillers.

The isocyanate may be selected from the group consisting of methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate, toluene diisocyanate (TDI), hexamethylene diisocyanate, trimethyl But are not limited to, trimethyl hexamethylene diisocyanate, phenylene diisocyanate, dimethyl diphenyl diisocyanate, tetramethylene diisocyanate, isoholon diisocyanate, Diisocyanate, triphenyl methane triisocyanate, and mixtures thereof. The polyol is at least one compound selected from the group consisting of polyethylene glycol, polypropylene One kind of paper selected from the group consisting of phenols, polyglycols, amine-terminated polyethers, polytrimethylene ether glycols, polytrimethylene ether ester glycols, polytrimethylene-co-ethylene ether glycols, polytetramethylene ether glycols, Wherein the surfactant is a polyether siloxane, the foaming agent is water, and the filler is a cerium oxide having a diameter of 2.4 占 퐉, the catalyst is a tertiary amine type tetraethyldiamine, the surfactant is polyether siloxane, , Calcium carbonate (CaCO3) having a diameter of 6.1 mu m, silica having a diameter of 30 nm, carbon black (thermally conductive filler).

The sheet-shaped polyurethane sponge is inserted into a mold and subjected to the primary compression molding and the secondary compression molding, wherein the polyurethane sponge is preheated at 100 DEG C for 1 minute before inserting the mold, The polyurethane sponge was maintained in the mold for 1 minute without removing the mold by applying a pressure of 85 kg / cm < 2 > at 100 DEG C into a mold composed of an upper mold and a lower mold, A cold compression process is performed under a pressure of 150 kg / cm 2 at room temperature, and the polyurethane sponge can be maintained in the mold for one minute without removing the mold.

Wherein the polyurethane foam composition further comprises 5 to 12 parts by weight of the shape memory polyurethane fiber relative to 100 parts by weight of the polyurethane foam material for foam, wherein the shape memory polyurethane fiber is a mixture of N, N-dimethylacetate 4,4-methylene diphenyl isocyanate (MDI), an isocyanate in poly (N, N-dimethyl acetamide), polyol, polycaprolactone diol having a molecular weight (Mn) (caprolactone diol, PCL-diol), 1,4-butane diol (BD) as a chain extender, and dibutyltin dilaurate as a catalyst were synthesized and synthesized with a polyurethane polymer (MDI), polycaprolactone diol (PCL-diol) and 1,4-butanediol (BD) in a molar ratio of 4,4-methylenediphenyl diisocyanate May be 6: 1: 5.

Wherein the press working apparatus comprises a first press roll having a pattern formed on an outer surface thereof and a pair of first press rolls and at least one second press roll having a pair of smoothly formed outer faces and the second press rolls are sequentially provided, A second press roll, a second press roll, and a second press roll, wherein the polyurethane sponge is passed through the first press roll at room temperature and is provided on the outer surface of the first press roll The pattern is transferred to the outer surface of the polyurethane sponge by the pattern that is formed on the surface of the polyurethane sponge, and the polyurethane sponge on which the pattern is formed is preheated through the second-1 pressing roll at a temperature of 85 캜 to 95 캜, The sponge is compressed with a polyurethane compression sponge by thermocompression of the second-2 compression roll for a period of 3 seconds to 16 minutes at a temperature of 180 ° C to 230 ° C, Can be cooled by passing through the 2-3 compression roll at a temperature of 10 [deg.] C to 15 [deg.] C.

In the aging step, cold air of 10 ° C is sprayed with the polyurethane compression sponge for 1 hour to 2 hours, and after the injection is completed, the polyurethane compression sponge is kept in a chamber of 10 ° C for 3 hours, The compressed sponge can be aged at a humidity of 20 to 50%, a temperature of 20 to 30 ° C and a time of 48 to 90 hours.

Wherein the surface treatment step comprises coating a surface of the polyurethane compression sponge with a non-softening coating agent to provide the polyurethane compression sponge with a softening function, wherein the surface treatment step comprises: preparing a non-softening coating agent; Spraying the non-softening coating agent onto the surface of the polyurethane compression sponge; And drying the polyurethane compressed sponge.

The nonflammable coating agent is prepared by mixing 20 g of ammonium polyphosphate powder, 25 g of ammonium sulfate powder and 25 g of a polymeric dispersant, stirring the mixture at 300 rpm to 500 rpm for 30 minutes at an intermediate speed, 2 mixture, the mixture is stirred at a high speed of from 1500 rpm to 3000 rpm for 30 minutes, maintained at 5 DEG C for 12 hours, distilled water is added to the second mixture, and the mixture is stirred at an intermediate speed for 20 minutes at 300 rpm to 500 rpm have.

According to another aspect of the present invention, the present invention includes a polyurethane compression sponge made according to the method described above.

As described above, according to the present invention, there is provided a method of manufacturing a polyurethane compression sponge having a water repellent surface capable of improving the water repellency performance of the surface by having a uniform uniform mechanical strength through the pretreatment of the polyurethane sponge, The polyurethane compression sponge produced can be provided.

According to the present invention, there is also provided a method for producing a polyurethane compression sponge having a water repellent surface capable of providing an improved water-repellent ability on the surface of a polyurethane compression sponge using a novel coating agent and a method, and a polyurethane compression sponge produced thereby can do.

1 and 2 are photographs of a polyurethane compression sponge according to an embodiment of the present invention.
3 is a flowchart illustrating a method of manufacturing a polyurethane compression sponge according to an embodiment of the present invention.
Figure 4 is a flow chart illustrating the method of the surface treatment step of Figure 3;
5 is a view schematically showing first and second squeeze rolls used in the pressing step of Fig.
Fig. 6 is a view showing the first squeeze roll of Fig. 3;

The details of other embodiments are included in the detailed description and drawings.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described below, but may be embodied in various forms. In the following description, it is assumed that a part is connected to another part, But also includes a case in which other media are connected to each other in the middle. In the drawings, parts not relating to the present invention are omitted for clarity of description, and like parts are denoted by the same reference numerals throughout the specification.

Hereinafter, the present invention will be described with reference to the accompanying drawings.

1 and 2 are photographs of a polyurethane compression sponge according to an embodiment of the present invention. 3 is a flowchart illustrating a method of manufacturing a polyurethane compression sponge according to an embodiment of the present invention. Figure 4 is a flow chart illustrating the method of the surface treatment step of Figure 3; 5 is a view schematically showing first and second squeeze rolls used in the pressing step of Fig. Fig. 6 is a view showing the first squeeze roll of Fig. 3;

An embodiment of the present invention is a method of manufacturing a polyurethane compression sponge, comprising the steps of: preparing the polyurethane sponge; A pressing step of pressing the polyurethane sponge with a polyurethane compression sponge by means of a compression processing device; An aging step of discharging the gas generated during the thermocompression bonding; And a surface treatment step of imparting functionality to the surface of the polyurethane compression sponge.

In the surface treatment step, the surface of the polyurethane compression sponge may be coated with a super water-repellent coating agent to provide the polyurethane compression sponge with super water-repellent functionality.

Wherein the surface treatment step comprises: preparing an super water repellent coating agent; Spraying the super-water-repellent coating agent onto the surface of the polyurethane compression sponge; And drying the polyurethane compressed sponge to remove the solvent contained in the super water repellent coating agent.

Referring to FIGS. 1 and 2, the polyurethane compression sponge according to the present embodiment may be provided with super water-repellent function on the surface. Therefore, other liquids other than the water are simply retained without penetrating the polyurethane compression sponge, and the water flows down in the form of droplets on the surface of the polyurethane compression sponge, and water wettability is not generated. Accordingly, the polyurethane compression sponge according to the present embodiment can be applied to various applications such as cushion puffs in cosmetics as well as interior and exterior materials for construction.

The water-repellent coating agent is prepared by dispersing a silica airgel powder in methanol at room temperature. The silica airgel powder is prepared by adding methanol to methyltriethoxysilane at room temperature, adding oxalic acid solution thereto, stirring the mixture for 30 to 50 minutes The mixture was stirred at room temperature for 24 hours, added with ammonium hydroxide solution and stirred for 10 minutes to 20 minutes, then methanol was added, followed by stirring for 5 minutes to homogenize to prepare a mixture, 110 DEG C and a rotation speed of 5,000 to 15,000 rpm using a centrifugal rotary atomizer.

By preparing the silica airgel powder by the above-described method, the porosity included in the silica airgel powder can be improved and particles of smaller and uniform size can be produced. By coating the surface of the polyurethane compression sponge with an ultra water-repellent coating agent containing the silica airgel powder, the polyurethane compression sponge can be imparted with functionality to prevent water from being absorbed on the surface of the polyurethane compression sponge, Cushion, insulation, building interior and exterior materials, and so on.

The mixture may be spray dried with a centrifugal rotary atomizer at a temperature of 80 to 110 ° C and a rotation speed of 5,000 to 15,000 rpm. If the temperature is less than 80 ° C, the particle size of the prepared silica airgel powder is not uniform, Pores are unevenly distributed in the produced silica airgel powder particles. If the rotation speed is less than 5,000 rpm, the particle size becomes too large and a problem is caused. If the rotation speed is over 15,000 rpm, the particle size is small, but the particle size distribution of the silica airgel powder produced in the whole is formed in a wide range, Which causes a decrease in process efficiency.

The polyurethane compression sponge can be controlled in thickness by compression and can range from 0.3 mm to 150 mm. If the thickness of the polyurethane compression sponge is less than 0.3 mm, most of the pores in the polyurethane compression sponge are compressed, it is problematic because it does not have the elasticity of foam. When it is more than 150 mm, the thickness is too thick, its use is limited, and the polyurethane compression sponge is difficult to have a predetermined strength. Preferably, the polyurethane compression sponge has a thickness of 0.3 mm to 50 mm.

The density of the polyurethane compressed sponge may be 0.014 kg / ㎣ to 500 kg / 있는데. If it is less than 0.014 kg / 에는, the polyurethane compressed sponge is too easily deformed by external force and is difficult to be applied commercially reproducibly. Is lowered. Preferably, the density of the polyurethane compressed sponge may be between 250 kg / kg and 300 kg / kg.

In the preparation step, 100 parts by weight of polyurethane raw material for foaming is mixed with 1 to 49 parts by weight of an additive to prepare a polyurethane foam composition, and the polyurethane foam composition is injected into a sheet-shaped mold to form a polyurethane sponge The sheet-shaped polyurethane sponge is inserted into a metal mold and subjected to primary compression molding. The polyurethane sponge that has undergone the primary compression molding is punched out of the polyurethane sponge using a punching plate having a plurality of metal fins protruding therefrom. A plurality of holes are formed in the polyurethane sponge, a polyurethane sponge having a hole is impregnated in the polyurethane foam composition, and the resultant is inserted into a mold to be subjected to secondary compression molding, and a polyurethane sponge, which has been subjected to the secondary compression molding, ≪ / RTI >

In the preparing step, the polyurethane sponge is compressed so that the pressure is uniformly transferred to the polyurethane sponge before the compression sponge is manufactured, and the pore shape of the polyurethane sponge is deformed with respect to a strong external force, It is possible to prevent the elasticity from deteriorating.

The sheet-like polyurethane sponge is subjected to primary compression molding, and then the polyurethane sponge can be punched using a punching plate having a plurality of metal fingers projected thereon. The polyurethane sponge may be formed with a plurality of holes, and the polyurethane sponge having such holes may be impregnated into the polyurethane foam composition which is the raw material of the polyurethane sponge. The polyurethane foam composition is impregnated into the holes formed in the polyurethane sponge and partly coated on the outer surface of the polyurethane foam composition. As described above, the polyurethane sponge, which has been subjected to the secondary compression molding using the punching plate, has a higher density of the pores on the surface of the polyurethane sponge and improves the strength of the polyurethane sponge without increasing the thickness of the polyurethane sponge .

The polyurethane raw material for foaming is composed of an isocyanate and a polyol, and the additive may be composed of a foaming agent, a surfactant, a catalyst and a filler.

The isocyanate may be selected from the group consisting of methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate, toluene diisocyanate (TDI), hexamethylene diisocyanate, trimethyl But are not limited to, trimethyl hexamethylene diisocyanate, phenylene diisocyanate, dimethyl diphenyl diisocyanate, tetramethylene diisocyanate, isoholon diisocyanate, Naphthalene diisocyanate, triphenyl methane triisocyanate, and a mixture thereof. [0044] The term " a "

The polyol is selected from the group consisting of polyethylene glycol, polypropylene glycol, amine terminated polyether, polytrimethylene ether glycol, polytrimethylene ether ester glycol, polytrimethylene-co-ethylene ether glycol, polytetramethylene ether glycol, ≪ / RTI >

The catalyst may be a tertiary amine type tetraethyldiamine.

The surfactant includes not only a silicone surfactant but also a nonionic polyether surfactant. Silicone surfactants include commercially available polysiloxane / polyether copolymers such as Tegostab B-8462 and B-8404, Niax L-6900 and L -6910 surfactants and DC-198 and DC-5043 surfactants (Dow Corning).

Nonionic polyether surfactants include ethylene oxide / propylene oxide and ethylene oxide / butylene oxide block copolymer. The surfactant improves the miscibility by lowering the surface tension, uniformizes the size of the generated bubbles, and regulates the cell structure of the foamed composite to impart stability to the foamed composite.

Preferably, the surfactant is a polyether siloxane.

The polyether siloxane improves the miscibility by lowering the surface tension of the silicone system, disperses the components finely and uniformly, generates a plurality of uniform bubbles, blocks the aggregation of bubbles, cell.

The foaming agent is preferably water. In addition to water, the foaming agent may be used in combination with the above-mentioned water and a foaming agent. Examples of the blowing agent other than water include n-pentane, isopentane, cyclopentane, methylene chloride, 1,1,1,2-tetrafluoroethane, 1,1,1,3,3-pentafluoropropane , 1,1,1,3,3-pentafluorobutane, 1,1-dichloro-1-fluoroethane, 1-chloro-1,1-difluoroethane and chlorodifluoromethane have.

The filler may be added to improve the physical properties of the polyurethane compression sponge. The filler may include at least one of cerium oxide having a diameter of 2.4 占 퐉, calcium carbonate (CaCO3) having a diameter of 6.1 占 퐉, silica having a diameter of 30 nm, and carbon black (heat conductive filler).

The cerium oxide has a hardness higher than that of the polyurethane resin, and when added to the polyurethane resin composition, the hardness of the entire polyurethane sponge formed of the polyurethane resin composition is increased. On the other hand, when the content of the cerium oxide is excessively increased, the compressive strength and the hardness are greatly increased, so that the surface of the polyurethane compression sponge may be cracked due to the compression of the sponge.

The polyurethane raw material for foaming is composed of isocyanate and polyol. The isocyanate may be included in an amount of 55 to 65 parts by weight based on 100 parts by weight of the polyol. When the content of isocyanate is less than 55 parts by weight, the crosslinking density is too low to have low compressive strength and mechanical strength. When the amount of isocyanate exceeds 65 parts by weight, the crosslinking density becomes high and the elasticity is lowered. It is difficult to form it in a thickness.

Preferably, the additive may comprise from 4 to 8 parts by weight of blowing agent, from 1 to 2 parts by weight of surfactant, from 1 to 2 parts by weight of catalyst and from 0.5 to 47.5 parts by weight of filler based on 100 parts by weight of polyurethane raw material for foaming .

The additive is added based on 100 parts by weight of the raw polyurethane foam. When the amount of the blowing agent is less than 4 parts by weight, the pore size is not uniformly formed. When the amount is more than 8 parts by weight, the compressive strength is lowered. The surfactant and the catalyst should be present in the above-mentioned amounts so that the polymerization reaction of the polyurethane raw material for foaming can be performed smoothly without any excess. If the amount of the filler is less than 0.5 parts by weight, the function of the filler is not sufficiently exhibited. If the amount of the filler exceeds 47.5 parts by weight, the compression strength, hardness and density of the polyurethane compression sponge are too large, The process is not easy and is problematic.

The sheet-shaped polyurethane sponge is inserted into a mold and subjected to the primary compression molding and the secondary compression molding, wherein the polyurethane sponge is preheated at 100 DEG C for 1 minute before inserting the mold, The polyurethane sponge was maintained in the mold for 1 minute without removing the mold by applying a pressure of 85 kg / cm < 2 > at 100 DEG C into a mold composed of an upper mold and a lower mold, A cold compression process is performed under a pressure of 150 kg / cm 2 at room temperature, and the polyurethane sponge can be maintained in the mold for one minute without removing the mold.

The polyurethane sponge can be more precisely controlled in the process of compressing and molding the polyurethane sponge in the form of a sheet preliminarily in a mold to control the thickness and strength by subsequent pressing. In addition, uniform quality can be ensured so as not to cause a difference in physical properties between batches or workers in the process of producing a large quantity of products.

In the process of inserting the sheet-shaped polyurethane sponge into a mold and performing the primary compression molding and the secondary compression molding, the polyurethane sponge is preheated at 100 DEG C for 1 minute to heat the polyurethane sponge as a whole So that it is possible to prevent the surface from being preferentially deformed by direct contact with the metal mold.

The polyurethane sponge may be charged into a mold made of an upper mold and a lower mold to perform a heat compression process. At this time, the thickness of the polyurethane sponge as a final target and the thickness of the polyurethane sponge It is preferable that only 25% to 35% of the thickness reduction ratio is reduced in thickness.

Also, by keeping the polyurethane sponge in the mold for one minute without removing the mold, the polyurethane sponge is not exposed to a sudden low temperature and the polyurethane sponge texture is aligned and partial heat is concentrated The physical properties of the polyurethane sponge can be improved.

Then, the polyurethane sponge was subjected to a cold compression process under a pressure of 150 kg / cm < 2 > at room temperature, and kept for 1 minute without removing the mold, thereby compressing the polyurethane sponge The compressed form can be fixed.

Alternatively, the polyurethane foam composition may further comprise 5 to 12 parts by weight of the shape memory polyurethane fiber per 100 parts by weight of the polyurethane foam material.

The shape memory polyurethane fiber is prepared by mixing 4,4-methylene diphenyl isocyanate (MDI), an isocyanate, in a solvent, N, N-dimethyl acetamide, Poly (caprolactone diol), PCL-diol) having a molecular weight Mn of 4000 g / mol, 1,4-butane diol (BD) as a chain extender and dibutyltin Dibutyltin dilaurate is added and synthesized as a polyurethane polymer and then melt-spun using an extruder to produce an undrawn yarn.

The molar ratio of 4,4-methylenediphenyl diisocyanate (MDI) to polycaprolactone diol (PCL-diol) and 1,4-butanediol (BD) may be 6: 1: 5.

When the shape memory polyurethane fiber is contained in an amount of less than 5 parts by weight based on 100 parts by weight of the polyurethane foam material, the effect of the shape memory polyurethane fibers is insignificant. When the amount exceeds 12 parts by weight, It is difficult to form a uniform thickness in the process of forming into a sheet.

The polyurethane foam composition further includes shape memory polyurethane fibers so that even after compression molding to a thin thickness, flexural stiffness can be improved flexibly even though it is high in strength, and the elasticity of the polyurethane compression sponge can be improved to improve durability . Further, by further including the shape memory polyurethane fiber, even if the thickness of the polyurethane compression sponge is made thinner, it is possible to have the same or higher strength as the conventional one.

In the pressing step, the polyurethane sponge can be processed with a polyurethane pressing sponge by means of the crimping apparatus 100. The squeezing apparatus 100 may include a first squeezing roll 110 having a pattern formed on its outer surface and a pair of first squeezing rolls 120 having a smooth outer surface and a pair of squeezing rolls. The second squeezing roll 120 may include a second squeezing roll 121, a second squeezing roll 122, and a second squeezing roll 123, which are sequentially provided and have the same shape. have.

The polyurethane sponge 10 is passed through the first squeezing roll 110 at a normal temperature and is pressed against the surface of the polyurethane sponge 10 by the patterns 111 and 112 provided on the outer surface of the first squeezing roll 110. [ The pattern is transferred to the outer surface. Then, the polyurethane sponge 10 on which the pattern is formed is preheated through the second-1 pressing roll 120 at a temperature of 85 ° C to 95 ° C, and the preheated polyurethane sponge 10 is heated Pressed with a polyurethane compression sponge by thermocompression of the second-2 compression roll 120 at a temperature of 230 DEG C for 3 seconds to 16 minutes, and the polyurethane compression sponge is compressed at a temperature of 10 DEG C to 15 DEG C 2-3 can be cooled through the press roll 123.

The polyurethane sponge 10 is formed by sequentially pressing the first pressing roll 110, the second-1 pressing roll 121, the second-2 pressing roll 122, and the second- 3 While passing through the press roll 123, a process of pattern formation, preheating, hot pressing, and cooling can be performed.

 The compression bonding apparatus 100 is configured such that the polyurethane sponge 10 has a predetermined thickness and strength, preferably a thickness of 0.3 mm to 150 mm and a density of 0.014 kg / cm 2 to 500 kg / (10) can be crimped. The squeezing device 100 comprises a first squeezing roll 100, a second squeezing roll 121, a second squeezing roll 122 and a second squeezing roll 123, and the polyurethane sponge 10 is pressed through the pressing and forming apparatus 100 in order from the second pressing roll 100. The squeezing apparatus 100 may further include a pair of winding rolls 130 provided at a front end of the first squeezing roll 110 and a rear end of the second squeezing roll 123, . The winding roll 130 can support the polyurethane sponge 10 such that the polyurethane sponge 10 easily passes through the first squeezing roll 110 and the second squeezing roll 120. [

A pattern may be formed on the outer surface of the first pressing roll 110. The pattern formed on the first press roll 110 may be recessed inwardly in a regular shape. For example, the pattern of the first squeezing roll 110 may be provided on a surface of the first squeezing roll 110 on which the polyurethane sponge 10 is pressed, and may include an inwardly recessed groove 111 and a flat surface 112, A plurality of such patterns may be provided in a pattern of a constant shape. The outer surface of the polyurethane sponge 10 passing through the first squeezing roll 110 may be provided with an embossed pattern so as to have the same pattern as the pattern provided on the outer surface of the first squeezing roll 110.

The pattern is first formed by the first squeezing roll 110 before the heat is applied to the polyurethane sponge 10 so that the thermal stress is applied to the polyurethane sponge 10 in the second squeezing roll 120, Pressure and heat are applied to the polyurethane sponge 10, and at the same time, the compression process can be performed so that the physical properties of the polyurethane sponge 10 are uniformly provided as a whole.

The polyurethane sponge 10 can be preheated by passing through the second-1 pressing roll 121 to heat the polyurethane sponge 10 uniformly as a whole. The polyurethane sponge 10, which has been preheated by the second-2 squeeze roll 122, may be compressed with a high temperature while being compressed to be provided with a polyurethane compression sponge. By preheating the polyurethane sponge 10 through the second-1 squeeze roll 121, the high-temperature heat is prevented from concentrating only on the central portion of the polyurethane sponge 10, and the polyurethane sponge 10 Can be prevented.

The polyurethane compression sponge may then be passed through a second to third press roll 123 to cool the outer surface. By compressing the polyurethane compression sponge squeezed at a high temperature through the 2-3 compression roll 123, the structure of the outer surface of the polyurethane compression sponge is densely provided so that the surface strength of the polyurethane compression sponge Can be improved.

In the aging step, cold air of 10 ° C is sprayed with the polyurethane compression sponge for 1 hour to 2 hours, and after the injection is completed, the polyurethane compression sponge is kept in a chamber of 10 ° C for 3 hours, The compressed sponge can be aged at a humidity of 20 to 50%, a temperature of 20 to 30 ° C and a time of 48 to 90 hours.

In the aging step, the polyurethane compression sponge maintains the compressed shape, while relieving the stress applied to the polyurethane compression sponge in the compression step and discharging the gas, thereby further improving the physical properties of the polyurethane compression sponge have. In the aging step, cold air of 10 ° C is injected for 1 hour to 2 hours, thereby allowing cool air to flow into the pores existing in the polyurethane compression sponge, thereby discharging the carbon dioxide generated in the compression step to the outside And also to cool the outer periphery of the pores. After completion of the cold air injection, the polyurethane compression sponge can be maintained in a chamber at 10 DEG C for 3 hours to allow the gas to be completely removed. The polyurethane compressed sponge can be aged at a humidity of 20 to 50%, at a temperature of 20 to 30 ° C, and at a time of 48 to 90 hours.

According to another aspect of the present invention, in the surface treatment step, a non-softening coating agent is coated on the surface of the polyurethane compression sponge after the super water-repellent functionality is provided, so that the polyurethane- . The non-softening coating agent may be coated after coating the super-water-repellent coating agent, or the super-water-repellent coating agent may be coated on one surface of the polyurethane compression sponge, and the non-softening coating agent may be coated on the other surface of the polyurethane compression sponge.

Wherein the surface treatment step comprises the steps of: preparing an unfired coating agent; Spraying the non-softening coating agent onto the surface of the polyurethane compression sponge; And drying the polyurethane compressed sponge.

The nonflammable coating agent is prepared by mixing 20 g of ammonium polyphosphate powder, 25 g of ammonium sulfate powder and 25 g of a polymeric dispersant, stirring the mixture at 300 rpm to 500 rpm for 30 minutes at an intermediate speed, 2 mixture, the mixture is stirred at a high speed of from 1500 rpm to 3000 rpm for 30 minutes, maintained at 5 DEG C for 12 hours, distilled water is added to the second mixture, and the mixture is stirred at an intermediate speed for 20 minutes at 300 rpm to 500 rpm have.

According to another aspect of the present invention, the present invention includes a polyurethane compression sponge produced by the method described above.

Hereinafter, examples and comparative examples of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the scope of the present invention is not limited by the following examples.

1. Preparation of Examples and Comparative Examples

Example 1

(1) Material

The polyisocyanate is a crude MDI (CMDI) having an NCO content of 28% in an industrial grade polymeric MDI and the polyol has a hydroxyl value OH value) of 56 was used. At this time, the functionality of the polyol having a hydroxyl value of 56 is 3. As the catalyst, tetraethyldiamine, which is a tertiary amine, and polyether siloxane, which is a surfactant, were used. The average particle size of the cerium oxide used as the filler was 2.4 占 퐉. Table 1 shows the materials used in Example 1.

division Rating Content (g) Isocyanate crude MDI (CMDI) 550 Polyol OH value: 56
molecular weight: 3000
functionality: 3 1000 Surfactants polyether siloxane 30 catalyst 테트라ethyldiamine 30 blowing agent water 80 filler cerium oxide (2.4 탆) 100

 (2) Manufacturing

The polyol, the catalyst, the surfactant, the foaming agent and the filler cerium oxide were mixed at 3000 rpm for 2 minutes using a high shear mixer at room temperature according to the defined contents shown in Table 1. After that, isocyanate was added and the mixing speed was increased at 4000 rpm and mixed again for 30 seconds to prepare a polyurethane foam composition. Only 50% by weight of the prepared polyurethane foam composition was put into a mold and foam-cured at 60 DEG C for 6 hours to prepare a polyurethane sponge in the form of a sheet having a thickness of 100 mm. The prepared sheet-like polyurethane sponge was placed in an oven and preheated at 100 ° C for 1 minute. The mold was then placed in a mold, and a pressure of 85 kg / cm 2 was applied at 100 ° C., and the upper mold was separated from the lower mold with the heat and pressure removed And maintained for 1 minute. After applying 150 kg / cm2 pressure to the room temperature, the mold was kept for 1 minute without being separated, and primary compression molding was performed. Then, the dried polyurethane sponge was uniformly punched uniformly with a punching plate having protruding metal pins, impregnated with the remaining polyurethane foam composition (50% by weight), placed in an oven, and dried at 60 ° C for 6 hours And was foam-cured. Subsequently, the resultant was inserted again into a mold and subjected to secondary compression molding in the same manner as in the above-described primary compression molding method so as to have a thickness of 70 mm, followed by aging at room temperature. The produced polyurethane sponge was subjected to the squeezing apparatus shown in Figs. 4 and 5, passed through a first squeeze roll at room temperature, passed through a second-1 squeeze roll heated to 90 ° C, -2 compression roll and passed through a 2-3 compression roll at a temperature of 15 캜 to produce a polyurethane compression sponge having a thickness of 10 mm.

Example 2

A polyurethane compression sponge was prepared by adding an inorganic filler such as calcium carbonate (CaCO3) having an average particle size of 6.1 mu m instead of cerium oxide as a filler in Table 1,

Example 3

100 g of methyltrimethoxysilane and 974.0 g of methanol were added at room temperature, and the mixture was stirred for 5 minutes. Then, 50 g (0.1 g) of oxalic acid solution was further added thereto, stirred for 30 minutes, and left at room temperature for 24 hours. To this, 61 g (11.2 M) of an ammonium hydroxide solution was further added, stirred for 15 minutes, and left at room temperature for 48 hours. Again, 10 g of methanol was mixed and homogenized for 5 minutes to prepare a mixture. Silica airgel powder was prepared by using a centrifugal rotary atomizer at a nozzle outlet temperature of 65 ° C, a drying chamber (chamber temperature) of 95 ° C, and a rotation speed of 9,000 rpm in a stirred state. 50 g of the prepared silica airgel powder was dispersed in 100 g of methanol to prepare an super water-repellent coating agent.

The polyol, the catalyst, the surfactant, the foaming agent and the filler cerium oxide were mixed at 3000 rpm for 2 minutes using a high shear mixer at room temperature according to the defined contents shown in Table 1. After that, isocyanate was added and the mixing speed was increased at 4000 rpm and mixed again for 30 seconds to prepare a polyurethane foam composition. Only 50% by weight of the prepared polyurethane foam composition was put into a mold and foam-cured at 60 DEG C for 6 hours to prepare a polyurethane sponge in the form of a sheet having a thickness of 100 mm. The prepared sheet-like polyurethane sponge was placed in an oven and preheated at 100 ° C for 1 minute. The mold was then placed in a mold, and a pressure of 85 kg / cm 2 was applied at 100 ° C., and the upper mold was separated from the lower mold with the heat and pressure removed And maintained for 1 minute. After applying 150 kg / cm2 pressure to the room temperature, the mold was kept for 1 minute without being separated, and primary compression molding was performed. Then, the dried polyurethane sponge was uniformly punched uniformly with a punching plate having protruding metal pins, impregnated with the remaining polyurethane foam composition (50% by weight), placed in an oven, and dried at 60 ° C for 6 hours And was foam-cured. Subsequently, the resultant was inserted again into a mold and subjected to secondary compression molding in the same manner as in the above-described primary compression molding method so as to have a thickness of 70 mm, followed by aging at room temperature. The produced polyurethane sponge was subjected to the squeezing apparatus shown in Figs. 4 and 5, passed through a first squeeze roll at room temperature, passed through a second-1 squeeze roll heated to 90 ° C, -2 compression roll and passed through a 2-3 compression roll at a temperature of 15 캜 to produce a polyurethane compression sponge having a thickness of 10 mm. The polyurethane compressed sponge was sprayed with a water repellent coating agent on one side and the other side, respectively, and then methanol was removed by drying at room temperature for 24 hours.

Example 4

20 g of ammonium polyphosphate powder, 25 g of ammonium sulfate powder and 1.75 g of a high molecular weight dispersant, Solsperse 20000 (manufactured by Nippon Lubrizol Corporation) were stirred at 400 rpm for 30 minutes and then mixed with 7.5 g of 25% by weight aqueous ammonia at 1500 rpm Lt; / RTI > Then, it was kept at 5 캜 in a cool place for 12 hours. Immediately before use, 445.75 g of distilled water was added and diluted by stirring at 300 rpm for 20 minutes to prepare an unfavorable coating agent.

The polyol, the catalyst, the surfactant, the foaming agent and the filler cerium oxide were mixed at 3000 rpm for 2 minutes using a high shear mixer at room temperature according to the defined contents shown in Table 1. After that, isocyanate was added and the mixing speed was increased at 4000 rpm and mixed again for 30 seconds to prepare a polyurethane foam composition. Only 50% by weight of the prepared polyurethane foam composition was put into a mold and foam-cured at 60 DEG C for 6 hours to prepare a polyurethane sponge in the form of a sheet having a thickness of 100 mm. The prepared sheet-like polyurethane sponge was placed in an oven and preheated at 100 ° C for 1 minute. The mold was then placed in a mold, and a pressure of 85 kg / cm 2 was applied at 100 ° C., and the upper mold was separated from the lower mold with the heat and pressure removed And maintained for 1 minute. After applying 150 kg / cm2 pressure to the room temperature, the mold was kept for 1 minute without being separated, and primary compression molding was performed. Then, the dried polyurethane sponge was uniformly punched uniformly with a punching plate having protruding metal pins, impregnated with the remaining polyurethane foam composition (50% by weight), placed in an oven, and dried at 60 ° C for 6 hours And was foam-cured. Subsequently, the resultant was inserted again into a mold and subjected to secondary compression molding in the same manner as in the above-described primary compression molding method so as to have a thickness of 70 mm, followed by aging at room temperature. The produced polyurethane sponge was subjected to the squeezing apparatus shown in Figs. 4 and 5, passed through a first squeeze roll at room temperature, passed through a second-1 squeeze roll heated to 90 ° C, -2 compression roll and passed through a 2-3 compression roll at a temperature of 15 캜 to produce a polyurethane compression sponge having a thickness of 10 mm. The polyurethane compressed sponge was sprayed sufficiently with a spray on one side and the other side of the sponge, and then dried at room temperature for 24 hours.

Comparative Example 1

The polyol, the catalyst, the surfactant, the foaming agent and the filler cerium oxide were mixed at 3000 rpm for 2 minutes using a high shear mixer at room temperature according to the defined contents shown in Table 1. After that, isocyanate was added and the mixing speed was increased at 4000 rpm and mixed again for 30 seconds to prepare a polyurethane foam composition. Only 50% by weight of the prepared polyurethane foam composition was put into a mold and foam-cured at 60 DEG C for 6 hours to prepare a polyurethane sponge in the form of a sheet having a thickness of 100 mm. Subsequently, the polyurethane sponge was repeatedly reciprocated several times by a press roll at a temperature of 200 캜 to prepare a polyurethane compressed sponge having a thickness of 10 mm.

Comparative Example 2

A polyurethane compressed sponge was prepared in the same manner as in Example 1, except that cerium oxide was omitted from the materials listed in Table 1.

2. Evaluation

density

A 20 mm x 20 mm x 25 mm specimen was prepared according to ASTM 3489 for the polyurethane compression sponge prepared according to Examples and Comparative Examples, and the density was measured. The results are shown in Table 2 and Fig.

The tensile strength

The tensile strength of the polyurethane compression sponge prepared according to Examples and Comparative Examples was measured using UTM (universal resting machine, Instron Series IX) after preparing samples according to ASTM 412 method. The tensile strength was measured at a sample rate of 10 pts / sec, a crosshead speed of 50 mm / min, and a full scale load range of 50 kgf. Five specimens were measured for each specimen. And the tensile strength of the polyurethane compression sponge was measured. The results are shown in Table 2 and FIG. 6.

Thermal conductivity

The thermal conductivity of the polyurethane compression sponge prepared according to the examples and the comparative examples was measured by a plate hot-pressing method. The size of the sample was 200 × 200 × 20 mm, and the results are shown in Table 2 and FIG. 6 .

Water contact angle

Water droplets were dropped on the surface of a polyurethane compressed sponge prepared according to Examples and Comparative Examples, and this was magnified by an optical lens and then measured using a scale line. At this time, the angle formed by the line connecting the edge of the liquid and the top of the liquid and the projected surface of the solid was confirmed as the water contact angle. Each specimen was measured five times, and the average value of the remaining values except for the minimum value and the maximum value was obtained.

Evaluation of unflammability

The polyurethane compressed sponge prepared according to Examples and Comparative Examples was fixed to a wire net and the flame was sprayed for 30 seconds at a high calorie 1300 占 폚 gas burner toward the sample. The distance from the sample to the gas burner port was about 90 mm.

3. Results

Table 2 and FIG. 6 show the results of evaluation of density, tensile strength and thermal conductivity according to Examples and Comparative Examples of the present invention.

density The tensile strength Thermal conductivity Inflammation Example 1 142㎏ / ㎣ 22Mpa 0.05 kcal / mh Ignition loss from 12 seconds Example 2 155㎏ / ㎣ 18 MPa 0.039 kcal / mh Ignition loss from 10 seconds Implementation 3 164㎏ / ㎣ 27Mpa 0.045 kcal / mh Ignition loss from 22 seconds Implementation 4 161㎏ / ㎣ 23Mpa 0.056 kcal / mh No ignition Comparative Example 1 70㎏ / ㎣ 10 MPa 0.041 kcal / mh Ignition loss from 8 seconds Comparative Example 2 110㎏ / ㎣ 12Mpa 0.028 kcal / mh Ignition loss from 11 seconds

Referring to Table 2, it can be seen that the density is similar to that of Examples 1 and 2 and Comparative Example 3, but that Comparative Example 1 has a low value. In Comparative Example 1, the density of the filler, cesium oxide, It was confirmed that the density of the polyurethane compressed sponge was affected in the process of producing the sponge without significant effect. Further, it can be confirmed that the density of Example 2 is slightly higher than that of Examples 1 and 2 because even if the filler contains cesium oxide and calcium carbonate in the same amount, the pores of the polyurethane foam sponge are smaller As shown in Fig. Comparing Example 1 with Examples 3 and 4, it can be seen that the use of cesium oxide, which is the same filler, is larger in Examples 3 and 4 than in Example 3 and Example 4, in which the super water-repellent coating agent and the non- It was judged that the coating was penetrated into the pores inside the polyurethane compression sponge while being coated.

It can be seen that the tensile strength of Example 1 is higher than that of 2, which is considered to be due to the fact that cesium oxide forms more uniform and smaller pores in the process of foaming polyurethane than calcium carbonate. Comparing Example 1 with Comparative Example 1, it can be seen that the tensile strength can be influenced not only by the effect of the filler but also by the process of making the compressed sponge. Comparing Example 1 with Examples 3 and 4, it can be seen that Examples 3 and 4 have higher tensile strength than Example 1. This means that in Examples 3 and 4, super-water-repellent It is judged that the tensile strength is improved by coating the coating agent and the non-softening coating agent.

When the thermal conductivity was examined, it was confirmed that Comparative Example 2 was the lowest, indicating that no filler was added. Comparing Example 1 and Example 2, it was confirmed that the performance against thermal conductivity was slightly better when cesium oxide was added. Comparing Example 1 with Examples 3 and 4, it can be confirmed that the thermal conductivity of Example 1 is higher than that of Example 1 even though the same cesium oxide is contained. This is because the surface of Embodiment 3 is coated with the super water- , And Example 4 was coated with the non-softening coating agent and had a thermal conductivity higher than 1 in the embodiment.

Comparing Example 1 and Example 3, it can be confirmed that the outer surface has the same shape because the silica airgel contained in the super water-repellent coating agent of Example 3 is transparent, so that the super water-repellent coating agent is also transparent, And it was confirmed that it did not affect the appearance. As a result of checking the contact angle with water (Static Contact Angle of water droplet), Example 1 and Example 3 were 132 ° and 168 °, respectively. In general, when the contact angle with the water droplet is 150 ° to 170 °, it is a super water repellent surface. Therefore, it can be confirmed that Example 3 has a super water repellent surface by coating the super water repellent coating agent.

Referring to Table 2, it can be confirmed that only the Example 4 was ignited in the unflammability evaluation, which is judged from the fact that the surface of Example 4 was coated with the non-softening coating agent. It was found that the silk was contained in the super water-repellent coating agent, and the silk was contained in the super water-repellent coating agent.

It will be understood by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. The scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning and scope of the claims and the equivalents thereof are included in the scope of the present invention Should be interpreted.

10: Polyurethane Sponge
100: Crimping device
110: first squeeze roll
120: second squeeze roll

Claims (9)

CLAIMS 1. A method of making a polyurethane compressed sponge,
Preparing a polyurethane sponge;
A pressing step of pressing the polyurethane sponge with a polyurethane compression sponge by means of a compression processing device;
An aging step of discharging the gas generated in the pressing step; And
And a surface treatment step of providing functionality to the surface of the polyurethane compression sponge,
Wherein the surface treatment step comprises coating the surface of the polyurethane compression sponge with a super water repellent coating agent to provide the polyurethane compression sponge with super water repellent functionality,
Wherein the surface treatment step comprises:
Preparing a super water repellent coating agent;
Spraying the super-water-repellent coating agent onto the surface of the polyurethane compression sponge;
And drying the polyurethane compression sponge to remove the solvent contained in the super water-repellent coating agent,
The super water-repellent coating agent is prepared by dispersing a silica airgel powder at a room temperature in methanol,
Methanol was added to methyltriethoxysilane at room temperature and mixed. Then, an oxalic acid solution was added, and the mixture was stirred for 30 minutes to 50 minutes,
Allowed to stand at room temperature for 24 hours,
Ammonium hydroxide solution was added and stirred for 10 minutes to 20 minutes, then methanol was added, followed by homogenization for 5 minutes to prepare a mixture,
The mixture was spray-dried using a centrifugal rotary atomizer at 80 to 110 ° C and a rotation speed of 5,000 to 15,000 rpm,
In the preparation step,
A polyurethane foam composition is prepared by mixing an additive with a polyurethane raw material for foaming,
The polyurethane foam composition is injected into a sheet-shaped mold to prepare a sheet-like polyurethane sponge,
The sheet-form polyurethane sponge is inserted into a metal mold, subjected to primary compression molding,
The polyurethane sponge having been subjected to the primary compression molding is punched by using a punching plate having a plurality of metal fins protruded to form a plurality of holes in the polyurethane sponge,
A polyurethane sponge having a hole formed therein is impregnated in the polyurethane foam composition, and the resultant is inserted into a mold to perform secondary compression molding,
Aging the polyurethane sponge having undergone the secondary compression molding at room temperature,
Wherein the polyurethane raw material for foaming is made of isocyanate and polyol, and the additive has a water repellent surface composed of a foaming agent, a surfactant, a catalyst and a filler. delete delete The method according to claim 1,
The isocyanate may be selected from the group consisting of methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate, toluene diisocyanate (TDI), hexamethylene diisocyanate, trimethyl But are not limited to, trimethyl hexamethylene diisocyanate, phenylene diisocyanate, dimethyl diphenyl diisocyanate, tetramethylene diisocyanate, isoholon diisocyanate, A compound selected from the group consisting of naphthalene diisocyanate, triphenyl methane triisocyanate, and mixtures thereof,
The polyol is selected from the group consisting of polyethylene glycol, polypropylene glycol, amine terminated polyether, polytrimethylene ether glycol, polytrimethylene ether ester glycol, polytrimethylene-co-ethylene ether glycol, polytetramethylene ether glycol, And one species selected from the group consisting of
The catalyst is a tertiary amine-based tetraethyldiamine,
The surfactant is a polyether siloxane,
Wherein the foaming agent is water,
The filler comprises at least one of cerium oxide having a diameter of 2.4 占 퐉, calcium carbonate (CaCO3) having a diameter of 6.1 占 퐉, silica having a diameter of 30 nm, and carbon black (heat conductive filler)
In the polyurethane raw material for foaming, the isocyanate is contained in an amount of 55 to 65 parts by weight based on 100 parts by weight of the polyol,
A polyurethane compressed sponge having a water repellent surface consisting of 4 to 8 parts by weight of a blowing agent, 1 to 2 parts by weight of a surfactant, 1 to 2 parts by weight of a catalyst and 0.5 to 47.5 parts by weight of a filler, based on 100 parts by weight of the polyurethane raw material for foaming ≪ / RTI > 5. The method of claim 4,
The sheet-shaped polyurethane sponge is inserted into a metal mold to perform the primary compression molding and the secondary compression molding,
The polyurethane sponge was preheated at 100 占 폚 for 1 minute before the mold was inserted,
The pre-heated polyurethane sponge was placed in a mold composed of an upper mold and a lower mold, and a heat compression process was performed by applying a pressure of 85 kg / cm < 2 > at 100 DEG C,
Maintaining the polyurethane sponge in the mold for one minute without removing the mold,
A cold compression process was performed under a pressure of 150 kg / cm < 2 > at room temperature,
And a water repellent surface for retaining the polyurethane sponge in the mold for one minute without removing the mold. The method according to claim 1,
The polyurethane foam composition further comprises 5 to 12 parts by weight of the shape memory polyurethane fiber relative to 100 parts by weight of the polyurethane raw material for foaming,
The shape-memory polyurethane fiber is characterized in that,
4,4-methylene diphenyl isocyanate (MDI), a polyol having a molecular weight (Mn) of 4000 g / m < 2 > in N, N-dimethyl acetamide, (dibutyltin dilaurate), which is a chain extender, and 1,4-butane diol (BD), which are catalysts, and poly And synthesized as a polyurethane polymer,
Is produced as an unstretched yarn through melt spinning using an extruder,
A polyurethane compressed sponge having a water repellent surface in a molar ratio of 4,4-methylenediphenyl diisocyanate (MDI) to polycaprolactone diol (PCL-diol) and 1,4-butanediol (BD) of 6: ≪ / RTI > The method according to claim 1,
Wherein the press working apparatus comprises a first press roll having a pattern formed on an outer surface thereof and a pair of first press rolls and at least one second press roll having a pair of smoothly formed outer faces and the second press rolls are sequentially provided, A second-2 squeeze roll, and a second squeeze roll,
The pattern of the polyurethane sponge is transferred to the outer surface of the polyurethane sponge by a pattern provided on the outer surface of the first squeeze roll at a room temperature through the first squeezing roll,
The patterned polyurethane sponge is preheated through the second-1 squeeze roll at a temperature of 85 캜 to 95 캜,
The preheated polyurethane sponge is compressed with a polyurethane compression sponge by thermocompression of the second-2 compression roll at a temperature of 180 ° C to 230 ° C,
Wherein said polyurethane compression sponge has a water repellent surface that is cooled by passing through said 2-3 compression roll at a temperature of 10 占 폚 to 15 占 폚. The method according to claim 1,
In the aging step,
Cold air at 10 DEG C for 1 hour to 2 hours was sprayed with the polyurethane compression sponge,
After the injection was completed, the polyurethane compressed sponge was held in a chamber at 10 DEG C for 3 hours,
Wherein the polyurethane compressed sponge has a water repellent surface aged at a humidity of 20 to 50%, a temperature of 20 to 30 ° C, and a time of 48 to 90 hours. 9. A polyurethane compressed sponge produced according to any one of claims 1 to 8.

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