WO2017142244A1 - Method and apparatus for manufacturing composite sheet comprising aerogel sheet - Google Patents

Abstract

The present invention relates to a method for manufacturing a composite sheet comprising an aerogel sheet. The method may comprise the steps of: preparing an aerogel sheet (30) (S10); laminating fiber sheets (10) on both sides of the aerogel sheet (30), respectively (S20); and bonding the laminated aerogel sheet (30) and fiber sheets (10) by heat and pressure to manufacture a composite sheet (40) having the fiber sheet (10), the aerosol sheet (30), and the fiber sheet (10) laminated in sequence (S30).

Description

Composite sheet manufacturing method and apparatus including airgel sheet

Citation with Related Applications

This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0019833 dated February 19, 2016 and Korean Patent Application No. 10-2016-0095254 dated July 27, 2016. All content disclosed in the literature is included as part of this specification.

Technical Field

The present invention relates to a composite sheet manufacturing method and manufacturing apparatus comprising an airgel sheet, and more particularly, to a composite sheet manufacturing method and manufacturing apparatus comprising an airgel sheet having excellent heat insulation and durability and uniform thickness.

In general, aerogel sheet is a highly porous material having a high porosity of 90% or more and up to 99% of the solids known to date.The gel is prepared by sol-gel polymerization of a silica precursor solution and then under supercritical or atmospheric pressure conditions. Obtained by drying. That is, the airgel sheet has a pore structure filled with air.

Such airgel sheet has lightness and heat insulation, sound absorption, etc. due to its unique pore structure in which 90-99% of the interior space is empty, and the biggest advantage is 36mW / mk, which is the thermal conductivity of organic insulation materials such as styrofoam. It is a high thermal insulation with a thermal conductivity of less than 30mW / mk significantly lower.

The airgel sheet according to the prior art has a high raw material cost and manufacturing cost in spite of excellent thermal conductivity, and in particular, there is a limit to increasing the thickness due to the limitation of the manufacturing method. In other words, when the airgel sheets are laminated in multiple layers, an air layer is formed due to incomplete bonding between the airgel sheets, and thus there is a problem in that thermal conductivity and durability are reduced.

The present invention has been invented to solve the above problems, an object of the present invention is to laminate the airgel sheet and fiber sheet to increase the bonding and durability, in particular, a composite sheet manufacturing method comprising an airgel sheet that can significantly reduce the manufacturing cost And to provide a manufacturing apparatus.

Composite sheet manufacturing method comprising an airgel sheet according to a first embodiment of the present invention for achieving the above object comprises the steps of preparing an airgel sheet 30 (S10); Stacking the fiber sheets 10 on both sides of the airgel sheet 30 (S20); And bonding the laminated airgel sheet 30 and the fiber sheet 10 with heat and pressure to produce a composite sheet 40 laminated with the fiber sheet 10, the airgel sheet 30, and the fiber sheet 10. Step S30 may be included.

Between the step S10 and the step S20 may be further included a step (S15) for drying the airgel sheet 30.

Between step S20 and step S30 may be a step (S25) of temporarily fixing the need for the laminated airgel sheet 30 and the fiber sheet (10).

After the step S30, by cutting the composite sheet 40 to a predetermined size may further comprise the step (S40) of manufacturing a composite pad (50).

The step S20, (a) preparing a silica sol (2); (b) preparing a gel catalyst (3); (c) spraying and impregnating the silica sol (2) prepared in step (a) on the surface of the fiber sheet (1); (d) spraying the gelling catalyst (3) prepared in step (b) on the surface of the fiber sheet (1) impregnated with the silica sol (2) to prepare a gel sheet (20) gelled silica sol ; (e) aging the gel sheet 20 in which the silica sol is gelled; (f) adding a coating solution to the aged gel sheet 20 to modify the surface; (g) drying the gel sheet 20 having the surface modified to prepare an airgel sheet 30.

In the step (a), the silica sol 2 may be prepared by mixing TEOS (tetraethly orthosilicate) with ethanol.

The tetraethly orthosilicate (TEOS) may be hydrolyzed.

In step (b), the gelation catalyst 3 may be prepared by mixing ethanol and aqueous ammonia (NH 4 OH).

Step (c) and step (d) may be made in the conveyor belt for transporting the fiber sheet 1 from one side to the other side.

In the step (d), the gelling catalyst 3 may be injected onto the surface of the fiber sheet 1 at a rate of 0.035 to 0.012 L / min, and left for 8 to 12 minutes to gel the silica sol.

In the step (e), the silica sol gelled gel sheet 20 may be aged at a high temperature of 70 ° C. for 50 minutes.

The coating solution in step (f) may be prepared by mixing ethanol and ammonia water (NH ₄ OH).

In the step (f), 1.6 times of the silica sol (2) impregnated with the coating solution on the surface of the fiber sheet (1) is added, and the surface is modified by aging and HMDS (Hexamethyldisilazane) for 1 hour at a high temperature of 70 ℃. can do.

In the step (g), the surface-modified gel sheet 20 is dried by injecting carbon dioxide at a rate of 70 L / min for 10 minutes at a temperature of 28 ° C. and 70 bar, and drying by heating up to 50 ° C. for 1 minute 20 minutes. In the second drying step, and then injecting carbon dioxide at a rate of 0.7L / min for 20 minutes in the environment of 50 ℃ and 150bar, the third drying step to dry, and injecting carbon dioxide at a rate of 0.7L / min 20 minutes after 20 minutes It may include a fourth drying step of drying.

In the step (g), the third drying step may recover ethanol generated from the gel sheet 20 as the surface is modified while injecting carbon dioxide.

The step (g) may further include a discharge step of discharging carbon dioxide for 2 hours after the fourth drying step.

Steps (e), (f) and (g) can be made in a reaction vessel containing a gel sheet.

As described above, a manufacturing apparatus for performing the composite sheet manufacturing method including the airgel sheet according to the first embodiment of the present invention includes a gel sheet maker 100 for manufacturing a gel sheet 20; A reaction vessel 200 for aging, surface modifying, and drying the gel sheet 20 manufactured by the gel sheet maker 100 to produce an airgel sheet 30; It comprises a composite sheet maker 300 for manufacturing a composite sheet 40 by bonding the airgel sheet 30 and the fiber sheet 10 produced by the reaction vessel 200, the composite sheet maker 300 An airgel sheet feed roller 310 for supplying the airgel sheet 30, a plurality of fiber sheet feed rollers 320 for supplying the fiber sheet 10 so as to be laminated on both sides of the airgel sheet 30, and the airgel It may include a heat presser 330 for pressing the heat and pressure in the state in which the fiber sheet 10 is interposed between the sheet 30 to produce a composite sheet 40.

The composite sheet maker 300 is a drying member 340 for drying the airgel sheet 30 supplied from the airgel sheet supply roller 310 and the airgel sheet 30 is interposed with the fiber sheet 10 A needling member 350 may be further included by needling to temporarily join.

The gel sheet manufacturing machine 100 is a winding roller 110 in which the fiber sheet 1 is wound, a conveyor belt 120 for transferring the fiber sheet 1 wound in the winding roller 110 from one side to the other side, and the Silica sol supply member 130 for impregnating by spraying the silica sol (2) on the surface of the fiber sheet (1) located on the conveyor belt 120, the surface of the fiber sheet (1) located on the conveyor belt 120 A catalyst supply member 140 for producing a gel sheet 20 in which silica sol is gelled by spraying the gel catalyst 3 on the gelling agent, and the gel sheet 20 transferred to the other side by the conveyor belt 120. It may include a recovery roller 150 wound and recovered in a roll form.

Composite sheet manufacturing method according to a second embodiment of the present invention comprises the steps of preparing an airgel sheet 30 (S10); Stacking the fiber sheets 10 on both sides of the airgel sheet 30 (S20); And bonding the laminated airgel sheet 30 and the fiber sheet 10 with heat and pressure to produce a composite sheet 40 laminated with the fiber sheet 10, the airgel sheet 30, and the fiber sheet 10. Including the step (S30), in the airgel sheet preparation step (S10) the airgel sheet 30 is made of a composite comprising an airgel matrix and the reinforcing structure, the airgel matrix is continuous (continuous) through the reinforcing structure Wherein the reinforcing structure is a lofty fibrous batt, wherein the fibers are oriented along all three axes, and the bet is in the form of a sheet such that the composite is a lightweight, insulating product that is elastic and durable, and the lofty fibrous batt is thick Compressible to at least 50% of and recover to at least 70% of the original thickness after 5 seconds of compression, the density of the Lofty fibrous bets is between 0.001 and 0.26 g / cm3, The cross sectional area of the discernible fibers in the cross section of the composite may be less than 10% of the total cross sectional area.

The lofty fibrous batting may maintain at least 50% of the original thickness after addition of a gel forming liquid to form the airgel matrix.

The lofty fibrous bets may have elasticity that is compressible to at least 65% of the original thickness and that recovers to at least 75% of the original thickness after compression for 5 seconds.

The cross sectional area of the fibers of the Lofty fibrous bet identifiable in the cross section of the composite may be less than 8% of the total area of the cross section.

The present invention has the following effects.

First: The composite sheet manufacturing method comprising an airgel sheet according to the present invention can increase the bonding and durability by manufacturing a composite sheet by laminating the airgel sheet and fiber sheet, can significantly reduce the manufacturing cost, in particular to increase the thickness stably You can.

Secondly, the present invention can increase the thickness while maintaining the luxury of the outer shell by laminating the airgel sheet and the fiber sheet.

Thirdly, the present invention can produce an airgel sheet having excellent heat insulation and durability, in particular, a uniform thickness by using a method for producing an airgel sheet.

Fourth: In the method for producing an airgel sheet according to the present invention, high quality silica sol can be obtained by mixing TEOS (tetraethly orthosilicate) with ethanol.

Fifth: In the method for producing an airgel sheet according to the present invention, a high quality gelling catalyst can be obtained by mixing ethanol and ammonia water (NH ₄ OH).

Sixth: In the manufacturing method of the airgel sheet according to the present invention by using a conveyor belt for transferring the fiber sheet from one side to the other side it is possible to obtain the continuity of the work and simplify the process.

1 is a flow chart showing a manufacturing method of a composite sheet including an airgel sheet according to a first embodiment of the present invention.

Figure 2 is a flow chart showing a method of manufacturing an airgel sheet according to a first embodiment of the present invention.

3 is a view showing an apparatus for producing an airgel sheet according to a first embodiment of the present invention.

4 is a view showing an aging step using a reaction vessel according to a first embodiment of the present invention.

5 is a view showing a surface modification step using the reaction vessel according to the first embodiment of the present invention.

6 is a view showing a drying step using a reaction vessel according to the first embodiment of the present invention.

7 is a view showing an apparatus for manufacturing a composite sheet including an airgel sheet according to the first embodiment of the present invention.

8 is a view showing an airgel composite in a composite sheet including an airgel sheet according to a second embodiment of the present invention.

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. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like parts throughout the specification.

Composite sheet manufacturing method comprising an airgel sheet according to the first embodiment of the present invention, as shown in Figure 1, a composite sheet laminated with a fiber sheet 10, an airgel sheet 30 and a fiber sheet 10 In order to manufacture 40, the airgel sheet preparation step (S10), including a fiber sheet lamination step (S20), and a composite sheet manufacturing step (S30).

[Aerogel Sheet Preparation Steps]

Airgel sheet preparation step (S10) is to prepare the airgel sheet 30. First, the method of manufacturing an airgel sheet is demonstrated.

That is, a method of manufacturing an airgel sheet is to produce an airgel sheet having excellent heat insulation and durability, particularly uniform thickness, as shown in Figure 2, (a) preparing a silica sol (2) (b) preparing a gelation catalyst (3), (c) impregnating the surface of the fiber sheet (1) by impregnating the silica sol (2) prepared in the step (a), (d) silica Spraying the gelling catalyst (3) prepared in the step (b) on the surface of the sol-impregnated fiber sheet (1) to produce a gel sol gelled gel sheet 20, (e) the silica sol Aging the gelled gel sheet 20, (f) adding a coating solution to the aged gel sheet 20 to modify the surface, and (g) the gel sheet 20 having the surface modified. Drying to prepare the airgel sheet 30.

Hereinafter, the airgel sheet preparation step (S10) will be described in more detail.

(a) silica sol manufacturing step

(a) The silica sol manufacturing step is to obtain a silica sol, a silica sol (2) is prepared by mixing TEOS (tetraethly orthosilicate) and ethanol. That is, silica sol 2 is prepared by including 1.2 kg of TEOS and 2.7 kg of ethanol in a reactor (not shown).

On the other hand, TEOS is a solvent having excellent reactivity with water, using a hydrolyzed, it can further increase the reactivity. That is, by mixing the hydrolyzed TEOS and ethanol can be obtained a silica sol excellent in reactivity.

(b) gelation catalyst preparation step

(b) The gelation catalyst preparation step is to obtain a gelation catalyst, to prepare a gelation catalyst (3) by mixing ethanol and ammonia water (NH ₄ OH). That is, 0.5 kg of ethanol and 30 ml of ammonia water (NH ₄ OH) are mixed in a reaction tank (not shown) to prepare a gel catalyst 3.

On the other hand, the composite sheet manufacturing apparatus according to the first embodiment of the present invention is a gel sheet maker 100 for producing a gel sheet 20, a reaction vessel 200 for producing an airgel sheet through the gel sheet 20 and It includes a composite sheet maker 300 for manufacturing a composite sheet 40 through the airgel sheet 30.

Gel sheet maker

Here, (c) the silica sol injection step and (d) gelling catalyst injection step is performed by the gel sheet maker 100, which will be described in detail for the gel sheet maker 100.

That is, the gel sheet manufacturing machine 100 is, as shown in FIG. 3, the fiber sheet 1 is wound in a roll shape, the winding roller 110, the fiber sheet 1 wound on the winding roller 110 at one side. Silica sol supply member 130 for impregnating by spraying the silica sol (2) prepared in step (a) on the surface of the conveyor belt 120, the fiber sheet 1 located on the conveyor belt 120 to the other side, Catalyst supply member 140 for producing a gel sol gelled gel sheet 20 by injecting the gel catalyst (3) prepared in step (b) on the surface of the fiber sheet (1) located on the conveyor belt 120 , And a recovery roller 150 which winds and recovers the gel sheet 20 transferred to the other side by the conveyor belt 120 in a roll form.

In the gel sheet manufacturing apparatus 100, when the fiber sheet 1 is prepared on the winding roller 110, the conveyor belt 120 transfers the fiber sheet 1 wound on the winding roller 110 from one side to the other side. . At this time, the silica sol supply member 130 on the surface of the fiber sheet 1 conveyed by the conveyor belt 120 is impregnated silica sol by spraying the silica sol (2) prepared in step (a), and the catalyst supply The member 140 sprays the gelation catalyst 3 on the surface of the fiber sheet 1 impregnated with silica sol to produce a gel sheet 20 in which silica sol is gelled. And the gel sheet 20 transferred to the other side of the conveyor belt 120 is recovered while being wound again by the recovery roller 150.

Here, the conveyor belt 120 includes a scraper 160 for uniformly controlling the thickness of the silica sol 2 and the gelling catalyst 3 sprayed on the fiber sheet 1. That is, the scraper 160 includes a first scraper 161 for adjusting the thickness of the silica sol 2 sprayed on the surface of the fiber sheet 1, and a gelation catalyst 3 sprayed on the surface of the fiber sheet 1. And a second scraper 162 for adjusting the thickness of the substrate.

That is, the first scraper 161 and the second scraper 162 have the same shape and are installed on the upper surface of the conveyor belt 120 so as to be height-adjustable in the vertical direction, such as the silica sol 2 and the catalyst for gelation 3. ) To uniformly adjust the thickness, thereby obtaining a gel sheet 20 of uniform quality.

Hereinafter, the (c) silica sol injection step and (d) gel catalyst injection step using the aerogel maker 100 will be described in detail.

(c) silica sol injection step

(c) The silica sol spraying step is impregnated by spraying the silica sol (2) prepared in step (a) on the surface of the fiber sheet. That is, the silica sol (2) prepared in step (a) is injected into the silica sol supply member 130 and stored. Then, when the fiber sheet 1 is transferred to the lower portion of the silica sol supply member 130 by the conveyor belt 120, the silica sol 2 is sprayed through the silica sol supply member 130 to form the fiber sheet 1. Impregnate the surface.

At this time, the silica sol 2 sprayed on the fiber sheet 1 has a uniform thickness while passing through the first scraper 161 installed on the conveyor belt 120. That is, the first scraper 161 may uniformly control the thickness of the silica sol 2 by blocking the silica sol 2 having a predetermined thickness or more from passing therethrough.

(d) gel injection catalyst

(d) The gel catalyst catalyst spraying step may inject gelation catalyst 3 onto the surface of the fiber sheet 1 impregnated with silica sol by step (c) to gel the silica sol. That is, the gel catalyst 3 prepared in step (b) is injected into the catalyst supply member 140 and stored. Then, when the fiber sheet 1 impregnated with silica sol is transferred to the lower portion of the catalyst supply member 140 by the conveyor belt 120, the gelling catalyst 3 is transferred to the fiber sheet through the catalyst supply member 140. By spraying on the surface of 1) to gel the silica sol, a gel sheet 20 in which the silica sol is gelled can be obtained.

Here, the catalyst supply member 140 is sprayed at a set speed of the stored gelling catalyst 3, and left for a set time to stably gel the silica sol. That is, the catalyst supply member 140 sprays the gelling catalyst 3 on the surface of the fiber sheet 1 at a rate of 0.035 to 0.012 L / min, and is allowed to stand for 8 to 12 minutes to gradually gel the silica sol.

In particular, the catalyst supply member 140 may uniformly control the gelling of the silica sol by varying the injection speed of the gelling catalyst 3 in accordance with the density of the silica sol (2) impregnated in the fiber sheet (1).

That is, (1) when the silicasol density is 40 kg / m ³ , the injection speed of the gelling catalyst 3 is adjusted to 0.035 L / min. At this time, the silica sol 2 impregnated in the fiber sheet 1 has a content of 30wt% and a thermal conductivity of 14.9mW / mK.

(2) When the silica sol has a density of 60 kg / m ³ , the injection speed of the gelling catalyst (3) is adjusted to 0.017 L / min. At this time, the silica sol 2 impregnated in the fiber sheet 1 has a content of 38 wt% and a thermal conductivity of 14.1 mW / mK.

(3) When the silicasol density is 80 kg / m ³ , the injection speed of the gelling catalyst (3) is adjusted to 0.014 L / min. At this time, the silica sol 2 impregnated in the fiber sheet 1 has a content of 38 wt% and a thermal conductivity of 13.6 mW / mK.

(4) When the silicasol density is 100 kg / m ³ , the injection speed of the gelling catalyst (3) is adjusted to 0.012 L / min. At this time, the silica sol 2 impregnated in the fiber sheet 1 has a content of 55wt% and a thermal conductivity of 13.0mW / mK.

As such, as the density of the silica sol increases, the injection speed of the gelling catalyst decreases, thereby inducing stable gelation of the silica sol.

On the other hand, the gel sheet 20 manufactured as described above is recovered while being wound in a roll form by the recovery roller 150, the recovered gel sheet 20 by using the reaction vessel 200 (e) gel sheet aging The airgel sheet 30 may be prepared by performing the step, (f) gel sheet surface modification, and (g) gel sheet drying.

Reaction vessel

Here, the reaction vessel 200 has an accommodation space 210 for hermetically receiving the gel sheet 20 recovered in the form of a roll, as shown in FIGS. 4 to 6, and is connected to the accommodation space at one end. An injection port 220 and an outlet 230 connected to the accommodation space 210 is formed at the other end.

Hereinafter, (e) gel sheet aging step, (f) gel sheet surface modification step, and (g) gel sheet drying step will be described using the reaction vessel 200.

(e) Gel Sheet Aging Step

(e) Gel sheet aging step ages the gel sheet 20, as shown in FIG. That is, the gel sheet 20 recovered in step (d) is accommodated in the accommodation space 210 of the reaction vessel 2000. Next, the accommodating space 210 of the reaction vessel 200 is heated to 70 ° C. for 50 minutes to uniformize the tissue of the gel sheet 20.

Here, the (e) gel sheet aging step is left for 10 minutes at room temperature (or 25 ℃) before aging in the reaction vessel 200, the aging proceeds. That is, by inducing stable gelation of the silica sol 2 and then aging, the structure of the gel sheet 20 can be made more uniform.

(f) gel sheet surface modification step

(F) gel sheet surface modification step is to modify the surface by spraying the coating liquid on the aged gel sheet 20, as shown in FIG. That is, (f) gel sheet surface modification step to prepare a coating solution by mixing ethanol and ammonia water (NH ₄ OH). Then, the coating liquid is injected into the accommodation space 210 through the injection port 220 of the reaction vessel 200 into which the gel sheet 20 is inserted to modify the surface of the gel sheet 20. At this time, the coating solution is sprayed 1.6 times the silica sol impregnated on the surface of the fiber sheet in the step (c), the reaction vessel 200 is aged by aging and HMDS (Hxamethyldisilazane) for 1 hour at a high temperature of 70 ℃ gel sheet (20) Modify the surface of the.

On the other hand, HMDS (Hexamethyldisilazane) is used to change the surface of the gel sheet 20 to hydrophobic.

(g) gel sheet drying step

(g) Gel sheet drying step, as shown in Figure 6, to dry the gel sheet 20, the surface is modified to complete the airgel sheet 30. At this time (g) gel sheet drying step is a supercritical drying is carried out in a state that the gel sheet 20 is accommodated in the reaction vessel (200). That is, (g) gel sheet drying step is the first drying step of drying the surface-modified gel sheet 20 by injecting carbon dioxide at a rate of 70L / min for 10 minutes at 28 ℃ and 70 bar environment, 50 ℃ for 1 minute 20 minutes The secondary drying step of heating and drying to a furnace, and the third drying step of drying by injecting carbon dioxide at a rate of 0.7 L / min for 20 minutes at 50 ° C. and 150 bar, and 0.7 L / min for 20 minutes after 20 minutes of rest. And a fourth drying step of drying by injecting at a speed. As the drying step is performed, the drying rate of the gel sheet 20 may be increased.

On the other hand, (g) the third drying of the gel sheet drying step is ethanol is generated in the reaction vessel 200 by the chemical reaction of carbon dioxide and the gel sheet 20, the ethanol generated in the reaction vessel 200 is discharge port 230 Discharge through and recover.

And (g) the gel sheet drying step includes a discharge step of discharging carbon dioxide for 2 hours after the fourth drying, thereby inducing a gentle environmental change in the gel sheet 20 to uniformize the tissue of the gel sheet 20. do.

Through this process, the airgel sheet 30 is manufactured. When the manufacturing of the airgel sheet 30 is completed, the step of laminating the fiber sheet 10 on both sides of the airgel sheet 30 is performed.

[Fiber Sheet Lamination Step]

Fiber sheet lamination step (S20), as shown in Figure 7, to increase the thickness of the composite sheet in order to increase the bonding of the airgel sheet, and prepare a fiber sheet 10 such as a blanket (blanket). Then, the prepared fiber sheet 10 is mounted on each of the plurality of fiber sheet feed rollers 320 to supply the fiber sheet 10 to be laminated on both sides of the airgel sheet 30.

[Composite Sheet Manufacturing Method]

Composite sheet manufacturing method (S30) is a composite sheet 40 by manufacturing the laminated fiber sheet 10, the airgel sheet 30, and the fiber sheet 10 by heat and pressure. In this case, a composite sheet maker is used.

Composite Sheet Maker

The composite sheet maker 300 according to the first embodiment of the present invention, as shown in Figure 7, the airgel sheet feed roller 310 for supplying the airgel sheet 30, the fiber on both sides of the airgel sheet 30 A plurality of fiber sheet supply roller 320 for supplying the sheet 10, respectively, the airgel sheet 30 and the heat-compressor 330 for pressing the fiber sheet 10 with heat and pressure to produce a composite sheet 40 In addition, the composite sheet 40 may be obtained while passing through the heat presser 330.

Here, the composite sheet maker 300 according to the first embodiment of the present invention further includes a drying member 340 for drying the airgel sheet 30 supplied from the airgel sheet supply roller 310, and the drying member 340. Increases the drying rate of the airgel sheet 30 further improves the bonding to the fiber sheet 10.

In addition, the composite sheet manufacturing apparatus 300 according to the first embodiment of the present invention further includes a needling member 350 for needlessly bonding the airgel sheet 30 having the fiber sheet 10 interposed therebetween, and the needle The ring member 350 prevents irregular bonding from occurring as a result of temporarily bonding the airgel sheet 30 and the fiber sheet 10.

On the other hand, the composite sheet maker 300 according to the first embodiment of the present invention further includes a cutting member 360 for cutting the composite sheet 40 to a predetermined size to process the composite pad 50, the cutting member ( 360 is processed to the composite pad 50 by cutting the composite sheet 40 to increase the efficiency of use and storage.

The composite sheet manufacturing step (S30) using the composite sheet maker 300 according to the first embodiment of the present invention having such a configuration will be described.

Composite Sheet Manufacturing Steps

When the lamination of the fiber sheet 10, the airgel sheet 30 and the fiber sheet 10 by the airgel sheet preparation step (S10) and the fiber sheet lamination step (S20) is completed, the laminated fiber sheet 10, airgel sheet 30 and the fiber sheet 10 are bonded by heat and pressure to produce a composite sheet 40.

At this time, between the step S10 and step S20 further comprises the step of drying the prepared airgel sheet 30 (S15).

That is, in the drying step S15, the airgel sheet 30 is dried by high temperature heat through the drying member 340 to evaporate moisture, thereby increasing the drying rate of the airgel sheet 30.

In addition, between the step S20 and step S30 includes the step of temporarily fixing the laminated airgel sheet 30 and the fiber sheet 10 by needling (S25).

That is, the temporary fixing step (S25) is temporarily fixed by needling the airgel sheet 30 and the fiber sheet 10 in order to prevent movement when the laminated airgel sheet 30 and the fiber sheet 10 is compressed.

In this way, as the drying step and the temporary fixing step are further performed, the composite sheet 40 of uniform quality can be obtained.

Herein, in the first embodiment of the present invention, the composite sheet 40 laminated with the airgel sheet 30, the fiber sheet 10, and the airgel sheet 30 has been described as one embodiment. A composite sheet 40 in which 30 and one or more fiber sheets 10 are laminated may also be manufactured.

On the other hand, the composite sheet 40 prepared as described above can be cut to a predetermined size to obtain a composite pad 50. That is, the composite pad 40 may be cut to a predetermined size through the cutting member 360 to obtain the composite pad 50.

By using the composite sheet manufacturing method and apparatus including an airgel having such a configuration and method, it is possible to obtain a composite sheet and a composite pad having high adhesion and durability, low manufacturing cost, and particularly stable thickness.

Hereinafter, in describing other embodiments according to the present invention, the same components as the above-described embodiments will be denoted by the same reference numerals, and redundant descriptions thereof will be omitted.

Composite sheet manufacturing method according to a second embodiment of the present invention shows another embodiment of the airgel sheet preparation step (S10) in the composite sheet manufacturing method according to the first embodiment described above.

That is, in the manufacturing method of the composite sheet according to the second embodiment of the present invention, referring to FIG. 1, preparing the airgel sheet 30 (S10), respectively, the fiber sheet 10 is formed on both sides of the airgel sheet 30. Laminating step (S20), and the laminated airgel sheet 30 and the fiber sheet 10 by bonding the heat and pressure of the composite sheet laminated with the fiber sheet 10, the airgel sheet 30, and the fiber sheet 10 40, a step (S30) is prepared.

Here, the airgel sheet preparation step (S10), as shown in FIG. 8, prepares the airgel sheet 30 from the composite 20 including the airgel matrix and the reinforcing structure 21.

The airgel composite 20 is composed of two phases. The first phase is a low density airgel matrix and the second phase is a reinforcing phase. The reinforcing phase is primarily composed of a lofty fibrous material, preferably a lofty batting and a mixture of one or more fibrous materials of significantly different thickness, length or aspect ratio. Suitable mixtures of the two fibrous material systems are such that when short, high aspect ratio microfibers (one fibrous material) are dispersed throughout a continuous aerogel matrix that penetrates lofty fiber batting (other fibrous materials). Is made.

And the airgel matrix is continuous through the reinforcing structure 21, the reinforcing structure 21 is a ropety fibrous bet, wherein the fibers are oriented along all three axes, and the Lofty fibrous bet is In the form of a sheet, the composite 20 is a resilient, durable lightweight insulation product, and the lofty fibrous bet is compressible to at least 50% of the thickness and recovers to at least 70% of the original thickness after 5 seconds of compression, and the lofty The density of the fibrous batting is between 0.001 and 0.26 g / cm 3 and the cross sectional area of the discernible fibers in the cross section of the composite 20 may be less than 10% of the total cross sectional area.

That is, the airgel matrix may be an organic airgel, an inorganic airgel or a mixture thereof.

The organic airgel is polyacrylate, polystyrene, polyacrylonitrile, polyurethane, polyimide, polyfurfural alcohol, phenyl furfuryl alcohol, melamine formaldehyde, resorcinol formaldehyde, cresol formaldehyde, phenol formaldehyde , Polyvinyl alcohol dialdehyde, polycyanurate, polyacrylamide, various epoxy, agar, agarose, or a mixture of two or more of them (CS Ashley, CJ Brinker and DM Smith, Journal of Non Crystalline Solid, Volume 285, 2001).

And the main synthetic route of inorganic airgel production is the hydrolysis and condensation of suitable metal alkoxides. Most suitable metal alkoxides are those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms in each alkyl group. Specific embodiments of such compounds include tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetra-n-propoxysilane, aluminum isopropoxide, aluminum sec-butoxide, cerium isopropoxide, Hafnium tert-butoxide, magnesium aluminum isopropoxide, yttrium isopropoxide, titanium isopropoxide, zirconium isopropoxide and the like. In the case of silica precursors, these materials can be partially hydrolyzed and stabilized at low pH with polymers of polysilic acid esters, for example polydiethoxysiloxanes. These materials are commercially available as alcohol solutions (eg Silbond®40, 40% silica content, Silbond Corporation). Pre-polymerized silica precursors are particularly suitable for the airgel composite 20 of the present invention.

Suitable materials for producing airgels used at low temperatures are non-refractory metal alkoxides based on oxide-forming metals. Suitable such metals are silicon, magnesium, mixtures thereof. Suitable alkoxides for high temperatures are generally refractory metal alkoxides capable of forming oxides, for example zirconia, yttria, hafnia, alumina, titania, ceria and the like and mixtures thereof such as zirconia and yttria. It is also possible to use non-refractory metals and refractory metals such as silicon and / or mixtures of magnesium and aluminum. An advantage of using one or more metal oxide matrix materials in an airgel structure is the enhancement of IR clouding achieved by providing chemical functionalities that absorb radiation at a wide range of wavelengths.

Finely dispersed dopants such as carbon black, titania, iron oxides, silicon, carbides, molybdenum, silicides, manganese oxides, polydialkylsiloxanes, where the alkyl groups have from 1 to 4 carbon atoms Can be added to improve thermal performance at high temperatures by increasing the opacity of the airgel to IR transmission. Suitable amounts of such dopants are generally from 1 to 20 wt%, preferably from 2 to 10% of the weight of the final composite.

Lofty fibrous bets are defined as fibrous materials that exhibit bulk properties and significant elasticity (complete bulk recovery zones). A suitable form is a soft web. The use of Lofty batting reinforcements avoids substantial deterioration of the thermal performance of the airgel while minimizing the volume of the unsupported airgel. Suitably, batting means a layer or sheet of fibrous material that is used as a lining cover, cotton or container, or a blanket for thermal insulation.

The reinforcing fibrous material used in the second embodiment of the present invention is one or a plurality of lofty fibrous batting layers. The use of lofty batting reinforcements avoids substantial deterioration of the thermal performance of the airgel while minimizing the volume of the unsupported airgel.

Generally, "batting" is a product made from carding or Garnetting fibers that form a smooth web of fibers in the form of a sheet, but in the present invention a "batting" is a non-sheet that is sufficiently open to "rope". Web in the form of, for example, Primaloft® products from Albany International. Generally, batting refers to a layer or sheet of fibrous material used as a lining cover, cotton or container, or a blanket for thermal insulation. Fibers suitable for producing batting are relatively thin and have deniers of 15 or less, preferably 10 or less. The softness of the web is a by-product of the relatively thin and oriented fibers that are used to make the fibrous web.

In a second embodiment of the present invention, the batting retains a small number of individual threads (or fibers) so as not to significantly alter the thermal properties of the reinforced composite 20 compared to non-reinforced aerogels of the same material. In this case, it is called "lofty". This means that the cross section of the fiber in the cross section of the final airgel composite 20 is less than 10%, preferably less than 8%, most preferably less than 5% of the total cross section of the cross section. Suitably, the lofty bets have a thermal conductivity of 50 mW / m-K or less at room temperature and pressure to promote the formation of low thermal conductivity airgel composite 20.

Another method of confirming that a bet is sufficiently lofted in the second embodiment of the present invention is to measure its compressibility and elasticity. In such a case, the Lofty bet is (i) compressible to at least 50%, preferably at least 65%, most preferably at least 80% of the intrinsic thickness and at least 70%, preferably at least at least after a few seconds of compression 75%, most preferably at least 80%. According to this definition, lofty bets can be substantially restored to their original size and shape by removing air (bulk) in the case of compression. For example, a HolofilTM bet can be compressed to a minimum of 0.2 "from the original 1.5" thickness and will return to the original thickness when the load is removed. The bet may be considered to have 1.3 "air (bulk) and 0.2" fibers. It is compressible up to 87% and recovers to almost 100% of its original thickness. Glass fiber batting used for home insulation can be recovered to approximately 80% of its original thickness, although compressed and slowed to a similar degree.

The batting used in the second embodiment of the present invention is substantially different from the fibrous mat. A fibrous mat is a "tightly woven or tangle of lumps", that is, a dense and relatively rigid fibrous structure that retains minimal open space between adjacent fibers. The mat has a density of 2.5 lbs / ft3 (0.41 g / cc), while the ropet bets used herein have a much smaller density, i.e. 0.1-16 lbs / ft3 (0.001-0.26 g / cc), preferably 2.4 To 6.1 lbs / ft 3 (0.04-0.1 g / cc). In general, the mat is compressible to less than 20% and shows little elasticity. In the aerogel composite 20 made of mat reinforcement, the cross section of the mat fiber accounts for up to 30-50% of the total cross section.

Suitably, the bet maintains at least 50% thickness after the gel forming liquid is poured.

For a method for understanding the need for openness of the fiber reinforcement used in the second embodiment of the present invention, referring to FIG. 8, the fiber composite material traveling in the z-axis (heat flow direction) acts as a heat conduit to produce To significantly increase the thermal conductivity of

In particular, bets that retain almost straight (non-curly) fibers in the x-y horizontal plane are more rigid than typical lofty bets of equal density where the bent or curly fibers run in all three axes. To minimize heat flow in the z direction (required for most insulating materials), the bet should show less heat flow in the z axis (heat flow direction).

Thus, a sufficient amount of fiber is oriented in the z axis so that suitable bets do not compromise the insulating properties of the insulating composite. The fibers in the z axis can be composed of a material different from that in the x and y axes (preferably, a material having a lower thermal conductivity). The z-axis fibers may be made more pliable than the fibers in the x-y direction to provide a more twisted path for heat conduction. The same fiber materials and methods can be used throughout the batting to minimize thermal conduction on all axes, but using many of these materials and methods will reduce the elasticity of the resulting composites, since in many insulating products the heat flow is treated in a particular direction. Can be. An ideal lofty bet has fine, curly fibers evenly distributed throughout the composite 20.

The scope of the present invention is shown by the following claims rather than the detailed description, and various embodiments derived from the meaning and scope of the claims and their equivalents are possible.

Claims (24)

1. Preparing an airgel sheet 30 (S10);

   Stacking the fiber sheets 10 on both sides of the airgel sheet 30 (S20); And

   Manufacturing the composite sheet 40 laminated with the fiber sheet 10, the airgel sheet 30, and the fiber sheet 10 by bonding the laminated airgel sheet 30 and the fiber sheet 10 with heat and pressure. Composite sheet manufacturing method comprising an airgel sheet containing (S30).
2. The method according to claim 1,

   Method of manufacturing a composite sheet comprising an airgel sheet further comprises the step (S15) of drying the airgel sheet 30 between the step S10 and the step S20.
3. The method according to claim 1,

   Method of manufacturing a composite sheet comprising an airgel sheet comprising a step (S25) between the step S20 and the step S30 by needling the laminated airgel sheet 30 and the fiber sheet (10).
4. The method according to claim 1,

   After the step S30, by cutting the composite sheet 40 to a predetermined size composite sheet manufacturing method comprising an airgel sheet further comprising the step (S40) of manufacturing a composite pad (50).
5. The method according to claim 1, wherein the step S10,

   (a) preparing a silica sol (2);

   (b) preparing a gel catalyst (3);

   (c) spraying and impregnating the silica sol (2) prepared in step (a) on the surface of the fiber sheet (1);

   (d) spraying the gelling catalyst (3) prepared in step (b) on the surface of the fiber sheet (1) impregnated with the silica sol (2) to prepare a gel sheet (20) gelled silica sol ;

   (e) aging the gel sheet 20 in which the silica sol is gelled;

   (f) adding a coating solution to the aged gel sheet 20 to modify the surface;

   (g) a method for producing a composite sheet comprising an airgel sheet comprising the step of manufacturing the airgel sheet 30 by drying the surface modified gel sheet 20.
6. The method according to claim 5,

   Silica sol (2) in the step (a) comprises a composite sheet manufacturing aerogel sheet prepared by mixing TEOS (tetraethly orthosilicate) and ethanol.
7. The method according to claim 6,

   The TEOS (tetraethly orthosilicate) is a composite sheet manufacturing method comprising an airgel sheet using a hydrolyzed.
8. The method according to claim 5,

   The gelation catalyst (3) in the step (b) comprises a composite sheet manufacturing method comprising an airgel sheet prepared by mixing ethanol and ammonia water (NH 4 OH).
9. The method according to claim 5,

   Step (c) and step (d) is a composite sheet manufacturing method comprising an airgel sheet made in a conveyor belt for transferring the fiber sheet (1) from one side to the other side.
10. The method according to claim 5,

    The step (d) comprises spraying the gelling catalyst 3 on the surface of the fiber sheet 1 at a rate of 0.035 ~ 0.012L / min, and left for 8 to 12 minutes to include an airgel sheet to gel the silica sol Composite sheet manufacturing method.
11. The method according to claim 5,

    The step (e) is a composite sheet manufacturing method comprising an airgel sheet for aging the gel sol gel sheet (20) gelled at a high temperature of 70 ℃ 50 minutes.
12. The method according to claim 5,

    The coating solution in step (f) is a composite sheet manufacturing method comprising an airgel sheet prepared by mixing ethanol and ammonia water (NH ₄ OH).
13. The method according to claim 12,

    In the step (f), 1.6 times of the silica sol (2) impregnated with the coating solution on the surface of the fiber sheet (1) is added, and the surface is modified by aging and HMDS (Hexamethyldisilazane) for 1 hour at a high temperature of 70 ℃. Composite sheet manufacturing method comprising an airgel sheet.
14. The method according to claim 5,

    In the step (g), the surface-modified gel sheet 20 is dried by injecting carbon dioxide at a rate of 70 L / min for 10 minutes at a temperature of 28 ° C. and 70 bar, and drying by heating up to 50 ° C. for 1 minute 20 minutes. In the second drying step, and then injecting carbon dioxide at a rate of 0.7L / min for 20 minutes in the environment of 50 ℃ and 150bar, the third drying step to dry, and injecting carbon dioxide at a rate of 0.7L / min 20 minutes after 20 minutes Composite sheet manufacturing method comprising an airgel sheet comprising a fourth drying step of drying.
15. The method according to claim 14,

    In the step (g), the third drying step comprises a composite sheet comprising an airgel sheet for recovering ethanol generated from the gel sheet 20 as the surface is modified while injecting carbon dioxide.
16. The method according to claim 14,

    The step (g) is a composite sheet manufacturing method comprising an airgel sheet further comprising a discharge step of discharging carbon dioxide for 2 hours after the fourth drying step.
17. The method according to claim 5,

    Step (e), (f) and (g) is a composite sheet manufacturing method comprising an airgel sheet made in a reaction vessel containing a gel sheet.
18. Preparing an airgel sheet 30 (S10);

    Stacking the fiber sheets 10 on both sides of the airgel sheet 30 (S20); And

    Manufacturing the composite sheet 40 laminated with the fiber sheet 10, the airgel sheet 30, and the fiber sheet 10 by bonding the laminated airgel sheet 30 and the fiber sheet 10 with heat and pressure. (S30),

    In the airgel sheet preparation step (S10) the airgel sheet 30 is made of a composite comprising an airgel matrix and a reinforcing structure,

    The airgel matrix is continuous through the reinforcing structure, the reinforcing structure is a ropety fibrous batting, wherein the fibers are oriented along all three axes, and the batting is in the form of a sheet such that the composite is elastic and durable Phosphorus lightweight insulation, the lofty fibrous bet is compressible to at least 50% of the thickness and recovers to at least 70% of the original thickness after compression for 5 seconds, the density of the lofty fibrous bet is 0.001 to 0.26 g / cm3 And a cross section of the identifiable fibers in the cross section of said composite comprising an airgel sheet of less than 10% of the total cross section.
19. The method according to claim 18,

    And said lofty fibrous batting comprises an airgel sheet maintaining at least 50% of its original thickness after addition of a gel forming liquid to form said airgel matrix.
20. The method according to claim 18,

    And the Lofty fibrous batting comprises an airgel sheet having an elasticity that is compressible to at least 65% of the original thickness and recovers to at least 75% of the original thickness after compression for 5 seconds.
21. The method according to claim 18,

    And wherein the cross sectional area of the fibers of the Lofty fibrous batt identifiable in the cross section of the composite comprises an airgel sheet of less than 8% of the total area of the cross section.
22. A gel sheet maker 100 for producing a gel sheet 20;

    A reaction vessel 200 for aging, surface modifying, and drying the gel sheet 20 manufactured by the gel sheet maker 100 to produce an airgel sheet 30;

    It comprises a composite sheet maker 300 for manufacturing a composite sheet 40 by bonding the airgel sheet 30 and the fiber sheet 10 produced by the reaction vessel 200,

    The composite sheet maker 300 is a plurality of fiber sheets for supplying the fiber sheet 10 to be laminated on both sides of the airgel sheet supply roller 310, the airgel sheet 30 for supplying the airgel sheet 30 The air roller sheet including a feed roller 320, a heat presser 330 for pressing the heat and pressure in the state interposed between the airgel sheet 30 and the airgel sheet 30 to produce a composite sheet 40 Composite sheet manufacturing apparatus.
23. The method according to claim 22,

    The composite sheet maker 300 is a drying member 340 for drying the airgel sheet 30 supplied from the airgel sheet supply roller 310 and the airgel sheet 30 is interposed with the fiber sheet 10 Composite sheet manufacturing apparatus comprising an airgel sheet further comprising a needling member 350 for needlessly bonding.
24. The method according to claim 22,

    The gel sheet manufacturing machine 100 is a winding roller 110 in which the fiber sheet 1 is wound, a conveyor belt 120 for transferring the fiber sheet 1 wound in the winding roller 110 from one side to the other side, and the Silica sol supply member 130 for impregnating by spraying the silica sol (2) on the surface of the fiber sheet (1) located on the conveyor belt 120, the surface of the fiber sheet (1) located on the conveyor belt 120 A catalyst supply member 140 for producing a gel sheet 20 in which silica sol is gelled by spraying the gel catalyst 3 on the gelling agent, and the gel sheet 20 transferred to the other side by the conveyor belt 120. Composite sheet manufacturing apparatus comprising an airgel sheet including a recovery roller 150 to be wound and recovered in a roll form.

Images