KR20170003278A

KR20170003278A - Shrink-resistance laminate, method for manufacturing the shrink-resistance laminate and device for manufacturing the shrink-resistance

Info

Publication number: KR20170003278A
Application number: KR1020150093722A
Authority: KR
Inventors: 정봉현; 문식원; 노태근; 민근기; 이정배; 변수진
Original assignee: 주식회사 엘지화학
Priority date: 2015-06-30
Filing date: 2015-06-30
Publication date: 2017-01-09

Abstract

TECHNICAL FIELD The present invention relates to a heat shrinkable laminate, a method of manufacturing the heat shrinkable laminate, and an apparatus for manufacturing the heat shrinkable laminate.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a shrinkable laminate, a method for manufacturing the shrinkable laminate, and an apparatus for manufacturing the shrinkable laminate.

BACKGROUND ART Reinforcing membranes are used in fields requiring ion exchange ability such as cells and sensors. Specifically, the reinforced membranes are used as ion exchange membranes for fuel cells, chemical sensors, and flow batteries.

Recently, as energy resources such as oil and coal are predicted to be exhausted, there is an increasing need for energy that can replace them. Interest in fuel cells, metal secondary batteries, and flow batteries is becoming an alternative energy source.

As one of such alternative energies, fuel cells are highly efficient, do not emit pollutants such as NOx and SOx, are enriched with fuel, and related researches are actively proceeding. At the same time, it is necessary to study a reinforced membrane provided with a polymer electrolyte membrane of a fuel cell.

Metal secondary batteries are being studied to increase the efficiency of charging and discharging. Especially, researches on metal air secondary batteries are being carried out by attaching air electrodes of fuel cells. Accordingly, there is a growing interest in a reinforced membrane provided as an electrolyte membrane of a metal secondary battery.

The flow battery is a secondary battery in which charging and discharging are performed while circulating an electrolyte in which energy is stored. Research on a flow battery together with a reinforcing film provided as an electrolyte membrane of the flow has been actively conducted.

Korean Patent Publication No. 10-2003-0045324 (published on Jun. 11, 2003)

The present specification is intended to provide a shrinkable laminate, a method of manufacturing the shrinkable laminate, and an apparatus for manufacturing the shrinkable laminate.

The present disclosure relates to a heat-shrinkable substrate; An adhesive layer provided on the shrinkable substrate; A shrinkable substrate provided on the adhesive layer; And a coating layer provided on the shrinkable substrate.

The present invention also relates to a method of manufacturing a light-shrinkable substrate, comprising: laminating a shrinkable substrate on an adhesive layer of an anti-shrinkable substrate having an adhesive layer on at least one surface thereof; And applying the coating composition onto the laminated shrinkable substrate.

Further, the present specification is concerned with a shrinkable substrate preparation unit; A shrink-resistant substrate providing apparatus for providing a shrink-resistant substrate having at least one surface thereof an adhesive layer; A shrinkable laminate recovery unit; A pressurizing roll for pressurizing the shrinkable base material having the adhesive layer and the shrinkable base material so that the shrinkable base material provided from the shrinkable base material supplier is in contact with the adhesive layer of the shrinkable base material; And a coating portion for applying the coating composition onto the shrinkable substrate of the resistant shrinkable laminate which has passed through the pressing roll.

The manufacturing method of the shrinkable laminate of the present invention can minimize the deformation of the porous material or the reinforcing film in the step of producing the laminate.

1 is a cross-sectional view of an anti-shrinkage laminate according to an embodiment of the present invention.
Fig. 2 is a schematic diagram of shrinkage of the dried and comparative examples after drying. Fig.
Fig. 3 shows the state after drying of the example.
Fig. 4 shows the dried state of the comparative example.

Hereinafter, the present invention will be described in detail.

The above-mentioned shrinkable laminate refers to a laminate having resistance to shrinkage, and refers to a laminate resistant to shrinkage due to heat. Particularly, the above-mentioned shrinkable laminate can have heat shrinkability at 200 ° C. Specifically, the shrinkable laminate may have a dimensional change of less than 5% at 200 ° C. More specifically, the shrinkable laminate has a tensile strength at 170 ° C for 30 minutes in a machine direction (MD) Can have a length variation within 3%, and can have a length variation within 3% in the machine direction perpendicular direction (TD). In this case, the shrinkage of the laminate can be prevented in the step of drying or curing the laminate provided with the coating layer, and the dimensional stability of the laminate can be ensured.

The thickness of the above resistant shrinkable laminate is not particularly limited, but the thickness of the shrink resistant laminate may be 50 탆 or more and 500 탆 or less. Here, the thickness of the resistance shrinkable laminate means the total thickness of the resistance shrinkable laminate including the shrinkable substrate, the adhesive layer, the shrinkable substrate, and the coating layer.

The above-mentioned shrinkable substrate means a substrate having resistance to shrinkage, and refers to a substrate resistant to shrinkage due to heat. In particular, the above-mentioned shrinkable base material may have heat shrinkability at 200 占 폚. Specifically, the shrinkable substrate may have a dimensional change of less than 5% at 200 ° C. More specifically, the shrinkable substrate preferably has a thickness of less than 3% in a machine direction (MD) for 30 minutes at 170 ° C. , And can have a length variation within 3% in the direction TD perpendicular to the machine direction. The dimensional stability of the laminate can be ensured by complementing the shrinkage resistance of the laminate provided with the shrinkable base material.

For example, the shrinkable substrate may be made of polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), or the like. , Polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyimide (PI).

The thickness of the shrinkable substrate is not particularly limited, but the thickness of the shrinkable substrate may be 20 m or more and 300 m or less. In this case, it satisfies the shrinkage resistance, and it is wound in roll form and is easy to store.

The width of the shrinkable substrate may be at least 1 times and not more than 2 times the width of the shrinkable substrate, and may be 1.1 times or more and 1.2 times or less. In this case, the width of the shrinkable substrate is minimized by minimizing the portion other than the width of the shrinkable substrate, thereby reducing the use of the expensive shrinkable substrate.

The width of the shrinkable substrate may be 100 mm or more and 2 m or less. The larger the shrinkable substrate is, the larger the shrinkable substrate can be made, and the wide-width coating can be performed.

The adhesive layer may be a layer having an adhesive force capable of adhering the shrink-resistant substrate to the shrinkable substrate and a peeling force capable of removing the shrinkable substrate later from the shrinkable substrate. The adhesive layer allows the shrinkable base material to adhere to the shrinkable base material and can compensate the shrinkage resistance of the shrinkable base material during the process.

The adhesive force or peeling force of the pressure-sensitive adhesive layer is not particularly limited as long as it can adhere the shrink-resistant substrate to the shrinkable substrate and remove the shrink-resistant substrate from the shrinkable substrate.

The adhesive layer is not particularly limited as long as it has an adhesive force capable of sticking to the shrinkable substrate and a peeling force capable of removing the shrinkable substrate from the shrinkable substrate at a later stage, and the adhesive layer generally employed in the related art .

The thickness of the adhesive layer is not particularly limited, but the thickness of the adhesive layer may be 1 m or more and 200 m or less.

The shrinkable substrate includes a material which is weak to heat and is shrunk by heat. In particular, the shrinkable substrate may comprise a material which is shrunk at 100 DEG C or higher. Specifically, the shrinkable substrate may have a dimensional change of 10% or more at 170 ° C. More specifically, the shrinkable substrate may have a lengthwise change of 10% or more in a width direction perpendicular to the longitudinal direction at 170 ° C.

The thickness of the shrinkable substrate is not particularly limited, but the thickness of the shrinkable substrate may be 10 탆 or more and 300 탆 or less.

The width of the shrinkable substrate may be 10 mm or more and 2 m or less.

The shrinkable substrate may be a porous substrate. The porous substrate refers to a substrate having a plurality of pores provided therein and on the surface thereof.

The porosity of the porous substrate may be 20% or more and 80% or less, and the higher the porosity, the higher the degree of shrinkage due to the more space that can be shrunk by heat.

The size of the pores of the porous substrate may be 50 nm or more and 5 占 퐉 or less.

The porous substrate may be formed of at least one selected from the group consisting of polyimide (PI), polysulfone (PSF), polybenzimidazole (PBI), nylon, polyethylene terephthalate (PET), polytetrafluoroethylene Polytetrafluoroethylene (PTFE), polyethylene (PE), polypropylene (PP), polyarylene ether sulfone (PAES), polyetheretherketone (PEEK), polyaramide, Fluorinated ethylene propylene (FEP), poly (ethene-co-tetrafluoroethene), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride And may include at least one of polyvinylidene fluoride (PVDF) and perfluoroalkoxy polymer (PFA).

The coating layer may be provided on the shrinkable substrate. When the shrinkable substrate is a porous substrate, the coating layer may be provided on a part of the pores of the porous substrate and on the surface of the porous substrate.

The coating layer may comprise a polymer. The polymer is not particularly limited, and those generally used in the art can be used.

The polymer may be a polymer having ionic conductivity. Specifically, the polymer may be an ionic conductor.

The polymer may be a polymer having hydrogen ion conductivity. In this case, those conventionally known in the art can be used so far as they have hydrogen ion conductivity. The polymer having hydrogen ion conductivity may be a polymer having one or two or more cation-exchange groups selected from the group consisting of a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, and derivatives thereof in the side chain.

The polymer having hydrogen ion conductivity may be a hydrocarbon-based polymer, a partially fluorinated polymer, or a fluorinated polymer.

The hydrocarbon-based polymer may be a hydrocarbon-based sulfonated polymer having no fluorine group. Alternatively, the fluorinated polymer may be a sulfonated polymer saturated with a fluorine group, and the partially fluorinated polymer may be a sulfonated polymer that is not saturated with a fluorine group have.

The polymer having hydrogen ion conductivity may be at least one selected from the group consisting of a perfluorosulfonic acid polymer, a hydrocarbon polymer, an aromatic sulfon polymer, an aromatic ketone polymer, a polybenzimidazole polymer, a polystyrene polymer, a polyester polymer, a polyimide polymer, Based polymer, a polyether sulfone-based polymer, a polyphenylene sulfide-based polymer, a polyphenylene oxide-based polymer, a polyphosphazene-based polymer, a polyethylene naphthalate-based polymer, a polyester-based polymer, a doped polybenzimide Based polymer may be one or two or more polymers selected from the group consisting of a polyolefin-based polymer, a polyetherketone-based polymer, a polyphenylquinoxaline-based polymer, a polysulfone-based polymer, a polypyrrole-based polymer and a polyaniline-based polymer. The polymer may be a single copolymer, an alternating copolymer, a random copolymer, a block copolymer, a multi-block copolymer or a graft copolymer, but is not limited thereto.

Specifically, the polymer having hydrogen ion conductivity may be at least one selected from the group consisting of Nafion, sulfonated polyetheretherketone (sPEEK) sulfonated polyetherketone (sPEK), polyvinylidene fluoride At least one of poly (vinylidene fluoride) -graft-poly (styrene sulfonic acid), PVDF-g-PSSA) and sulfonated poly (fluorenyl ether ketone) .

The polymer may be an ion conductive polymer capable of transferring anions, and is not particularly limited as long as it can transfer anions, and those conventionally known in the art can be used. For example, the ion conductive polymer capable of transferring the anion may include styrene, vinylbenzyl chloride (VBC), divinylbenzene (DVB), trimethylamine (TMA), and amine functional groups And an anion exchange polymer having an anion exchange group.

The polymer may have a weight average molecular weight of several thousands to several tens of millions. Specifically, the weight average molecular weight of the polymer may be 1,000 g / mol to 10,000,000 g / mol, but is not limited thereto.

The coating layer may further include at least one of inorganic particles and carbon particles. The inorganic particles and the carbon particles may be nanoparticles having nano-sized particles. The inorganic particles and the carbon particles may be spherical or plate-shaped particles. Herein, the inorganic material includes a metal, a metal oxide, a metal nitride, a mineral and the like.

The inorganic particles may comprise at least one of silica, silicate minerals, silver, nickel and copper. Specifically, the inorganic particles may include at least one of silica nanoparticles, montmorillonite (MMT), Ag, Ni, and Cu.

The carbon particles may include at least one of graphene oxide, carbon black, and carbon nanotubes.

When the shrinkable laminate is a porous substrate, the shrinkable laminate may be a reinforcing film precursor. Here, the reinforcing film precursor refers to a material before the reinforcing film is formed, and the reinforcing film may be formed by removing the heat-shrinkable substrate from the heat-shrinkable laminate.

And a reinforcing film from which the shrink-resistant substrate is removed from the shrink-resistant laminate. Specifically, the electrochemical cell may be a fuel cell, a metal secondary battery, or a flow battery.

The reinforcing film; An air electrode provided on one surface of the reinforcing film; And a fuel electrode provided on the other surface of the reinforcing film.

The fuel cell may be a fuel cell such as a PAFC, an AFC, a PEMFC, a direct methanol fuel cell, a MCFC, a biofuel cell, cell, BFC) and a solid oxide fuel cell (SOFC).

The fuel cell including the reinforcing membrane may be a polymer electrolyte fuel cell or a biofuel cell, but is not limited thereto.

In the fuel cell, the reinforcing membrane may be an electrolyte membrane, and may be specifically a polymer electrolyte membrane.

The air electrode and the fuel electrode each include a gas diffusion layer and a catalyst layer. The catalyst layer of the air electrode and the catalyst layer of the fuel electrode are in contact with the electrolyte membrane, and can be manufactured according to a conventional method known in the art.

A catalyst selected from the group consisting of platinum, ruthenium, osmium, a platinum-ruthenium alloy, a platinum-osmium alloy, a platinum-palladium alloy, and a platinum-transition metal alloy may be used as the catalyst layer of the fuel electrode, have.

The catalyst layer of the air electrode is a place where a reduction reaction of the oxidizing agent occurs, and a platinum or platinum-transition metal alloy can be used as a catalyst.

The catalysts can be used not only by themselves but also by being supported on a carbon-based carrier.

Examples of the carbon-based material include graphite, carbon black, acetylene black, denka black, cacao black, activated carbon, mesoporous carbon, carbon nanotube, carbon nanofiber, carbon nanohorn, , Carbon nanowire, fullerene (C60), and super P black (a mixture of two or more) may be preferable examples.

The process of introducing the catalyst layer can be performed by a conventional method known in the art. For example, the catalyst ink may be directly coated on the electrolyte membrane or coated on the gas diffusion layer to form the catalyst layer. The method of coating the catalyst ink is not particularly limited, but spray coating, tape casting, screen printing, blade coating, die coating or spin coating may be used.

The catalyst ink may typically consist of a catalyst, a polymer ionomer and a solvent.

As the polymer ionomer, a sulfonated polymer such as a Nafion ionomer or a sulfonated polytrifluorostyrene may be used.

As the solvent contained in the catalyst ink, any one or a mixture of two or more selected from the group consisting of water, butanol, isopropanol, methanol, ethanol, n-propanol, n-butyl acetate and ethylene glycol is preferably used Can be used.

The gas diffusion layer serves as a current conductor and serves as a passage for reacting gas and water, and has a porous structure. Therefore, the gas diffusion layer may include a conductive base material.

As the conductive base material, any conventional materials known in the art can be used. For example, carbon paper, carbon cloth or carbon felt can be preferably used. It does not.

In a fuel cell, the most basic unit for generating electricity is a membrane electrode assembly (MEA), which is composed of an electrolyte membrane and air electrodes and fuel electrodes formed on both sides of the electrolyte membrane. Hydrogen ions (H ⁺ ) and electrons (e ^- ) are generated in the fuel electrode due to the oxidation reaction of hydrogen such as hydrocarbons such as methanol or butane, and hydrogen ions move to the air electrode through the electrolyte membrane. In the air electrode, hydrogen ions transferred through the electrolyte membrane react with oxidants and electrons such as oxygen to produce water. This reaction causes electrons to migrate to the external circuit.

The membrane electrode assembly for a fuel cell may include an electrolyte membrane and an air electrode and a fuel electrode positioned opposite to each other with the electrolyte membrane interposed therebetween.

The air electrode may be provided with an air electrode catalyst layer and a cathode air diffusion layer sequentially from the electrolyte membrane, and the fuel electrode may be provided with a fuel electrode catalyst layer and a fuel electrode diffusion layer sequentially from the electrolyte membrane.

As the fuel that can be supplied to the fuel cell, gas or liquid hydrogen or hydrocarbon fuel may be used. Examples of hydrocarbon fuels include methanol, ethanol, propanol, butanol or natural gas.

The reinforcing film; An anode provided on one surface of the reinforcing film; And a cathode provided on the other surface of the reinforcing film.

The anode includes a metal capable of emitting electrons when the battery is discharged, and may include at least one of a metal, a composite metal oxide, a metal oxide, and a composite metal oxide.

The type of the metal secondary battery can be determined depending on the type of the metal included in the anode. For example, when the anode includes lithium metal, it can be said to be a lithium secondary battery. When the anode includes zinc metal Zinc secondary battery. When the anode includes aluminum metal, it can be said to be an aluminum secondary battery.

The cathode refers to an electrode that receives electrons when a battery is discharged. The cathode may be formed by combining an air electrode of a fuel cell and an air electrode using air or oxygen as an oxidizing agent.

The shape of the metal secondary battery is not limited, and may be, for example, a coin type, a flat plate type, a cylindrical type, a horn type, a button type, a sheet type or a laminate type.

The present disclosure relates to a cathode; anode; A reinforcing film disposed between the cathode and the anode and made according to the present disclosure; A negative electrode tank and a positive electrode tank for respectively storing the negative electrode electrolyte solution and the positive electrode electrolyte solution; A pump connected to the negative electrode tank and the positive electrode tank to supply the electrolyte solution to the negative electrode or the positive electrode; A cathode inlet and a cathode inlet through which the cathode electrolytic solution or the anode electrolytic solution flows respectively from the pump; And a cathode outlet and a cathode outlet through which the electrolyte solution is discharged from the cathode or the anode to the cathode tank and the cathode tank, respectively.

The negative electrode electrolytic solution and the positive electrode electrolytic solution may include an electrolyte and a solvent, respectively.

The electrolyte and the solvent are not particularly limited, but those generally used in the art can be employed.

In one embodiment of the present disclosure, the redox flow battery uses a V (IV) / V (V) redox couple as the positive electrode electrolyte and a V (II) / V Can be used.

In another embodiment of the present disclosure, the redox flow battery may use a halogen redox couple as the positive electrode electrolyte and a V (II) / V (III) redox couple as the negative electrode electrolyte.

In another embodiment of the present invention, the redox flow battery uses a redox couple as a cathode electrolyte and a sulfurized redox couple as a cathode electrolyte.

In another embodiment of the present invention, the redox flow battery uses a halogen redox couple as a positive electrode electrolyte and a zinc redox couple as a negative electrode electrolyte.

The flow battery may be a redox flow battery.

The redox flow battery includes, but is not limited to, a vanadium redox flow battery, a lead redox flow battery, a polysulfide bromine (PSB) redox flow battery, a zinc-bromine (Zn-Br) redox flow Battery or the like.

The shape of the flow battery is not limited, and may be, for example, a coin, a flat plate, a cylinder, a horn, a button, a sheet or a laminate.

The present invention provides a battery module including the electrochemical cell as a unit cell.

The battery module may be specifically used as a power source for an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, or a power storage device.

The present specification provides a battery module including the fuel cell as a unit cell.

Wherein the battery module comprises: a stack including a unit cell including the fuel cell and a separator provided between the unit cells; A fuel supply unit for supplying fuel to the stack; And an oxidant supply for supplying the oxidant to the stack.

The present invention provides a battery module including the metal secondary battery as a unit battery.

The battery module may be formed by stacking a bipolar plate between the metal secondary batteries.

When the metal secondary battery is a metal air secondary battery, the bipolar plate may be porous to supply air supplied from the outside to the cathode included in each of the metal air secondary batteries. For example, porous stainless steel or porous ceramics.

The present specification provides a battery module including the flow battery as a unit cell.

The battery module may be formed by stacking a bipolar plate between the flow batteries.

The present invention relates to a method for manufacturing a light-shrinkable substrate, comprising: laminating a shrinkable substrate on an adhesive layer of an anti-shrinkable substrate having an adhesive layer on at least one side; And applying the coating composition onto the laminated shrinkable substrate.

In the manufacturing method of the above-mentioned shrinkable laminate, the description overlapping with the constitution of the above-mentioned shrinkable laminate can be cited as described above.

The step of coating the pressure-sensitive adhesive layer on the shrinkable substrate before the step of laminating the shrinkable substrate on the coated pressure-sensitive adhesive layer may be further included.

In the coating step of the adhesive layer, a method of coating the adhesive layer on at least one surface of the shrinkable substrate is not particularly limited, but the adhesive layer may be coated by, for example, comma coating, capillary coating or slot-die coating .

The step of laminating the shrinkable substrate may be a step of laminating the shrinkable substrate on the surface of the surface of the shrinkable substrate with the adhesive layer.

When the shrinkable substrate is a porous substrate, the step of laminating the shrinkable substrate on the coated adhesive layer may be a step of laminating the porous substrate.

The method may further include the step of hydrophilizing the porous substrate before the step of laminating the shrinkable substrate. In this case, when the coating composition is applied onto the porous substrate, the coating composition may be susceptible to penetration into the pores of the porous substrate.

The applying step of the coating composition may be a step of applying the coating composition on a surface opposite to the surface provided with the adhesive layer of the shrinkable substrate laminated on the surface of the surface of the shrinkable substrate with the adhesive layer.

If the shrinkable substrate is a porous substrate, a portion of the coating composition applied to the porous substrate may be impregnated into the pores of the porous substrate, and the step of applying the coating composition may include impregnating the coating composition in the pores of the porous substrate.

The method of applying the coating composition is not particularly limited, but it is possible to apply the coating composition by, for example, a dip coating, a capillary coating, a slot die coating or a comma coating.

In the application step of the coating composition, the coating composition may include a polymer and a solvent capable of dissolving the polymer well. The polymer may be a polymer having ionic conductivity. Specifically, the polymer may be an ionic conductor.

The coating composition may further comprise at least one of inorganic particles and carbon particles. The inorganic particles and the carbon particles may be nanoparticles having nano-sized particles. The inorganic particles and the carbon particles may be spherical or plate-shaped particles. Herein, the inorganic material includes a metal, a metal oxide, a metal nitride, a mineral and the like.

The polymer is not particularly limited, and those generally used in the art can be used.

The solvent is not particularly limited as long as it is a substance capable of dissolving the polymer, and conventional materials known in the art can be used.

The manufacturing method of the shrinkable laminate of the present invention may further include a step of applying the coating composition and then drying the coating composition.

In the drying step, the drying conditions of the shrinkable laminate are not particularly limited. For example, the drying temperature may be 80 ° C or more and 200 ° C or less, and the drying time may be 1 minute or more and 1 hour or less. In terms of productivity, it is preferable to dry at a high temperature for a short time, but it can be suitably adjusted according to the size of the drying facility, the coating speed, and the drying condition of the coating layer.

The manufacturing method of the shrinkable laminate of the present invention may further include a step of applying the coating composition, followed by drying the coating composition and curing the coating composition after drying.

The drying step is a step of removing the solvent in the coating composition, and the curing step may be a step of curing the solids in the coating composition.

In the curing step, the curing conditions are not particularly limited. For example, the curing temperature may be 100 ° C or more and 200 ° C or less, and the curing time may be 1 minute or more and 1 hour or less.

Shrinkage can occur during coating and / or curing after coating the shrinkable substrate with the coating composition. In order to prevent this, a method has been proposed in which tension is maintained in the longitudinal direction while pulling the shrinkable substrate, or the substrate is placed on the supporting substrate. However, in such a case, the coating composition may have a reduced width or a non-flat surface during drying of the coated shrinkable substrate.

It is advantageous that the shrinkable substrate is provided on at least one side so that deformation of the shrinkable substrate can be minimized during the drying and / or curing process.

The manufacturing method of the shrinkable laminate of the present invention may further include removing the shrinkable substrate from the shrinkable laminate of the shrinkable laminate after the step of drying or curing the coating composition on the shrinkable substrate.

The present disclosure relates to a shrinkable substrate preparation apparatus, A shrink-resistant substrate providing apparatus for providing a shrink-resistant substrate having at least one surface thereof an adhesive layer; A shrinkable laminate recovery unit; A pressurizing roll for pressurizing the shrinkable base material having the adhesive layer and the shrinkable base material so that the shrinkable base material provided from the shrinkable base material supplier is in contact with the adhesive layer of the shrinkable base material; And a coating portion for applying the coating composition onto the shrinkable substrate of the resistant shrinkable laminate which has passed through the pressing roll.

In the apparatus for producing a shrinkable laminate, the description overlapping with the constitution of the method for manufacturing the shrinkable laminate and the shrinkable laminate can be cited as described above.

The shrinkable substrate providing portion and the shrink-resistant substrate providing portion may be configured to provide the shrinkable substrate having the shrinkable substrate and the adhesive layer, respectively.

The shrinkable laminate collector may be configured to recover the shrinkable laminate including a coating layer formed by coating a coating composition on a shrinkable substrate laminated on an adhesive layer of an intrinsically shrinkable substrate.

When the shrinkable substrate is removed after the coating composition is coated on the shrinkable substrate laminated on the adhesive layer of the shrinkable substrate, the shrinkable laminate collector can recover the laminate from which the shrinkable substrate has been removed.

In the case where the coating composition is coated on the shrinkable substrate laminated on the adhesive layer of the shrinkable substrate and the shrinkable substrate together with the adhesive layer is removed, the shrinkable laminate collecting unit is provided with the adhesive layer and the laminate Can be recovered.

The shrinkable substrate providing unit, the shrink-resistant substrate providing unit, and the shrink-resistant laminate collecting unit are not particularly limited in structure, material, form, and the like, provided that the shrinkable substrate and the shrink-resistant substrate are provided and the shrink- Those generally used in the technical field can be employed.

The shrinkable substrate providing portion, the shrink-resistant substrate providing portion, and the shrink-resistant laminated body collecting portion may each be a shrinkable substrate unwinder, a shrink-resistant substrate unwinder, and a shrink-resistant laminate rewinder.

In one embodiment of the present invention, the shrinkable substrate providing portion and the shrink-resistant substrate providing portion may continuously supply the shrinkable substrate and the shrink-resistant substrate. For example, the shrinkable substrate supply unit, the shrink-resistant substrate supply unit, and the shrink-resistant laminate shrink unit are respectively a shrinkable substrate unwinder, an shrinkable substrate unwinder, and a shrinkable laminate rewinder , The shrinkable substrate winding portion and the shrinkable substrate winding portion are continuously rotated to continuously supply the shrinkable substrate and the shrinkable substrate, and the shrinkable laminate winding portion is imparted to the shrinkable laminate by the force of recovering the shrinkable laminate And the rotational speed of the roller during each process can be determined.

In one embodiment of the present invention, the shrinkable substrate supply, the shrink-resistant substrate supply, and the shrink-resistant laminate-collecting unit may intermittently and continuously supply the shrinkable substrate and the shrink-resistant substrate. Here, the intermittent continuous means to supply the shrinkable base material and the shrinkable base material while repeating the supply of the shrinkable base material and the shrinkable base material at a time interval for a certain period of time and continuously supplying the same. For example, the supply of the shrinkable substrate can be stopped when the shrinkable substrate is supplied to the region to be coated, and the supply of the shrinkable substrate and the shrinkable substrate can be stopped for precise coating at the moment the shrinkable substrate is coated.

The pressure roll may pressurize the shrinkable base material and the shrinkable base material provided with the adhesive layer so that the shrinkable base material provided from the shrinkable base material providing part is in contact with the adhesive layer of the shrinkable base material.

The pressure roll may include two or more rolls provided on both sides of the shrinkable laminate so as to apply pressure to both surfaces of the shrinkable laminate.

The coating portion may include two or more coating portions that apply the same or different coating composition to the opposite surface of the surface provided with the adhesive layer of the shrinkable substrate.

If the shrinkable substrate is a porous support, the coating composition applied by the coating can be applied to penetrate into the pores of the porous support.

The configuration of the coating portion is not particularly limited as long as the coating portion can apply the same or different coating composition to the opposite surface of the surface of the shrinkable substrate on which the adhesive layer is provided and employs a coating device generally used in the related art .

The apparatus for manufacturing a shrinkable laminate is disposed between a shrinkable substrate providing portion and an shrinkable laminate collecting portion and between an shrinkable substrate providing portion and an shrinkable laminated body collecting portion to form a shrinkable substrate, a shrinkable substrate and a shrinkable laminate And may further include one or more guide rolls for changing the proceeding direction.

And one or more drying units positioned between the coating unit and the shrinkable laminate collecting unit.

The drying part includes at least two drying parts, and the resistant shrinkable laminate to which the coating composition is applied can be dried under different conditions of each drying part.

The drying unit may include a first drying unit configured to set a condition for volatilizing the solvent of the coating composition and a second drying unit configured to set a condition for curing the volatile coating composition.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following embodiments are for illustrative purposes only and are not intended to limit the specification.

[Example]

(PTFE, porosity of 70%, thickness of 30 占 퐉, size (20 mm 占 100 mm), 450 nm average pore size) on a PET film (100 占 퐉 thick and 200 mm 占 200 mm thick) having a pressure- (PTFE, porosity of 70%, thickness of 30 μm, size (20 mm × 100 mm), 450 nm average pore size) were laminated on a hydrophilic treated substrate, and then 15 wt% of ion exchange resin and NMP methylpyrrolidone) in an amount of 85% by weight for 10 minutes to prepare an intrinsically shrinkable laminate.

[Comparative Example]

(PTFE, porosity of 70%, thickness of 30 占 퐉, size of 20 mm 占 100 mm, thickness of 30 占 퐉, thickness of 30 占 퐉, size (20 mm 占 100 mm), 450 nm average pore size) and a hydrophilic treated porous substrate 450 nm average pore size) was impregnated in a coating solution containing 15% by weight of an ion exchange resin and 85% by weight of NMP as a solvent by 10 minutes, based on the total weight, and then dip coating.

[Experimental Example]

As a result of drying the above-described examples and comparative examples, it was expected that the comparative example would shrink more as shown in Fig. 2. The results of drying the above examples and comparative examples at 150 캜 for 30 minutes are shown in Figs. 3 (Comparative Example). In FIGS. 3 and 4, the relatively dark-colored left-browned porous substrate was hydrophilically treated, and the relatively transparent right-handed porous substrate was used.

As shown in FIG. 3, the shrinkage ratio in the examples was within 2% in the MD and TD directions, and it was found that the shrinkage was almost not shrunk by drying.

Fig. 4 shows the tension applied to the MD in the direction of the forceps for the process simulation. Specifically, one side is fixed in the MD direction of the comparative example, and the other side is tongued. Referring to FIG. 4, it can be seen that the shrinkage is severely in the MD and TD directions.

1: Insoluble shrinkable laminate
10: Shrinkable substrate
20: Adhesive layer
30: shrinkable substrate
40: Coating layer

Claims

Resistant substrate;
An adhesive layer provided on the shrinkable substrate;
A shrinkable substrate provided on the adhesive layer; And
And a coating layer provided on the shrinkable substrate.

The shrinkable laminate according to claim 1, wherein the shrinkable substrate is a porous substrate.

The shrinkable laminate according to claim 2, wherein the coating layer provided on the porous substrate is provided on a part of the pores of the porous substrate and on the surface of the porous substrate.

4. The shrinkable laminate according to claim 3, wherein the coating layer comprises a polymer having ion conductivity.

2. The shrink-resistant laminate according to claim 1, wherein the shrink-resistant substrate has shrinkage resistance at 200 deg.

2. The shrinkable laminate according to claim 1, wherein the shrinkable laminate has shrink resistance at 200 deg.

[2] The method according to claim 1, wherein the shrinkable substrate comprises at least one or more copolymer of polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) And the shrinkable laminate.

The method of claim 2, wherein the porous substrate is selected from the group consisting of polyimide (PI), polysulfone (PSF), polybenzimidazole (PBI), nylon, polyethylene terephthalate (PET), polytetrafluoro (PEEK), polypropylene (PP), polyarylene ether sulfone (PAES), polyether etherketone (PEEK), polyetheretherketone (PEEK) Polyaramid, fluorinated ethylene propylene (FEP), poly (ethene-co-tetrafluoroethene), polychlorotrifluoroethylene (PCTFE) , Polyvinylidene fluoride (PVDF), and perfluoroalkoxy polymer (PFA). 2. The shrinkable laminate according to claim 1, wherein the polyvinylidene fluoride (PVDF) and the perfluoroalkoxy polymer (PFA)

The shrink-resistant laminate according to claim 1, wherein the thickness of the shrinkable base material is 20 μm or more and 300 μm or less.

The shrink-resistant laminate according to claim 1, wherein the thickness of the adhesive layer is 1 μm or more and 200 μm or less.

The shrinkable laminate according to claim 1, wherein the thickness of the shrinkable substrate is 10 μm or more and 300 μm or less.

Laminating a shrinkable substrate on an adhesive layer of an anti-shrinkable substrate having an adhesive layer on at least one surface thereof; And
And applying the coating composition onto the laminated shrinkable substrate.

[Claim 12] The method according to claim 12, wherein the step of laminating the shrinkable substrate is a step of laminating the porous substrate.

13. The method of claim 12, wherein the step of applying the coating composition is a step of impregnating the coating composition in the pores of the porous substrate.

13. The method of claim 12, wherein in the step of applying the coating composition, the coating composition comprises an ion conductive polymer and a solvent.

13. The method of claim 12, further comprising the step of applying the coating composition and then drying the coating composition.

Shrinkable substrate preparation;
A shrink-resistant substrate providing apparatus for providing a shrink-resistant substrate having at least one surface thereof an adhesive layer;
A shrinkable laminate recovery unit;
A pressurizing roll for pressurizing the shrinkable base material having the adhesive layer and the shrinkable base material so that the shrinkable base material provided from the shrinkable base material supplier is in contact with the adhesive layer of the shrinkable base material; And
And a coating portion for applying the coating composition onto the shrinkable base material of the resistant shrinkable laminate which has passed through the pressing roll.

18. The apparatus of claim 17, further comprising a drying section positioned between the coating section and the shrinkable laminate collection section.

18. The apparatus of claim 17, wherein the shrinkable substrate is a porous substrate.

18. The apparatus of claim 17, wherein the coating composition comprises an ion conductive polymer and a solvent.

[19] The apparatus according to claim 17, wherein the shrinkable substrate supply unit and the shrink-resistant laminate collecting unit are each a shrinkable substrate unwinder and a shrinkable laminate rewinder.