EP3344451A1 - Process for making a graphene-based multi-layer polyurethane membrane - Google Patents

Process for making a graphene-based multi-layer polyurethane membrane

Info

Publication number
EP3344451A1
EP3344451A1 EP16766630.4A EP16766630A EP3344451A1 EP 3344451 A1 EP3344451 A1 EP 3344451A1 EP 16766630 A EP16766630 A EP 16766630A EP 3344451 A1 EP3344451 A1 EP 3344451A1
Authority
EP
European Patent Office
Prior art keywords
membrane
polyurethane
graphene
process according
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP16766630.4A
Other languages
German (de)
French (fr)
Inventor
Elisabetta GASPARI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Windtex Vagotex SpA
Original Assignee
Windtex Vagotex SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Windtex Vagotex SpA filed Critical Windtex Vagotex SpA
Priority claimed from PCT/IB2016/055221 external-priority patent/WO2017037642A1/en
Publication of EP3344451A1 publication Critical patent/EP3344451A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/12Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/24Layered products comprising a layer of synthetic resin characterised by the use of special additives using solvents or swelling agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/34Layered products comprising a layer of synthetic resin comprising polyamides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/40Layered products comprising a layer of synthetic resin comprising polyurethanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/08Animal fibres, e.g. hair, wool, silk
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/20Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202Conductive
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00Clothing

Definitions

  • the present invention relates to a process for making a polyurethane multi-layer membrane, and a multi-layer membrane thus obtained.
  • the invention is advantageously used in the creation and production of articles or garments, such as shoes or industrial work clothes, and the like, or of technical-sport clothes, to which the following description will make explicit reference without thereby losing generality, in order to protect in an effective and optimal manner, in particular at low temperatures.
  • the process for making a multilayer membrane for use in industrial work and/or technical garments or clothes includes the mutual coupling of at least a first support layer (neutral support), formed by a polyurethane film in a solvent, with a weight of about 15 g/sqm, and a second layer, formed by a film of polyurethane in a solvent, with a weight of about 30 g/sqm, to which a determined amount of graphene nano powder, a white pigment, and a solvent (with a mixing carried out at ambient temperature) are also added.
  • a first support layer neutral support
  • a second layer formed by a film of polyurethane in a solvent, with a weight of about 30 g/sqm
  • the above-mentioned polyurethane film of the second layer is in a percentage varying from 50 to 55% (with best performance obtained experimentally at 52%), graphene is from 7 to 10% (with best performance experimentally obtained at 8%), a white pigment is from 0.2 to 1 %, and solvent, in particular DMF, is from 20 to 40%.
  • first and second layer forming the membrane are initially been obtained separately in laboratory, by lying the solution on an appropriate silicone-coated white paper, which is arranged through a "pilot", i.e, via a laboratory instrument that allows, by means of a blade, to apply the product on the above paper to obtain a thin layer. Then follows a period of polymerization, where the film on paper is inserted in the oven first at 100°C for one minute (drying) and then at 150°C for three minutes.
  • the two first and second layers are coupled together by means of glue spotting application, applying a pressure of between 2 and 4 bar and at a temperature between 140 and 160°C, assuming a total thickness between 30 and 60 microns and a total weight of the membrane thus obtained in the range 40-70 g/sqm.
  • the creation of the finished membrane is carried out in an industrial double-head machine coater, where the membrane is formed in two consecutive layers and without having to couple them as in the laboratory: in a first tray the above-mentioned first layer (or 'neutral' polyurethane) is loaded, then on a cylinder the silicone-coated paper is wound that, once it is operated, collects the solution from the tray to carry it inside appropriate ovens. At the outlet there is a second tray, which instead contains the solution provided by the mentioned second polyurethane layer with graphene, which is thus deposited on the first layer of neutral polyurethane previously created.
  • the paper continues its movement through other ovens: therefore, at the end the same paper with the finished membrane (precisely formed by the two layers of film) will be rolled up on a reel. Finally, after an appropriate waiting period, the membrane will be 'solidified' and with the possibility of detachment from the above-mentioned paper support.
  • the process also provides for the application on the above membrane means of electrical connection to a portable battery, such as a conductive ribbon, which is also made from graphene, thus realizing a multilayer membrane provided with a high heating power.
  • the present innovative process may be advantageously provided with a further operative bonding step, during which the membrane itself is coupled with at least one laminate layer of predetermined material, preferably polyester (PES), polyamide (PA) or cotton (CO), polypropylene (PP), elastane (EA) and wool (WO), coupled to the membrane with 'spotting' or Open field' glue, also preferably added with graphene.
  • the above-mentioned membrane is disposed between two layers of laminated fabric as specified above.
  • a multilayer fabric with high impermeability and high windproof and thermal shock resistance capacities is therefore obtained, such as to be optimally used in clothing for use in industrial, technical and/or sport sectors.

Landscapes

  • Laminated Bodies (AREA)

Abstract

A process for making a polyurethane multi-layer membrane comprising the mutual coupling of a first support layer, formed by a polyurethane film, and a second layer, formed by a polyurethane film, which are added with a determined amount of graphene powder, a pigment, and a solvent substance.

Description

PROCESS FOR MAKING A GRAPHENE-BASED MULTI-LAYER POLYURETHANE MEMBRANE.
Applicant: WINDTEX VAGOTEX S.p.A.
Designated inventor: Elisabetta GASPARI
The present invention relates to a process for making a polyurethane multi-layer membrane, and a multi-layer membrane thus obtained.
In particular, the invention is advantageously used in the creation and production of articles or garments, such as shoes or industrial work clothes, and the like, or of technical-sport clothes, to which the following description will make explicit reference without thereby losing generality, in order to protect in an effective and optimal manner, in particular at low temperatures.
The structural and functional characteristics of the present invention and its advantages will be apparent from the underlying claims, and in particular from an examination of the following description made on the basis of a preferred but non- limiting schematic embodiment of the present process.
The process for making a multilayer membrane for use in industrial work and/or technical garments or clothes includes the mutual coupling of at least a first support layer (neutral support), formed by a polyurethane film in a solvent, with a weight of about 15 g/sqm, and a second layer, formed by a film of polyurethane in a solvent, with a weight of about 30 g/sqm, to which a determined amount of graphene nano powder, a white pigment, and a solvent (with a mixing carried out at ambient temperature) are also added.
According to the preferred formulation indicated below in the parameter table, the above-mentioned polyurethane film of the second layer is in a percentage varying from 50 to 55% (with best performance obtained experimentally at 52%), graphene is from 7 to 10% (with best performance experimentally obtained at 8%), a white pigment is from 0.2 to 1 %, and solvent, in particular DMF, is from 20 to 40%.
PU 25.9 kg 51.80%
GRAPHENE 4 kg 8.00%
WHITE 1/C pigment 0.1 kg 0.20%
DMF 20 kg 40.00%
Total 50 kg 100.00%
Note that the above-mentioned first and second layer forming the membrane are initially been obtained separately in laboratory, by lying the solution on an appropriate silicone-coated white paper, which is arranged through a "pilot", i.e, via a laboratory instrument that allows, by means of a blade, to apply the product on the above paper to obtain a thin layer. Then follows a period of polymerization, where the film on paper is inserted in the oven first at 100°C for one minute (drying) and then at 150°C for three minutes. Subsequently, the two first and second layers are coupled together by means of glue spotting application, applying a pressure of between 2 and 4 bar and at a temperature between 140 and 160°C, assuming a total thickness between 30 and 60 microns and a total weight of the membrane thus obtained in the range 40-70 g/sqm.
At the industrial level, however, the creation of the finished membrane is carried out in an industrial double-head machine coater, where the membrane is formed in two consecutive layers and without having to couple them as in the laboratory: in a first tray the above-mentioned first layer (or 'neutral' polyurethane) is loaded, then on a cylinder the silicone-coated paper is wound that, once it is operated, collects the solution from the tray to carry it inside appropriate ovens. At the outlet there is a second tray, which instead contains the solution provided by the mentioned second polyurethane layer with graphene, which is thus deposited on the first layer of neutral polyurethane previously created. Subsequently, the paper continues its movement through other ovens: therefore, at the end the same paper with the finished membrane (precisely formed by the two layers of film) will be rolled up on a reel. Finally, after an appropriate waiting period, the membrane will be 'solidified' and with the possibility of detachment from the above-mentioned paper support. With the aim of creating a fabric to be used particularly advantageously in the production of clothing in use in working activities or in sports, which is subject to external environmental weathering (e.g., cold places and/or harsh environments), exploiting particularly the very high conductivity of graphene, preferably the process also provides for the application on the above membrane means of electrical connection to a portable battery, such as a conductive ribbon, which is also made from graphene, thus realizing a multilayer membrane provided with a high heating power.
Indeed, from experimental tests, it has been shown that by applying to the membrane a 15 volt electric current, about 27mA and an increase of about 10°C than the surrounding environment have been detected, while at 30 volts about 53mA and an increase in temperature of about 25°C have been detected.
According to a preferable embodiment, after completion of the formation of the membrane by coupling the two above-mentioned first and second layers, the present innovative process may be advantageously provided with a further operative bonding step, during which the membrane itself is coupled with at least one laminate layer of predetermined material, preferably polyester (PES), polyamide (PA) or cotton (CO), polypropylene (PP), elastane (EA) and wool (WO), coupled to the membrane with 'spotting' or Open field' glue, also preferably added with graphene. Preferably, but not limited to, the above-mentioned membrane is disposed between two layers of laminated fabric as specified above.
A multilayer fabric with high impermeability and high windproof and thermal shock resistance capacities is therefore obtained, such as to be optimally used in clothing for use in industrial, technical and/or sport sectors.

Claims

1. Process for the production of a multilayer polyurethane membrane, characterized in that it comprises the step of coupling a first support layer defined by a film of polyurethane and a second layer defined by a polyurethane film added with a determined quantity of graphene powder, a pigment and a solvent substance.
2. Process according to claim 1 , characterized in that it also comprises the application on said membrane of means for electrical connection to a battery.
3. Process according to claim 1 or 2, characterized in that said first and second layers of said membrane are coupled together by applying adhesive or equivalent means.
4. Process according to claim 3, characterized in that to said application of adhesive or equivalent means follows a contacting union step of said first and second layers with a pressure ranging between 2 and 4 bar and at a temperature between 140 and 160 °C.
5. Process according to one or more of the preceding claims 1 to 4, characterized in that said polyurethane film of said second layer is in percentage varying from 50 to 55%, said graphene is in percentage from 7 to 10%, said pigment is a percentage from 0.2 to 1 %, and said solvent from 20 to 40%.
6. Process according to one or more of the preceding claims 1 to 5, characterized in that it further comprises an operational union step, during which takes place a coupling of said membrane with at least one laminate layer of predetermined material, preferably polyester (PES), polyamide (PA), or cotton (CO), polypropylene (PP), elastane (EA) and wool (WO) coupled to said membrane with glue or equivalent, said glue also preferably added with graphene.
7. Multilayer polyurethane membrane obtained by the process described in one or more of the preceding claims 1 to 6.
8. multilayer fabric, in particular for the realization of articles of clothing of industrial work, sports or the like, comprising the multilayer polyurethane membrane of claim
EP16766630.4A 2015-09-03 2016-09-01 Process for making a graphene-based multi-layer polyurethane membrane Withdrawn EP3344451A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITUB201553380 2015-09-03
PCT/IB2016/055221 WO2017037642A1 (en) 2015-09-03 2016-09-01 Process for making a graphene-based multi-layer polyurethane membrane

Publications (1)

Publication Number Publication Date
EP3344451A1 true EP3344451A1 (en) 2018-07-11

Family

ID=56940104

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16766630.4A Withdrawn EP3344451A1 (en) 2015-09-03 2016-09-01 Process for making a graphene-based multi-layer polyurethane membrane

Country Status (1)

Country Link
EP (1) EP3344451A1 (en)

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