EP3030596A1 - Manufactured product made of resin - Google Patents

Manufactured product made of resin

Info

Publication number
EP3030596A1
EP3030596A1 EP14777827.8A EP14777827A EP3030596A1 EP 3030596 A1 EP3030596 A1 EP 3030596A1 EP 14777827 A EP14777827 A EP 14777827A EP 3030596 A1 EP3030596 A1 EP 3030596A1
Authority
EP
European Patent Office
Prior art keywords
semi
finished product
manufactured product
polyurethane resin
elastomeric polyurethane
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Withdrawn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
EP14777827.8A
Other languages
German (de)
French (fr)
Inventor
Paolo Cappelletti
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.)
Materiko Srl
Original Assignee
Materiko Srl
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 Materiko Srl filed Critical Materiko Srl
Publication of EP3030596A1 publication Critical patent/EP3030596A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered 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
    • B32B7/04—Interconnection of layers
    • B32B7/08—Interconnection of layers by mechanical means
    • B32B7/09—Interconnection of layers by mechanical means by stitching, needling or sewing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered 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
    • B32B27/08—Layered 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/02—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch
    • B32B9/025—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising animal or vegetable substances, e.g. cork, bamboo, starch comprising leather
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00—Clothing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings

Definitions

  • the present invention relates to a product manufactured from elastomeric polyurethane resin optionally associated with other materials, such as leather, fabric, non-woven fabric or other polymeric resins.
  • the manufactured product of the invention is a fashion article, a clothing article or accessory, a design article, a household and furnishing article, a leatherware and luggage article, or an architectural finishing surface, such as wall and floor coverings.
  • PVC bags can be entirely obtained from a sheet of that material, in different colours and thicknesses, by cutting and sewing the desired shape. PVC can also be combined with other materials for the final construction of the bag, for example a fabric or another plastic material. Typically, these bags are "shiny" in appearance and completely smooth (i.e. devoid of reliefs, unless applied by sewing) and have low scratch resistance.
  • PVC yellows under exposure to light and over time tends to deteriorate, becoming brittle and forming cracks.
  • bas-reliefs grammages
  • PVC is not recyclable and the manufacturing process is highly polluting.
  • eco-leather also called eco-friendly leather, eco-hide, eco-friendly hide or low environmental impact leather
  • Such objects are, for example, bags, shoes, wallets, etc.
  • Eco-leather is normally a bilayer material consisting of a layer of fabric impregnated or spread with polyurethane resins, which can have an appearance like natural leather. With eco-leather one can achieve surfaces in which the typical aspect of natural leather is more or less accentuated, depending on consumer demands and product quality. It is also possible to achieve surface reliefs, normally a few millimetres in height, which are not to be considered true bas-reliefs.
  • Eco-leather has the great disadvantage of being, in the case of most products on the market, very poorly resistant to scratching, with the consequence that the aesthetics of the product can be compromised even after the object has been used for very little time.
  • Mono-material objects manufactured from hard or soft bi-component resin using injection moulds are also known.
  • Such objects are, for example, handles for bags, pendants, bracelets or complete bags or trolley bags.
  • the disadvantage of the aforesaid products consists in not being able to develop three-dimensional textures and high-definition bas-reliefs (as can in contrast be achieved with the material of the invention).
  • the present invention aims to achieve the above-listed objects by providing a manufactured product, in particular a clothing accessory or a furnishing object, manufactured from a semi-finished product made of an elastomeric polyurethane obtained from the reaction of a formulated polyol and a prepolymer isocyanate, in the presence of a catalyst.
  • the semifinished product is preferably a monolayer, i.e. it consists entirely of the elastomeric polyurethane according to the invention; it is therefore not a multilayer obtained by combining polymeric materials of varying nature.
  • the product can be manufactured entirely from a semi-finished product made of an elastomeric polyurethane or can be obtained by combining the semi-finished elastomeric polyurethane product with other materials, such as, for example, fabric, non-woven fabric, leather, and polymeric resins of various nature other than polyurethane, preferably by sewing and/or gluing.
  • the manufactured product can also be obtained by combining the semi-finished product made of an elastomeric polyurethane resin with another semi-finished product made of an elastomeric polyurethane resin, preferably having the same formulation, that is, by combining two or more semi-finished products made of an elastomeric polyurethane resin according to the invention.
  • the combination can take place by gluing and/or sewing the semi-finished products.
  • two or more semi-finished products having the desired shape are joined by gluing and/or sewing so as to compose the desired manufactured product.
  • the manufactured product is a bag
  • the bag can be obtained from a single semi-finished product made of an elastomeric polyurethane resin, to which the desired shape is given by means of a specific mould, or various semi-finished products can be prepared from an elastomeric polyurethane resin and then joined together by gluing and/or sewing so as to impart the desired shape and look to the bag.
  • the manufactured product of the invention can be obtained through a process of spraying the starting materials (formulated polyol and prepolymer isocyanate) on a special mould having surfaces of the desired shape or through a process of injection into the cavity of a mould having the desired shape.
  • the manufactured product of the invention is a fashion article, a clothing article or accessory, a design article, a household and furnishing article, a leatherware and luggage article, or an architectural finishing surface like wall and floor coverings.
  • the clothing accessory can be, for example, a bag, a belt, a wallet, a briefcase, a watch or jewellery.
  • a clothing article can be, preferably, footwear, dresses, jackets, overcoats, skirts, trousers, bodices or hats.
  • a fashion accessory is preferably a tech device cover for mobile telephones and tablets.
  • An architectural finishing surface can be a cladding for the interior and exterior of locomotive means, for example boats, aeroplanes, automobiles, helicopters, motorcycles and helmets.
  • a product for furnishing and for households for example, an object in various shapes for interior and exterior use, such as, for example, couches, armchairs, poufs, lamps, desks, chairs, vases, bins, sex toys, beakers, cutlery, furniture and lighting in general, or an architectural finishing surface such as wall and floor coverings.
  • the manufactured product is a bag, a belt or a covering for walls or floors.
  • Figure 1 is a photograph of a semi-finished product made of polyurethane obtained at the end of the process of the invention
  • Figure 2 is a photograph of the semi-finished product of Figure 1 bent
  • Figure 3 is a photograph of the front of the manufactured product (bag) of the invention obtained from the semi-finished product of Figure 1 ;
  • Figure 4 is a side view photograph of the bag of Figure 3;
  • Figure 5 is a photograph of a detail of the bas-reliefs of the bag of Figure 3;
  • Figure 6 is a photograph of a belt made of a polyurethane material according to the invention.
  • Figure 7 is a photograph of some decorating panels made with the polyurethane material of the invention.
  • Figures 8 and 9 represent the front and back of a holbas-relief of great depth obtainable with the resin of the invention
  • Figure 10 represents a detail of a fabric strand copied and reproduced with the spraying process according to the invention, in very high definition
  • Figures 1 1 and 12 represent a detail of a mono-material object obtained with the spraying process according to the invention.
  • the invention relates to a manufactured product, in particular a clothing accessory or a furnishing object, entirely or partially obtained from a semifinished product made of a polyurethane resin, wherein the resin is obtained from the reaction of a formulated polyol and a prepolymer isocyanate, in the presence of a catalyst.
  • the manufactured product can be obtained by combining the semi-finished polyurethane product with another material, for example a fabric, such as cotton, silk, hemp, linen etc., a non-woven fabric, another polymeric resin or natural or synthetic leather.
  • the manufactured product can also be obtained by combining two or more semi-finished products made of an elastomeric polyurethane resin (having the same formulation), preferably by sewing and/or gluing so as to obtain a manufactured product of the desired shape.
  • the semi-finished product of the invention is, preferably, a monolayer consisting entirely of the elastomeric polyurethane resin according to the invention.
  • a formulated polyol means a mixture of polyester polyols, polyether polyols, chain extenders and/or cross-linking agents.
  • polyester polyols preferably used are of an aliphatic nature, preferably obtained from adipic acid and ethylene or di-ethylene glycols.
  • the polyether polyols are preferably obtained by alkoxylation of di- functional or tri-functional initiators (for example glycerol).
  • the chain extenders preferably used are butanediol and ethylene or propylene glycols.
  • the formulated polyol can advantageously comprise further additives such as, by way of example, moisture sequestrants, fluidifiers, antioxidants, stabilizers and, when required, flame retardants.
  • the formulated polyol preferably has an oxydril number comprised between 174 and 192.
  • the viscosity of the formulated polyol is preferably comprised between 500 and 700 cps, measured at 30°C.
  • the prepolymer isocyanate is preferably obtained from a reaction of isomers and/or oligomers of 4,4'-diphenyl methane di-isocyanate with propylene glycols or polyether polyols having a low molecular weight.
  • polypropylene glycols di- and tri-propylene glycol are particularly preferred.
  • low molecular weight polyether polyols those with a molecular weight of lower than 1000 and an oxydril number of greater than 1 10 are particularly preferred.
  • the prepolymer isocyanate preferably has an NCO% titre comprised between 24 and 26.
  • the viscosity of the prepolymer isocyanate is comprised between 400 and 600 cps.
  • the catalyst used to prepare the polyurethane of the invention is preferably selected from among organometallic compounds and tertiary amines.
  • Organotin-based compounds such as, for example, dioctyltin dineodecanoate, are particularly preferred among organometallic compounds.
  • tertiary amines the use of triethylenediamine is particularly preferred.
  • Mixtures of different catalysts can be conveniently used.
  • the catalysts can be conveniently diluted, for example with ethylene or propylene glycols.
  • the catalyst is advantageously added to the formulated polyol prior to polymerization with the isocyanate.
  • the manufactured product of the invention essentially consists of a polyurethane elastomeric polymer obtained starting from the reagents and additives specified above.
  • the manufactured product can be obtained by combining the polyurethane polymer with other materials of varying nature, such as natural or synthetic leather, fabric, non-woven fabric, polymeric resins.
  • the elastomeric polyurethane represents the main constituent of the semi-finished product used, entirely or partially, to obtain the manufactured product of the invention, representing 90-95% of the semi-finished product by weight.
  • One or more of such additives, as well as the catalyst, can be added, if convenient, to the formulated polyol immediately prior to use.
  • the manufactured product of the invention is a fashion article, a clothing article or accessory, a design article, a household or furnishing article, a leatherware or luggage article, or an architectural finishing surface such as wall and floor coverings.
  • the clothing accessory can be for example a bag, a belt, a wallet, a document holder, a watch, or jewellery.
  • a clothing article can be, preferably, footwear, dresses, jackets, overcoats, skirts, trousers, bodices or hats.
  • a fashion accessory is preferably a tech device cover for mobile telephones and tablets.
  • An architectural finishing surface can be a cladding for helmets and for the interior and exterior of locomotive means, for example boats, aeroplanes, automobiles, helicopters and motorcycles.
  • a product for furnishing and for households is for example an object for interior and exterior use, preferably couches, armchairs, poufs, lamps, desks, chairs, vases, bins, sex toys, beakers, cutlery, furniture and lighting in general, or an architectural finishing surface such as a wall and floor covering.
  • the manufactured product of the invention comprises bas-reliefs up to a height of 50 cm or 80 cm.
  • the manufactured product of the invention is a bag with bas-reliefs up to a height of 80 cm.
  • the bas- reliefs can arrive up to 80 cm with the possibility of obtaining a variable thickness in the event that it is desired to obtain reliefs that are hollow, or full of material for the entire extent thereof.
  • the manufactured product of the invention can be obtained through a process of spraying the starting materials on a mould having the desired shape or through a process of injecting the same into the cavity of a mould having the desired shape.
  • reaction mixture comprising the formulated polyol, suitably catalyzed, and the prepolymer isocyanate is then sprayed, by means of a spraying machine, onto the mould, heated if necessary to a temperature comprised between 35 and 45°.
  • a release agent can be applied to the mould if necessary to enable easy detachment of the polyurethane from the mould.
  • the release agent is for example a silicone or waxy material.
  • the amount of formulated polyol sprayed onto the mould by means of the spraying machine is, for example, 100 parts by weight, whilst the amount of prepolymer isocyanate is, for example, comprised between 50 and 70 parts by weight, preferably between 58 and 65 parts by weight.
  • reaction catalyst can preferably be added to the formulated polyol just before the spray application on the mould in an amount comprised, for example, between 0.2 and 5 parts by weight.
  • the colourant can be added to the formulated polyol prior to the spray application, or else it is possible to coat the manufactured product obtained at the end of the process.
  • the colourant can be applied on the mould together with the release agent, if present.
  • the spraying machine applies the two starting components (formulated polyol and prepolymer isocyanate) at a flow rate comprised, for example, between 6 and 15 g/sec, preferably between 8 and 12 g/sec, for the polyol, and between 3 and 10 g/sec, preferably between 4 and 7 g/sec, for the isocyanate.
  • the spraying machine deposits one or more layers of the reactive mixture consisting of polyol and isocyanate according to the thickness it is desired to obtain.
  • the thickness of a single layer varies with variations in the final thickness it is desired to obtain.
  • the starting materials are allowed to polymerize for a time comprised between 5 and 20 minutes, preferably between 9 and 15 minutes.
  • the mould can be heated to the temperatures specified above to accelerate the polymerization.
  • the semi-finished product can be coupled (for example sewn or glued) to another material (for example a fabric) to obtain the desired object, i.e. the manufactured product.
  • the semi-finished product can be used as such prior to final finishing as a blank or can be glued or sewn to various components to obtain the desired shape.
  • the semi-finished product can be combined with another semi-finished product of the polymeric nature by gluing and/or sewing to obtain the manufactured product having the desired shape.
  • the mould is opened and it can be prepared, for example, by spray depositing, on the walls of the same, a release agent which facilitates removal of the resin at the end of the process.
  • a polyurethane coating film is applied by spray on the walls of the mould.
  • the mould is closed and the polyol and isocyanate, mixed beforehand, are poured in the necessary amounts into the head of the foam machine.
  • the polymerization reaction takes place inside the mould. At the end of the reaction, the semi-finished product is extracted, checked and subjected to removal of any burr.
  • the refined semi-finished product can be subjected to stabilization in an oven when required to increase its hardness.
  • the polymerization time can vary from 6-7 minutes to about 10-20 minutes in relation to the type of density one wishes to obtain.
  • the semi-finished product obtained with the injection process is monolayer.
  • the semi-finished product can be coupled (for example sewn or glued) to another material (for example a fabric) to obtain the desired object.
  • the semi-finished product can be used as such after a final refining and gluing of the various components to obtain the desired shape.
  • the semi-finished product can be combined with another semi-finished product of the same polymeric nature by gluing and/or sewing to obtain the manufactured product having the desired shape.
  • Figure 1 shows a semi-finished product made of a polyurethane material obtained by means of a spray process used to prepare a bag.
  • the mould used made of metallic material, has the shape of the bag it is desired to obtain, including the bas-reliefs, stitching and decorations.
  • the semi-finished product represented in Figures 1 and 2
  • the semi-finished product has one substantially smooth side which will represent the internal part of the bag, and a moulded side, in which the bas-reliefs and stitching of the original model, reproduced with excellent definition, are clearly evident.
  • Figure 3 shows the finished bag obtained by adding polyurethane handles - obtained with the same spray process on a mould or by injection - to the semi-finished product by gluing. Moreover, the semifinished bag product has been sewn to white fabric, which holds together the semi-finished product, imparting to it the final form of a bag, as can also be seen in Figure 4.
  • FIG. 5 is a photograph of a detail of the bag of Figures 1 and 3, from which one may observe how well defined the bas-reliefs and stitching of the original model are.
  • the technique of the invention it is in fact possible to prepare bas-reliefs even up to heights of 50 cm or up to 80 cm, versus a few cm, of poor definition, with PVC, and with eco-leather the bas-reliefs can be at most a few millimetres.
  • Figure 6 shows an example of another manufactured product, a belt, produced with the technique of the invention
  • Figure 7 shows 3 wall panels produced with the method of the invention.
  • Figures 8 and 9 show a face (front and back) obtained with the resin and the processes of the invention and in which one can note the depth of the bas-relief and the fact that the bas-relief is hollow.
  • Figure 10 represents a detail of a strand of fabric copied and reproduced with the spray process according to the invention, in very high definition; it is possible to note how many sub-strands the strand itself is composed of;
  • Figures 1 1 and 12 represent a detail of a mono-material object obtained with the spray process according to the invention; the three-dimensional bas-relief has reduced width in a plan view (1 mm) and reduced depth (4mm); one may note the detail of the background combined with the smooth three-dimensional bas-relief.
  • the material of the invention unlike PVC and the eco-leather normally used to manufacture clothing accessories or other objects, has the characteristic of being practically scratchproof, and thus of maintaining its aesthetic appearance for a long time. Furthermore, the process of the invention makes it possible to reproduce, with absolute definition, any type of decoration, bas-reliefs of up to 50 cm or up to 80 cm and designs of varying shape, unlikely to be obtainable with an equivalent aesthetic result using PVC.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Insulators (AREA)
  • Organic Insulating Materials (AREA)
  • Apparatus For Radiation Diagnosis (AREA)

Abstract

The invention relates to a manufactured product entirely or partially obtainable from a semi-finished product made from an elastomeric polyurethane resin, wherein the resin is obtained from the reaction of a formulated polyol and a prepolymer isocyanate, in the presence of a catalyst. The manufactured product of the invention is a fashion article, a clothing article or accessory, a design article, a household and furnishing article, a leatherware and luggage article, or an architectural finishing surface, like wall and floor coverings. In particular, the manufactured product of the invention is a bag entirely obtained from a semi-finished product made of an elastomeric polyurethane resin or obtained by combining, by sewing and/or gluing, the semi-finished product with another material, or obtained by combining, by sewing and/or gluing, the semi-finished product with another semi-finished product made of an elastomeric polyurethane resin having the same formulation.

Description

DESCRIPTION
"MANUFACTURED PRODUCT MADE OF RESIN"
Technical field
The present invention relates to a product manufactured from elastomeric polyurethane resin optionally associated with other materials, such as leather, fabric, non-woven fabric or other polymeric resins. The manufactured product of the invention is a fashion article, a clothing article or accessory, a design article, a household and furnishing article, a leatherware and luggage article, or an architectural finishing surface, such as wall and floor coverings.
Background art
In the sector of clothing accessories, objects manufactured from polyvinyl chloride (PVC), such as, for example bags of various shapes and sizes, are well known. PVC bags can be entirely obtained from a sheet of that material, in different colours and thicknesses, by cutting and sewing the desired shape. PVC can also be combined with other materials for the final construction of the bag, for example a fabric or another plastic material. Typically, these bags are "shiny" in appearance and completely smooth (i.e. devoid of reliefs, unless applied by sewing) and have low scratch resistance.
Moreover, PVC yellows under exposure to light and over time tends to deteriorate, becoming brittle and forming cracks. With PVC it is possible to produce bas-reliefs (grammages), but of a coarse type, i.e. without definition.
Moreover, PVC is not recyclable and the manufacturing process is highly polluting.
Objects manufactured from so-called eco-leather, also called eco-friendly leather, eco-hide, eco-friendly hide or low environmental impact leather, are also well known. Such objects are, for example, bags, shoes, wallets, etc.
Eco-leather is normally a bilayer material consisting of a layer of fabric impregnated or spread with polyurethane resins, which can have an appearance like natural leather. With eco-leather one can achieve surfaces in which the typical aspect of natural leather is more or less accentuated, depending on consumer demands and product quality. It is also possible to achieve surface reliefs, normally a few millimetres in height, which are not to be considered true bas-reliefs.
Eco-leather has the great disadvantage of being, in the case of most products on the market, very poorly resistant to scratching, with the consequence that the aesthetics of the product can be compromised even after the object has been used for very little time.
Mono-material objects manufactured from hard or soft bi-component resin using injection moulds are also known.
Such objects are, for example, handles for bags, pendants, bracelets or complete bags or trolley bags.
The disadvantage of the aforesaid products consists in not being able to develop three-dimensional textures and high-definition bas-reliefs (as can in contrast be achieved with the material of the invention).
Therefore, in this sector there remains a need to provide innovative materials for manufacturing clothing accessories and furnishing objects characterized by good resistance to wear (to scratching in particular), an attractive aesthetic appearance for consumers, a soft-touch characteristic, a good definition of details, and in particular the possibility of obtaining bas-reliefs of great depth, both hollow and full of material throughout their extent.
Disclosure of the invention
The present invention aims to achieve the above-listed objects by providing a manufactured product, in particular a clothing accessory or a furnishing object, manufactured from a semi-finished product made of an elastomeric polyurethane obtained from the reaction of a formulated polyol and a prepolymer isocyanate, in the presence of a catalyst. The semifinished product is preferably a monolayer, i.e. it consists entirely of the elastomeric polyurethane according to the invention; it is therefore not a multilayer obtained by combining polymeric materials of varying nature. The product can be manufactured entirely from a semi-finished product made of an elastomeric polyurethane or can be obtained by combining the semi-finished elastomeric polyurethane product with other materials, such as, for example, fabric, non-woven fabric, leather, and polymeric resins of various nature other than polyurethane, preferably by sewing and/or gluing. The manufactured product can also be obtained by combining the semi-finished product made of an elastomeric polyurethane resin with another semi-finished product made of an elastomeric polyurethane resin, preferably having the same formulation, that is, by combining two or more semi-finished products made of an elastomeric polyurethane resin according to the invention. The combination can take place by gluing and/or sewing the semi-finished products. In other words, two or more semi-finished products having the desired shape are joined by gluing and/or sewing so as to compose the desired manufactured product. For example, if the manufactured product is a bag, the bag can be obtained from a single semi-finished product made of an elastomeric polyurethane resin, to which the desired shape is given by means of a specific mould, or various semi-finished products can be prepared from an elastomeric polyurethane resin and then joined together by gluing and/or sewing so as to impart the desired shape and look to the bag.
The manufactured product of the invention can be obtained through a process of spraying the starting materials (formulated polyol and prepolymer isocyanate) on a special mould having surfaces of the desired shape or through a process of injection into the cavity of a mould having the desired shape.
The manufactured product of the invention is a fashion article, a clothing article or accessory, a design article, a household and furnishing article, a leatherware and luggage article, or an architectural finishing surface like wall and floor coverings.
Preferably, the clothing accessory can be, for example, a bag, a belt, a wallet, a briefcase, a watch or jewellery. A clothing article can be, preferably, footwear, dresses, jackets, overcoats, skirts, trousers, bodices or hats.
A fashion accessory is preferably a tech device cover for mobile telephones and tablets.
An architectural finishing surface can be a cladding for the interior and exterior of locomotive means, for example boats, aeroplanes, automobiles, helicopters, motorcycles and helmets.
A product for furnishing and for households, for example, an object in various shapes for interior and exterior use, such as, for example, couches, armchairs, poufs, lamps, desks, chairs, vases, bins, sex toys, beakers, cutlery, furniture and lighting in general, or an architectural finishing surface such as wall and floor coverings.
In a particularly preferred embodiment of the invention, the manufactured product is a bag, a belt or a covering for walls or floors.
Brief description of drawings
The invention will be described below, also with reference to the appended figures, in which:
Figure 1 is a photograph of a semi-finished product made of polyurethane obtained at the end of the process of the invention;
Figure 2 is a photograph of the semi-finished product of Figure 1 bent;
Figure 3 is a photograph of the front of the manufactured product (bag) of the invention obtained from the semi-finished product of Figure 1 ;
Figure 4 is a side view photograph of the bag of Figure 3;
Figure 5 is a photograph of a detail of the bas-reliefs of the bag of Figure 3;
Figure 6 is a photograph of a belt made of a polyurethane material according to the invention;
Figure 7 is a photograph of some decorating panels made with the polyurethane material of the invention;
Figures 8 and 9 represent the front and back of a holbas-relief of great depth obtainable with the resin of the invention;
Figure 10 represents a detail of a fabric strand copied and reproduced with the spraying process according to the invention, in very high definition;
Figures 1 1 and 12 represent a detail of a mono-material object obtained with the spraying process according to the invention.
Detailed Description of the Invention
The invention relates to a manufactured product, in particular a clothing accessory or a furnishing object, entirely or partially obtained from a semifinished product made of a polyurethane resin, wherein the resin is obtained from the reaction of a formulated polyol and a prepolymer isocyanate, in the presence of a catalyst. The manufactured product can be obtained by combining the semi-finished polyurethane product with another material, for example a fabric, such as cotton, silk, hemp, linen etc., a non-woven fabric, another polymeric resin or natural or synthetic leather. The manufactured product can also be obtained by combining two or more semi-finished products made of an elastomeric polyurethane resin (having the same formulation), preferably by sewing and/or gluing so as to obtain a manufactured product of the desired shape.
The semi-finished product of the invention is, preferably, a monolayer consisting entirely of the elastomeric polyurethane resin according to the invention.
A formulated polyol means a mixture of polyester polyols, polyether polyols, chain extenders and/or cross-linking agents.
The polyester polyols preferably used are of an aliphatic nature, preferably obtained from adipic acid and ethylene or di-ethylene glycols.
The polyether polyols are preferably obtained by alkoxylation of di- functional or tri-functional initiators (for example glycerol).
The chain extenders preferably used are butanediol and ethylene or propylene glycols.
The formulated polyol can advantageously comprise further additives such as, by way of example, moisture sequestrants, fluidifiers, antioxidants, stabilizers and, when required, flame retardants.
The formulated polyol preferably has an oxydril number comprised between 174 and 192.
The viscosity of the formulated polyol is preferably comprised between 500 and 700 cps, measured at 30°C.
The prepolymer isocyanate is preferably obtained from a reaction of isomers and/or oligomers of 4,4'-diphenyl methane di-isocyanate with propylene glycols or polyether polyols having a low molecular weight.
Among the polypropylene glycols, di- and tri-propylene glycol are particularly preferred. Among the low molecular weight polyether polyols, those with a molecular weight of lower than 1000 and an oxydril number of greater than 1 10 are particularly preferred.
The prepolymer isocyanate preferably has an NCO% titre comprised between 24 and 26. Preferably, the viscosity of the prepolymer isocyanate is comprised between 400 and 600 cps.
The catalyst used to prepare the polyurethane of the invention is preferably selected from among organometallic compounds and tertiary amines. Organotin-based compounds, such as, for example, dioctyltin dineodecanoate, are particularly preferred among organometallic compounds. Among the tertiary amines, the use of triethylenediamine is particularly preferred. Mixtures of different catalysts can be conveniently used. Likewise, the catalysts can be conveniently diluted, for example with ethylene or propylene glycols.
The catalyst is advantageously added to the formulated polyol prior to polymerization with the isocyanate.
The manufactured product of the invention essentially consists of a polyurethane elastomeric polymer obtained starting from the reagents and additives specified above. Alternatively, the manufactured product can be obtained by combining the polyurethane polymer with other materials of varying nature, such as natural or synthetic leather, fabric, non-woven fabric, polymeric resins.
The elastomeric polyurethane, including the additives, represents the main constituent of the semi-finished product used, entirely or partially, to obtain the manufactured product of the invention, representing 90-95% of the semi-finished product by weight. One or more of such additives, as well as the catalyst, can be added, if convenient, to the formulated polyol immediately prior to use.
The manufactured product of the invention is a fashion article, a clothing article or accessory, a design article, a household or furnishing article, a leatherware or luggage article, or an architectural finishing surface such as wall and floor coverings.
Preferably, the clothing accessory can be for example a bag, a belt, a wallet, a document holder, a watch, or jewellery. A clothing article can be, preferably, footwear, dresses, jackets, overcoats, skirts, trousers, bodices or hats.
A fashion accessory is preferably a tech device cover for mobile telephones and tablets.
An architectural finishing surface can be a cladding for helmets and for the interior and exterior of locomotive means, for example boats, aeroplanes, automobiles, helicopters and motorcycles.
A product for furnishing and for households is for example an object for interior and exterior use, preferably couches, armchairs, poufs, lamps, desks, chairs, vases, bins, sex toys, beakers, cutlery, furniture and lighting in general, or an architectural finishing surface such as a wall and floor covering.
In a preferred embodiment, the manufactured product of the invention comprises bas-reliefs up to a height of 50 cm or 80 cm. In particular, the manufactured product of the invention is a bag with bas-reliefs up to a height of 80 cm. For example, in the bag of Figures 1 -5 there are bas- reliefs with a thickness of up to 3 cm. In the wall panel in Figure 7, the bas- relief can arrive up to 80 cm with the possibility of obtaining a variable thickness in the event that it is desired to obtain reliefs that are hollow, or full of material for the entire extent thereof.
The manufactured product of the invention can be obtained through a process of spraying the starting materials on a mould having the desired shape or through a process of injecting the same into the cavity of a mould having the desired shape.
Both in the case of the spray process and in the case of the injection process, it is necessary to prepare a mould having the desired shape of the object one wishes to prepare. In particular, from a model of the previously prepared object, a copy of its shape is obtained. A mould made of polymeric material or metallic material is prepared from this copy.
The reaction mixture comprising the formulated polyol, suitably catalyzed, and the prepolymer isocyanate is then sprayed, by means of a spraying machine, onto the mould, heated if necessary to a temperature comprised between 35 and 45°. A release agent can be applied to the mould if necessary to enable easy detachment of the polyurethane from the mould.
The release agent is for example a silicone or waxy material.
The amount of formulated polyol sprayed onto the mould by means of the spraying machine is, for example, 100 parts by weight, whilst the amount of prepolymer isocyanate is, for example, comprised between 50 and 70 parts by weight, preferably between 58 and 65 parts by weight.
As previously specified, the reaction catalyst can preferably be added to the formulated polyol just before the spray application on the mould in an amount comprised, for example, between 0.2 and 5 parts by weight.
If one wishes to colour the material, the colourant can be added to the formulated polyol prior to the spray application, or else it is possible to coat the manufactured product obtained at the end of the process. Alternatively, the colourant can be applied on the mould together with the release agent, if present.
The spraying machine applies the two starting components (formulated polyol and prepolymer isocyanate) at a flow rate comprised, for example, between 6 and 15 g/sec, preferably between 8 and 12 g/sec, for the polyol, and between 3 and 10 g/sec, preferably between 4 and 7 g/sec, for the isocyanate.
The spraying machine deposits one or more layers of the reactive mixture consisting of polyol and isocyanate according to the thickness it is desired to obtain. The thickness of a single layer varies with variations in the final thickness it is desired to obtain.
Once the application of the one or more layers on the mould has ended, the starting materials are allowed to polymerize for a time comprised between 5 and 20 minutes, preferably between 9 and 15 minutes. The mould can be heated to the temperatures specified above to accelerate the polymerization.
At the end of polymerization, one obtains a semi-finished monolayer product, which is allowed to cool and then removed from the mould. The contours of the semi-finished product are finished so as to give the desired shape.
The semi-finished product can be coupled (for example sewn or glued) to another material (for example a fabric) to obtain the desired object, i.e. the manufactured product. Alternatively, the semi-finished product can be used as such prior to final finishing as a blank or can be glued or sewn to various components to obtain the desired shape.
Alternatively, the semi-finished product can be combined with another semi-finished product of the polymeric nature by gluing and/or sewing to obtain the manufactured product having the desired shape. In the case of an injection process, the mould is opened and it can be prepared, for example, by spray depositing, on the walls of the same, a release agent which facilitates removal of the resin at the end of the process.
If required for aesthetic needs, a polyurethane coating film is applied by spray on the walls of the mould.
After this possible initial preparation, the mould is closed and the polyol and isocyanate, mixed beforehand, are poured in the necessary amounts into the head of the foam machine.
The polymerization reaction takes place inside the mould. At the end of the reaction, the semi-finished product is extracted, checked and subjected to removal of any burr.
The refined semi-finished product can be subjected to stabilization in an oven when required to increase its hardness.
The polymerization time can vary from 6-7 minutes to about 10-20 minutes in relation to the type of density one wishes to obtain.
The semi-finished product obtained with the injection process is monolayer.
The semi-finished product can be coupled (for example sewn or glued) to another material (for example a fabric) to obtain the desired object. Alternatively, the semi-finished product can be used as such after a final refining and gluing of the various components to obtain the desired shape. Alternatively, the semi-finished product can be combined with another semi-finished product of the same polymeric nature by gluing and/or sewing to obtain the manufactured product having the desired shape.
An example of a manufactured product obtained with the method of the invention is shown in the appended figures.
Figure 1 shows a semi-finished product made of a polyurethane material obtained by means of a spray process used to prepare a bag. The mould used, made of metallic material, has the shape of the bag it is desired to obtain, including the bas-reliefs, stitching and decorations.
After the spray application of the starting materials specified above and subsequent cooling, the semi-finished product, represented in Figures 1 and 2, can be removed from the mould. In Figure 2 it is possible to note that the semi-finished product has one substantially smooth side which will represent the internal part of the bag, and a moulded side, in which the bas-reliefs and stitching of the original model, reproduced with excellent definition, are clearly evident.
Figure 3, in contrast, shows the finished bag obtained by adding polyurethane handles - obtained with the same spray process on a mould or by injection - to the semi-finished product by gluing. Moreover, the semifinished bag product has been sewn to white fabric, which holds together the semi-finished product, imparting to it the final form of a bag, as can also be seen in Figure 4.
Figure 5 is a photograph of a detail of the bag of Figures 1 and 3, from which one may observe how well defined the bas-reliefs and stitching of the original model are. With the technique of the invention it is in fact possible to prepare bas-reliefs even up to heights of 50 cm or up to 80 cm, versus a few cm, of poor definition, with PVC, and with eco-leather the bas-reliefs can be at most a few millimetres.
Figure 6 shows an example of another manufactured product, a belt, produced with the technique of the invention, whilst Figure 7 shows 3 wall panels produced with the method of the invention.
Figures 8 and 9 show a face (front and back) obtained with the resin and the processes of the invention and in which one can note the depth of the bas-relief and the fact that the bas-relief is hollow.
Figure 10 represents a detail of a strand of fabric copied and reproduced with the spray process according to the invention, in very high definition; it is possible to note how many sub-strands the strand itself is composed of; Figures 1 1 and 12 represent a detail of a mono-material object obtained with the spray process according to the invention; the three-dimensional bas-relief has reduced width in a plan view (1 mm) and reduced depth (4mm); one may note the detail of the background combined with the smooth three-dimensional bas-relief.
The material of the invention, unlike PVC and the eco-leather normally used to manufacture clothing accessories or other objects, has the characteristic of being practically scratchproof, and thus of maintaining its aesthetic appearance for a long time. Furthermore, the process of the invention makes it possible to reproduce, with absolute definition, any type of decoration, bas-reliefs of up to 50 cm or up to 80 cm and designs of varying shape, unlikely to be obtainable with an equivalent aesthetic result using PVC.

Claims

1 . A manufactured product entirely or partially obtainable from a semifinished product made of an elastomeric polyurethane resin, wherein said resin is obtained from a reaction of a formulated polyol having an oxydril number comprised between 174 and 192 and comprising a mixture of: polyester polyols, polyether polyols, chain extenders and/or cross-linking agents; with a prepolymer isocyanate obtained from a reaction of isomers and/or oligomers of 4,4'-diphenyl methane di-isocyanate with propylene glycols or polyether polyols having a low molecular weight, in the presence of a catalyst.
2. The manufactured product according to claim 1 , wherein said semifinished product is a monolayer made of an elastomeric polyurethane resin.
3. The manufactured product according to claim 1 or 2, obtainable by combining, preferably by sewing and/or gluing, said semi-finished product made of an elastomeric polyurethane resin with another material, preferably a fabric, a polymeric resin or a natural or synthetic leather.
4. The manufactured product according to claim 1 or 2, obtainable by combining said semi-finished product with another semi-finished product made of an elastomeric polyurethane resin, preferably by gluing and/or sewing the semi-finished products to obtain the desired shape.
5. The manufactured product according to claim 1 , entirely obtainable from a semi-finished product made of an elastomeric polyurethane resin.
6. The manufactured product according to any one of claims 1 to 5, wherein said formulated polyol comprises a mixture of: polyester polyols, obtained from adipic acid and ethylene or di-ethylene glycols; polyester polyols, obtained by alkoxylation of di-functional or tri-functional initiators; chain extenders, selected from among butanediol and ethylene or propylene glycols; and/or cross-linking agents.
7. The manufactured product according to any one of claims 1 to 6, wherein said polypropylene glycols are di- and tri-propylene glycol; said low-molecular weight polyether polyols have a molecular weight lower than 1000 and an oxydril number greater than 1 10.
8. The manufactured product according to any one of claims 1 to 7, wherein said prepolymer isocyanate has an NCO% titre comprised between 24 and 26.
9. The manufactured product according to any one of claims 1 to 8, wherein said manufactured product is a fashion article, a clothing article or accessory, a design article, a household and furnishing article, a leatherware or luggage article, or an architectural finishing surface such as wall and floor coverings.
10. The manufactured product according to claim 9, wherein said clothing accessory is a bag, a belt, a wallet, a document holder, a watch, or jewellery; said clothing article is selected from: footwear, dresses, jackets, overcoats, skirts, trousers, bodices or hats; said fashion accessory is a tech device cover for mobile telephones and tablets; said architectural finishing surface is a cladding for interior and exterior surfaces of locomotive means, preferably for boats, aeroplanes, automobiles, helicopters, motorcycles and helmets, or a covering for walls and floors; said product for furnishing and for households is an object for interior and exterior use, preferably couches, armchairs, poufs, lamps, desks, chairs, vases, bins, sex toys, beakers, cutlery, furniture and lighting.
1 1 . The manufactured product according to any one of claims 1 to 10, comprising bas-reliefs up to a height of 50 cm.
12. The manufactured product according to any one of claims 1 to 10, wherein said bas-reliefs have height of up to 80 cm.
13. The manufactured product according to claim 1 1 or 12, wherein said bas-reliefs are hollow or full.
14. A manufactured product in the form of a bag entirely or partially obtainable from a semi-finished product made of an elastomeric polyurethane resin, wherein the resin is obtained by a reaction of a formulated polyol comprising a mixture of: polyester polyols, polyether polyols, chain extenders and/or cross-linking agents; with a prepolymer isocyanate obtained from a reaction of isomers and/or oligomers of 4,4'-diphenyl methane di-isocyanate with propylene glycols or polyether polyols having a low molecular weight, in the presence of a catalyst.
15. The manufactured product in the form of a bag according to claim 14, comprising bas-reliefs up to a height of 50 cm.
16. The manufactured product in the form of a bag according to claim 14, comprising bas-reliefs up to a height of 80 cm
17. The manufactured product according to any one of claims 14 to 16, wherein said bag is entirely obtained from a semi-finished product made of an elastomeric polyurethane resin as defined in claims 1 to 8, or is obtained by combining the semi-finished product with a fabric, a non-woven fabric, polymeric resins or a natural or synthetic leather, by means of sewing or gluing, or else obtained by combining the semi-finished product with another semi-finished product made of an elastomeric polyurethane resin.
18. A semi-finished product made of an elastomeric polyurethane resin, wherein the resin is obtained by a reaction of a formulated polyol and a prepolymer isocyanate in the presence of a catalyst, as specified in claim 1 .
19. A semi-finished product according to claim 18, wherein said semifinished product is a monolayer of an elastomeric polyurethane resin.
20. A process for obtaining a semi-finished product according to claim 18 to 19, comprising the steps of:
- providing a mould of a desired shape;
- applying, using a sprayer machine, one or more layers of a mixture of a formulated polyol, prepolymer isocyanate and a catalyst; or pouring a mixture of a formulated polyol, prepolymer isocyanate and catalyst into a mould which has been previously closed;
- allowing the mixture to polymerize for a time comprised between 5 and 20 minutes;
- removing the semi-finished product from the mould.
21 . A process for preparing a manufactured product according to any one of claims 1 to 17, wherein the semi-finished product obtained according to the process of claim 20 is sewn and/or glued so as to give a desired shape or is combined, by means of sewing and/or gluing, to another material, preferably to a fabric, a non-woven fabric, a natural or synthetic leather, or polymeric resins, in such a way as to obtain the desired shape, or is combined, by sewing and/or gluing, to another semi-finished product made of an elastomeric polyurethane resin.
EP14777827.8A 2013-08-06 2014-08-05 Manufactured product made of resin Withdrawn EP3030596A1 (en)

Applications Claiming Priority (2)

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IT001349A ITMI20131349A1 (en) 2013-08-06 2013-08-06 MADE IN RESIN
PCT/IB2014/063709 WO2015019287A1 (en) 2013-08-06 2014-08-05 Manufactured product made of resin

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CN107581739A (en) * 2017-08-23 2018-01-16 苏州井村服饰有限公司 A kind of durable type health care wallet
CN107364211A (en) * 2017-08-23 2017-11-21 苏州井村服饰有限公司 A kind of durable type wallet
CN107581736A (en) * 2017-08-31 2018-01-16 太仓雄鹰皮具有限公司 A kind of wallet with far-infrared health care function
CN107594805A (en) * 2017-08-31 2018-01-19 太仓雄鹰皮具有限公司 A kind of wallet with massage functions
IT201900004101U1 (en) * 2019-11-15 2021-05-15 Carlo Cristina Di MULTILAYER COUPLED

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JPS54961B1 (en) * 1969-04-24 1979-01-18
JPS5221561B2 (en) * 1972-12-28 1977-06-11
AU651378B2 (en) * 1990-09-28 1994-07-21 Kuraray Co., Ltd. Suede-like napped sheet excellent in sweat resistance
US6992134B2 (en) * 2002-10-29 2006-01-31 Tim Croley Polyurethane system and application thereof

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