WO2013174870A1 - Matériau multicouche comprenant du textile - Google Patents

Matériau multicouche comprenant du textile Download PDF

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Publication number
WO2013174870A1
WO2013174870A1 PCT/EP2013/060518 EP2013060518W WO2013174870A1 WO 2013174870 A1 WO2013174870 A1 WO 2013174870A1 EP 2013060518 W EP2013060518 W EP 2013060518W WO 2013174870 A1 WO2013174870 A1 WO 2013174870A1
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WO
WIPO (PCT)
Prior art keywords
fabric
multilayer material
layer
cellulose acetate
polymer
Prior art date
Application number
PCT/EP2013/060518
Other languages
English (en)
Inventor
Massimo DE RIGO
Roberto Pippa
Stefano ZUIN
Original Assignee
De Rigo S.P.A.
Consorzio Venezia Ricerche
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 De Rigo S.P.A., Consorzio Venezia Ricerche filed Critical De Rigo S.P.A.
Publication of WO2013174870A1 publication Critical patent/WO2013174870A1/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C5/00—Constructions of non-optical parts
    • G02C5/008—Spectacles frames characterized by their material, material structure and material properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D12/00—Producing frames
    • B29D12/02—Spectacle frames
    • 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
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/10—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose 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
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/14—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose characterised by containing special compounding ingredients
    • B32B23/18—Fillers
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06—Vegetal fibres
    • B32B2262/062—Cellulose fibres, e.g. cotton
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • 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
    • B32B2451/00—Decorative or ornamental articles
    • 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
    • B32B2479/00—Furniture
    • 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

  • Multilayer material comprising fabric
  • the present invention relates to a multilayer material comprising a fabric of natural fibres and plasticized cellulose acetate, a method for its production and an article, in particular a spectacle frame, comprising the multilayer material.
  • Cellulose acetate is a thermoplastic polymer directly obtainable from cotton or wood pulp (cellulose) by treatment with acetic anhydride.
  • cellulose acetate is normally plasticized to decrease its softening and processing temperatures and to transform it into sheets or plates, for example by extrusion.
  • plasticizing additives in fact, the softening temperature of ethyl acetate is very close to its decomposition temperature, which occurs with the formation of volatile substances and with irreversible changes of its characteristics.
  • Plasticized cellulose acetate (normally by addition of diethyl phthalate in amount 20- 40% w/w ) is one of most widely used polymers in the manufacture of spectacle frames(i.e. eyeglasses, eyewear ). It shows peculiar characteristics and well-known behaviour during processing, which make it virtually irreplaceable in the production of objects with shapes and designs that vary annually according to the market needs of the fashion industry. In fact, the possibility of operating on sheets of variable thickness and colour using highly automated mechanical technologies (cutting, milling etc.) allows to manufacture objects in different forms (patterns) also for the production of small-scale series of eyeglasses. This is an essential economical requirement for the productive sector of the spectacle frames.
  • the currently used multilayers of cellulose acetate essentially consist of sheets of the same polymer, optionally with different colours.
  • Various designs are obtained by different techniques, including screen printing and pad printing.
  • EP947313 discloses a multilayer laminate for waterproof and breathable garments comprising a fabric bonded to a coating of polypropylene via an adhesive layer made of olefin polymers.
  • EP922567 discloses a multilayer structure comprising a layer based on unsaturated polymer of acrylonitrile and a layer of an organic polymer.
  • EP2199728 discloses a material for applications in bulletproof fabrics, obtained by pasting a polymeric material of high strength of a base fabric by an adhesive based on polyurethane, polyethylene, polyamide and/or polyester.
  • US2010330333 describes a composite material comprising a fabric in the form of a sheet and a layer of polyurethane, provided with capillary holes that pass through it, which is joined to the fabric directly or via an additional adhesive layer.
  • W093/11927 discloses a multilayer material for use in motor vehicles with foams made of polyolefin particles and a decorative layer comprising a fabric with a mesh based on olefin polymers.
  • a multilayer textile material comprising an essentially transparent outer casing of polymer material, such as polyamide, polyurethane, teflon or acrylic polymer, and an inner filling consisting of textile fibres, natural and non-natural, in the form of tops and/or a web.
  • WO2011/091878 describes a composition comprising a multilayer fabric, at least one layer of foam made from polyvinyl chloride and an outer layer stabilizer comprising a compound of calcium and/or zinc.
  • WO2011/022031 describes a multilayer material that includes, in addition to a fabric, a layer comprising high modulus fibres, in a non-vowen form, that are not oriented in a thermoplastic matrix consisting of polyolefins, polyesters or polyamides.
  • WO2010049743 relates to a multilayer material comprising a fabric and a metallic layer joined together using an adhesive layer of plastic material.
  • US 2,036,424 relates to the impregnation of cellulose materials such as cloth, thread, paper etc. with an organic solvent solution of a cellulose ester or ether to obtain a material suited for electrical insulation or a moisture-resistant thread.
  • US 4,061,823 discloses a highly machinable, shapeable decorative laminate made from a non-abrasive base core consisting of a plurality of sheets, each sheet consisting essentially of cotton linter fibres in paper form containing a curd phenolic resin, the core having superimposed thereon a print sheet impregnated with a cured thermoset resin.
  • GB 2322099 provides wear-resistant laminated articles, in particular composite rotor blades of natural fibre or regenerated natural fibre -reinforced thermoset resin with an aramid fibre-fabric working surface to reduce erosion in use.
  • the plastic materials used for the preparation of the multilayer according to the prior art are, partially or totally, petroleum derivatives, i.e. deriving from a non-renewable source, and hardly recyclable and/or biodegradable.
  • the materials comprising multilayer fabrics according to the prior art are hardly treatable by the techniques normally used for the machining of spectacle frames, as they are subject to delamination of the layers or general deterioration during such treatments as cutting, milling, hot bending etc.
  • An object of the present invention is to provide a multilayer material that is more eco-friendly and bio-degradable than the prior art materials.
  • An aim of the present invention is to provide a multilayer material, comprising a fabric, which is readily-machinable by the techniques normally used in manufacturing, particularly in the production of frames for glasses.
  • Another aim of the present invention is to provide a material, preferably in the form of sheet or semi-finished plate, which can be used in the production of a manufactured product having the outer surface with a tactile sensation similar to a fabric and with designs and textures derived from those usually found on clothes.
  • a multilayer material comprising at least one layer a) and at least one layer b), alternating and permanently adhering to each other, wherein:
  • - layer a comprises a fabric of natural fibres impregnated with a substance selected from a plasticized cellulose acetate polymer, a polymer or copolymer of at least one alkyl acrylate, a polyester or a functionalized polyether urethane, or mixtures thereof, and
  • - layer b) comprises a polymer of cellulose acetate comprising at least one plasticizer.
  • This goal was also achieved by a sheet or a finished or semi-finished item, selected from an eyeglasses frame, an household good, a piece of furniture, an eyeglasses case, an automotive or vehicle component comprising said multilayer material.
  • This aim is also achieved by a process for the preparation of said multilayer material comprising the steps of:
  • step b) drying the impregnated fabric obtained in step a) completely or almost completely by removing the organic solvent or water;
  • step b) overlaying, in an alternating sequence, one layer of the impregnated and dried fabric obtained in step b) and a layer of cellulose acetate comprising at least a plasticizer, to obtain a semi-finished multilayer material;
  • step d) joining the layers of the semi-finished material of step c) forming a multilayer material by thermo compression at 120 to 190°C and with a closure force from 1 to 10 tons for 1 to 20 min, wherein temperature, pressure and time of the treatment may vary according to the number of layers and the thickness of the material to be obtained, and
  • step d) cooling multilayer material of step d) to 20-30°C under a closure force from 10 to 25 tons in 1 to 15 min.
  • Figure 2 Production Scheme for the multilayer material (e.g. with cellulose acetate as impregnation polymer) according to the invention.
  • Figure 3 Stress strain curve (UNI EN ISO 13934- 1) Jacky Royal8TM fabric as is (sample T) and Jacky Royal8TM impregnated with 77% w / w CA for treatment with a solution of CA 8% in acetone ( sample T-CA1, CA-T curve).
  • Figure 4 Photograph of Sample n. 120476 subjected to tests for eyeglasses frames according to ISO 12870.
  • an element or composition "comprising" a certain substance may consist of said substance or of a mixture including said substance, in addition to other substances.
  • a solvent or water is totally removed or almost completely from a composition when the content of free solvent after drying is reduced to less than 90% of the initial content, preferably to less than 95% or less than 99%.
  • alternating layers of two different materials having contact faces are layers in any sequence, wherein each layer can be adjacent, on each contact face, to a layer of the same material or of different material (e.g., naming the two materials A and B, the sequence of layers can be ABABAB, ABBA, BAABABABAABB etc.).
  • natural fibres includes fibres of vegetable origin such as, but not limited to, cotton, hemp and flax, and of animal origin such as, but not exclusively, wool and silk, and mixtures thereof.
  • fabrics and “cloth” indicate a product obtained by weaving (traditional fabric, denim cotton type) or through different methods (type “non- woven", for example, obtained by pressing of stacked layers).
  • alkyl acrylate means an acrylic (or polyacrylic) acid ester with methyl alcohol, ethyl and/or butyl.
  • cellulose acetate indicates a cellulose ester, normally diacetate or triacetate, obtained by acetylation of cellulose, which can have an acetylation degree between 50-62% by weight of acetic acid liberated by basic hydrolysis of cellulose acetate.
  • plasticized polymer means a mixture comprising a polymer and at least one plasticizer.
  • plasticizer means a substance, miscible with the polymer, which can reduce the glass transition temperature (Tg) of the polymer, so as to lower its softening temperature and the viscosity of the melt, and to allow the machining of the material at temperatures below the decomposition temperature, avoiding the loss of functional, visual and tactile properties.
  • Non- limiting examples of plasticizers in the present invention are esters of alkylphthalates (dialkylphtlalate as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di-2- methoxyethyl phthalate), trimellitates (trimethyl trimellitate, triethyl trimellitate and tributyl trimellitate), esters of orthophosphoric acid (triphenyl phosphate, triethyl phosphate, tricresyl phosphate, ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate), citrates and biodegradable plasticizer (triethyl citrate, acetyl triethyl citrate, acetyl tributyl citrate), benzoates (ethyl-or benzoyl benzoate), tartrate (dibutyl tartrate), etilftaliletilglioclato (EPEG)
  • a solution of plasticized cellulose acetate means a composition wherein a polymer is dissolved in an organic solvent to obtain a solution with a concentration by weight less than 30% and with suitable viscosity to penetrate and impregnate a fabric.
  • solvents for cellulose acetate are: acetone (also in mixtures with 5- 10% water), methyl-ethyl ketone, cyclohexanone, diacetone alcohol, methyl acetate, ethyl acetate, ethyl lactate, methyl glycol, methyl glycol acetate, dimethylformamide, tetrachlorofurane and methylene chloride (also in mixture with 10% methanol).
  • percentages of the components of a mixture refer to weight of the component with respect to the total weight of the mixture (w/w).
  • the present invention provides a multilayer material comprising at least one layer a) and at least one layer b), alternating and permanently adhering to each other, wherein:
  • - layer a comprises a fabric of natural fibres impregnated with a substance selected from a plasticized cellulose acetate polymer, a polymer or copolymer of at least one alkyl acrylate, a polyester or a functionalized polyethereurethane, or mixtures thereof, and
  • - layer b) comprises a polymer of cellulose acetate comprising at least one plasticizer.
  • the material according to the present invention when subjected to the machining typically used in the manufacture of eyeglasses frames, has characteristics of higher resistance compared to products comprising multilayer material of the prior art.
  • the comparison specimen obtained by thermo-compression (130- 160°C) of alternating layers of fabric and sheets of CA by 0.5 mm in thickness, shows a good surface appearance but an insufficient adhesion between the layers, such as to show detachments of layers for 90° bending of specimens, with evident de-laminations between the layers.
  • the delaminated layers show a low penetration of CA within the texture of the fabric and wires.
  • a cutting test using a rotary cutter results in a high formation of "unraveling" (with damaged/breaking yarns) of the fabric and detachment of the layers, which cannot be improved by changing the cutting parameters (type of mills, speed, etc.).
  • Test multilayer materials were obtained by thermo-compression of interposed layers of natural fibres fabrics and layers of plasticized cellulose acetate approximately 0.5 mm thick, wherein the latter layers are on one or on both sides of the fabric. Even these multilayer materials show a layer adhesion that is insufficient to ensure a good workability, for example by milling or cutting.
  • ratios of polymer / fabric can be achieved as high as needed, also, as a non-limiting example, in 1 : 1 polymer / fabric weight ratio.
  • said treated fabric (TP) is the layer which is alternated to the sheets of plasticized cellulose acetate (CAp) obtaining, for example, a sequence (TP / CAp / TP / CAp) n where n is a number equal to or greater than 1, up to the desired thickness of the sheet.
  • the natural fibre cloths that are evenly coated/impregnated by the polymer, after evaporation of the solvent, are more rigid than the un-impregnated/un- coated fibre.
  • the multilayer material according to the invention can be mechanically processed, for example cut or milled, causing substantially no ravellings, obtaining surfaces, either smooth or with the texture of the fabric, that are resistant and aesthetically pleasing and do not produce sharp edges or surfaces in case of breakage.
  • the plasticizer content of the layer a) and/or b) is from 20 to 40% by weight on the total weight of the layer.
  • the plasticizer of the layer and/or b) is diethyl phthalate.
  • layer a) is from 0.1 to 2.0 mm thick, preferably 0.5 mm, and layer b) is from 0.1 to 4, 0 mm thick.
  • the multilayer material according to the invention is a material with a greater quantity of components obtained from renewable resources (bio-based materials), therefore more environmentally friendly and, advantageously, also more bio-degradable.
  • the natural fibre consists of or comprises cotton.
  • the plasticizer used in the layers a) and/or b) of the multilayer material of the invention is obtained from completely or partially renewable resources (bio- plasticizer).
  • the plasticizer used in the layers a) and/or b) of the multilayer material of the invention is biodegradable or compostable.
  • the natural fibre is cotton, in particular in the form of denim fabric, and the fabric is up to 100% cotton, impregnated with the polymer of cellulose acetate plastic.
  • the multilayer material of the present invention may consist of alternating layers of: - Fabric of natural fibres, preferably cotton, with different texture and weight, preferably denim, which can be treated with products and processes normally used in the textile and clothing industry, such as natural dyes, for example indigo which can enable the effect "washed”, “aged” in the typical style of “jeans”, and with dyes or synthetic colours that are stable to washing.
  • natural dyes for example indigo which can enable the effect "washed”, “aged” in the typical style of "jeans”, and with dyes or synthetic colours that are stable to washing.
  • the choice of fabric is independent of the weft, warp, yarn weight.
  • Said fabric is modified by impregnation with a polymer such as plasticized cellulose acetate, or polar thermoplastic polymers "compatible" (i.e., able to adhere permanently after a process such as thermo-compression) with plasticized cellulose acetate, such as for example polyalkylacrilates or modified polyesters (sulfonates) or polyether urethanes.
  • a polymer such as plasticized cellulose acetate, or polar thermoplastic polymers "compatible” (i.e., able to adhere permanently after a process such as thermo-compression) with plasticized cellulose acetate, such as for example polyalkylacrilates or modified polyesters (sulfonates) or polyether urethanes.
  • the polymer impregnating/coating the natural fibre is at least one of cellulose acetate or methyl ethyl or butyl acrylate, and/or their copolymers, terpolymers, also bio-polymers, compatible, miscible or partially miscible with the cellulose acetate.
  • the plasticized cellulose acetate used as a layer adjacent to the layer of impregnated fabric may comprise a type and a quantity of plasticizer normally available from manufacturers of semi-finished materials in sheet (thickness 0.2-0.5 mm) or plate (thickness 1 - 10 mm).
  • plasticizer normally available from manufacturers of semi-finished materials in sheet (thickness 0.2-0.5 mm) or plate (thickness 1 - 10 mm).
  • these materials may be Mazzucchelli 1849 SpA: type OptiroidTM, LA / ES SpA: Type OptistyleTM 2000 (98-8688), or Mazzucchelli 1849 SpA M49TM-type bioplastic (For example, as the materials described in WO2012004727).
  • the amount of plasticizer is from 20 to 40%, more preferably from 30 to 40%, in weight / weight of the layer of plasticized cellulose acetate.
  • the thickness of the layer of plasticized cellulose acetate can be chosen in function of the mechanical properties and of the aesthetic requirements of the final multilayer material, for example, the thickness can be from 0.1 mm to 4 mm, preferably 0.5 mm.
  • the multilayer material of the invention can be obtained using thermo- compression and/or coupling, which provide the possibility of forming the alternating layers comprising, generally, a small number of high thickness layers for applications in the automotive sector or a small number of thin layers for the sector of textiles and clothing (waterproof, windproof, breathable technical fabrics etc.).
  • the multilayer material according to the invention obtained by thermo-compression, for example in press plates, can be of variable thickness, depending on the needs of subsequent machining, for example as high as 10 mm, comprising 13 layers of an impregnated denim fabric and 15 layers of cellulose acetate plastic (CAp).
  • CAp cellulose acetate plastic
  • the fabric may be impregnated with polymers other than cellulose acetate, for example with an emulsion or suspension polymers of the alkyl polyacrylates type, insoluble in water, or with a functionalized polyester (e.g., sulfonate) or with a polyether eurethane, or mixtures thereof.
  • polymers other than cellulose acetate for example with an emulsion or suspension polymers of the alkyl polyacrylates type, insoluble in water, or with a functionalized polyester (e.g., sulfonate) or with a polyether eurethane, or mixtures thereof.
  • the fabric may be impregnated with functionalized polyester in mixture with other substances, for example polyester sulfonate can be used in mixture with polyacrylic acid.
  • the fabric can be treated with a series of repeated impregnations and drying, preferably by impregnating it with a polymer of alkyl acrylate (Acr-T). These polymers are normally used in the technologies of finishing yarn and show good adhesion and compatibility with the fabric, in particular with cotton. Also in this embodiment, the amount of acrylic polymer that coats the fabric can be up to about 100% of the weight of the fabric. The subsequent stages of the preparation of the multilayer material are equal to those for the fabric impregnated with cellulose acetate.
  • the multilayer material according to the present invention is workable with all the mechanical cutting technologies, also automated, known to the person skilled in the art and normally used for the manufacture of spectacle frames from sheets of plasticized cellulose acetate alone.
  • the multilayer material according to the present invention shows an improved impact behaviour even at low temperatures with respect to the materials comprising only cellulose acetate normally used in eyeglasses frames of the prior art, particularly with a significant increase of notched IZOD resilience of ca. 500% both at +23°C and at -30/-20°C with typical morphology of the fracture surfaces of a tough material with incomplete rupture, without formation of sharp edges or surfaces.
  • the multilayer material of the invention can be prepared in various forms, including plates or sheets of different thicknesses.
  • the present invention relates to a plate comprising said multilayer material, which comprises at least one layer a) and at least one layer b), alternating and permanently adhering to each other, wherein a) and b) comprise: a) a fabric of natural fibres impregnated with a substance selected from a plasticized cellulose acetate polymer, a polymer or copolymer of at least one alkyl acrylate, a polyester or a functionalized polyethereurethane, or mixtures thereof, and
  • the multilayer material of the invention and the sheets/plates that comprise it can be used in eco-friendly manufacturing in various fields, e.g., as a non-limiting example, for furniture, household goods, cases for glasses, plates, thermoformed sheets to produce components for aesthetic finishing of internal and/or external surfaces in the automotive industry such as dashboards, inserts, etc.
  • the present invention relates to an artefact selected from a piece of furniture, a case for glasses, a component for automobiles or a vehicle comprising said multilayer material.
  • the present invention relates to an eyeglasses frame comprising said multilayer material.
  • the present invention relates to a process for the preparation of said multilayer material comprising the steps of:
  • step b) drying the impregnated fabric obtained in step a) completely or almost completely by removing the organic solvent or water;
  • step c) overlaying, in an alternating sequence, one layer of the impregnated and dried fabric obtained in step b) and a layer of cellulose acetate comprising at least a plasticizer, to obtain a semi-finished multilayer material; d) joining the layers of the semi-finished material of step c) to form a multilayer material by thermo-compression at 120 to 190°C, with a closure force from 1 to 10 tons for 1 to 20 min, wherein the temperature, pressure and time of treatment may vary according to the number of layers and the thickness of the material to be obtained, and
  • step a) of the method according to the invention a solution in acetone is used, if the polymer comprises cellulose acetate plasticized or a suspension, or an aqueous emulsion is used, if the polymer comprises an alkyl acrylate and/or a functionalized polyester and/or a polyether urethane.
  • the solution of cellulose acetate that is used to impregnate the fabric is obtained by dissolving plasticized cellulose acetate in the solvents normally used in the prior art, for example acetone, with concentrations varying according to the technique of impregnation, such as immersion and absorption, coating with or without pressure, brushing, spraying, etc. also using solutions containing plasticized cellulose acetate in 30% by weight / total weight of the solution, preferably in a concentration from 8 to 10% by weight / total weight of the solution, having a viscosity that suitable for the impregnation technique and penetration into the fabric and in the yarn.
  • the solvents normally used in the prior art for example acetone
  • concentrations varying according to the technique of impregnation such as immersion and absorption, coating with or without pressure, brushing, spraying, etc.
  • solutions containing plasticized cellulose acetate in 30% by weight / total weight of the solution preferably in a concentration from 8 to 10% by weight / total weight of the solution, having
  • the fabric is made of natural vegetable or animal fibres, in particular cotton, with various wefts and warps, in particular "denim", also with drawings, paintings etc. and with variable weight, for example from 150 to 1000 g / sqm.
  • indigo dyed with coloured indigo dye i.e. treated with a dispersion of indigo dye by addition of various substances, such as alkali, acid and other additives), deliberately chosen because extractable with water washing.
  • the plasticized cellulose acetate used in the examples contains diethyl phthalate as a plasticizer in amount of 20 to 38% by weight / total weight of the acetate and of the plasticizer.
  • Plasticized cellulose acetate used in the examples comprises (hereinafter: CAp) with standard synthetic diethyl phthalate plasticizers such as those available from Mazzucchelli 1849 SpA, or with plasticizers made from renewable resources and/or with biodegradable plasticizers, in the form of sheets or plates of the desired thickness, for example 0.2 - 4.0 mm, preferably 0.5 mm.
  • the fabric in continuous or discontinuous systems on sheets of the same size of the plate, is impregnated with a solution of CAp, preferably of the same type used for plasticized sheets or plates, in a solvent thereof, preferably acetone.
  • concentration of the solution of CAp may vary from 2% to 30% by weight / total weight of the solution, preferably 10% by weight in terms of its viscosity sufficient to penetrate into the fabric texture and impregnate the yarn.
  • the operation can be performed with various methods and equipment, such as for example: immersion and absorption, coating with or without pressure, brushing, spraying, etc.
  • the fabric may be impregnated with emulsion and/or aqueous suspensions of thermoplastic polymers compatible with CA, for example acrylic polymers or copolymers (alkyl acrylates), polyesters etc.
  • the drying can be performed with a variety of technologies known to those skilled in the art in controlled thermal environment, aspirated and suitable, according to the environmental regulations and safety, for the recovery and recycling of the organic solvent, for example acetone.
  • the amount of CAp (% by weight on the weight of the fabric) optimal for good adhesion in the multilayer may vary according to the type of fabric, for example from 1 to 200% by weight, preferably 50% by weight, if the amount of CA is not achieved with a cycle as described above, the above steps are repeated for the procedure cycles until it reaches the desired impregnation.
  • the impregnated fabric is more rigid than the non- impregnated one but it can be rolled without delamination of the polymer from the fabric. After drying, the impregnated fabric may contain a residual organic solvent in an amount less than the limits prescribed by the relevant regulations.
  • aqueous suspensions or emulsions of polymers compatible with CAp the procedure is similar to that already described for the CAp, with drying of the water up to a residual value of less than 0.1% by weight for example by drying at 60-70°C for 5-6 hours.
  • a variety of multilayer materials of fabric and CAp alternating sequence can be obtained with different possibilities of having both the outer layers of CAp, both of impregnated fabric or alternating.
  • Sheets of fabric treated and CAp equal to the measures of length and width of a flange-mold with variable thicknesses are cut out, for example, from 3 mm to 15 mm, preferably 6 mm.
  • the number of sheets is determined by the thickness of the sheets of the treated fabric and of those of CAp, so that the sum of the thicknesses of all sheets exceed 20-70% of the thickness of the flange-mold, preferably 40%, achieving a good ratio of compression in the next step. Molding by thermo-compression
  • the plate is detached from the mold and can be used as semi-finished product, in particular for the processing normally used for the manufacture of spectacle frames from plates of plasticized cellulose acetate polymer or for the production of objects, cases for glasses, aesthetic components for furniture or automotive also obtained for thermoforming.
  • Sample D Fabric Jacky Royal 8, impregnated as sample A, with a solution of cellulose acetate but with a concentration equal to 25% by weight / total weight of the solution in acetone;
  • sample E 7 layers of impregnated fabric Silverstone (sample E) alternating with 6 sheets of CA for the final plate thickness 6 mm;
  • the central sheet with a thickness of 2 mm is produced by LA-ES SpA type Optistyle 2000).
  • the sample is placed between the plates of an electrically heated hydraulic press, model P7 34E (Campana Sri; CVB Campana Ing Benedict) with dishes electrically heated to a temperature of 150-160°C and a maximum closure force of 2 tons is applied for 10 minutes, then the press plates are opened and the multilayer material are placed between air-cooled plates and under maximum closure force of 25 tons for 5 minutes. After cooling, multilayer plates are obtained with the following thicknesses:
  • the specimens are obtained by cutting in the shape and dimensions provided in the following physico- mechanical characterization.
  • Adhesion between the layer of impregnated or not-impregnated outer fabric and the sheet of CAp is evaluated by determining the force required for the separation according to the method ASTM D903 "Peeling Test" at 180°C, by dynamometer with the following criteria: from the apex is detached, with the use of any tool if needed, the fabric layer that adheres to the CA layer, the two flaps are locked in the terminals and the dynamometer crosshead is moved at a speed of 250 mm / min, recording the applied load, with cells from 10 KN. This determines the average load (N), which, divided by the width of the test, shows the peeling strength in N / mm.
  • the increase of adhesion strength (Fad) for the various samples can be expressed as the ratio between (Fad) sample / (Fad) of sample iii, which is taken as reference. This represents a remarkable advantage of the multilayer material of the invention, which shows a significant increase of adhesion strength between the layers compared to untreated materials.
  • the following example shows the physical-mechanical characteristics of the fabric / CAp multilayer plates compared to the slab of CAp such (4 mm thick) normally used (commercial material Optiroid - Mazzucchelli 1849 SpA).
  • sample vi. shows an improvement of the module at the different temperatures for sample vi., whereas sample L, with less rigidity, shows an important increase in the impact resistance, also detected by observations at the optical microscope of the fracture surfaces.
  • Sample i. does not show a complete rupture of the specimen, "hinge” effect, and no detachment is observed between the layers even at low temperatures (-20 °C).
  • Sample vi. shows a very high level of notched impact strength at low temperatures (-30°C), which allows to obtain manufactured articles, for example spectacle frames, which are not subject to brittle fracture with sharp, hence dangerous, edges.
  • the thermal properties (HDT) are substantially unchanged.
  • Multi-layer plates (size 80-180 mm. Thickness 6.5 mm) is prepared by thermo- compression in the manner described in Example 1) for sample F with: - Denim fabric, Jacky RoyalTM 8, impregnated (TCA) with 70% of its initial weight of plasticized cellulose acetate by application and drying of four coats of acetone solution with 8% w/w of plasticized cellulose acetate (OptiroidTM-Mazzucchelli 1849 SpA), 9 layers applied (TCA);
  • CAp Sheets of cellulose acetate plastic
  • OptiroidTM-Mazzucchelli SpA 8 layers (applied CAp);
  • the plates were mechanically processed (cut, milled, etc.). according to the usual mode of production of a spectacle frame, without ravellings or separation of the layers and with a very good and original surface appearance.
  • the multilayer sheets (semi-finished) obtained according to the present invention are suitable to produce eyeglasses frames or other items that are produced using similar technologies such as machining, thermoforming, gluing, etc.

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Ophthalmology & Optometry (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

La présente invention concerne un matériau multicouche comprenant des couches d'un polymère d'acétate de cellulose plastifié et d'un textile en fibres naturelles imprégné d'un polymère, le procédé de sa production, et un objet comprenant l'objet multicouche.
PCT/EP2013/060518 2012-05-23 2013-05-22 Matériau multicouche comprenant du textile WO2013174870A1 (fr)

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IT000895A ITMI20120895A1 (it) 2012-05-23 2012-05-23 Materiale multistrato comprendente un tessuto
ITMI2012A000895 2012-05-23

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Cited By (8)

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DE102013021686B3 (de) * 2013-12-19 2015-03-12 Langmatz Gmbh Verfahren zur Herstellung eines Brillengestells
EP2896987A1 (fr) 2014-01-17 2015-07-22 Marcolin S.P.A. Monture pour lunettes et procédé d'obtention associé
EP3045313A1 (fr) * 2015-01-19 2016-07-20 LA.ES. Laminati Estrusi Termoplastici Societa' per Azioni Procédé de production d'un matériau multicouche, en particulier pour lunettes, matériau multicouche pouvant être obtenu par un tel procédé
WO2017003352A1 (fr) * 2015-06-30 2017-01-05 Olsson-Sjöberg Lill Procédé de fabrication d'une pièce textile multicouche et pièce textile multicouche
IT201600097887A1 (it) * 2016-09-29 2018-03-29 Optimae Srl Montatura per occhiali in materiale polimerico termoplastico e relativo processo di produzione
US20180298181A1 (en) * 2015-04-29 2018-10-18 ElkaR&D S.r.l. Comprising methyl methacrylate for making optical device frames, in particular glass frames and glasses having frames made of such a material
WO2020016583A1 (fr) * 2018-07-19 2020-01-23 University Of Leeds Matériaux composites
US11485849B2 (en) 2021-03-04 2022-11-01 Balena Ltd. Composite biodegradable polymeric based material, a product and a method of making same

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GB2322099A (en) 1997-02-15 1998-08-19 Tenmat Ltd Wear-resistant laminated articles
EP0922567A2 (fr) 1997-12-12 1999-06-16 The Standard Oil Company Structures multicouches
EP0947313A1 (fr) 1998-04-03 1999-10-06 Borealis AG Produits laminés à caractère textile
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WO2011022031A1 (fr) 2009-08-19 2011-02-24 Milliken & Company Matériau composite multicouche
WO2011091878A1 (fr) 2010-02-01 2011-08-04 Benecke-Kaliko Ag Structure plane multicouche et son procédé de fabrication
WO2012004727A1 (fr) 2010-07-05 2012-01-12 Mazzucchelli 1849 S.P.A. Matière à base d'acétate de cellulose comprenant des plastifiants, et objet manufacturé produit à l'aide de cette matière

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Publication number Priority date Publication date Assignee Title
US2036424A (en) 1933-04-18 1936-04-07 Eastman Kodak Co Impregnation of cotton materials
US4061823A (en) 1975-12-11 1977-12-06 Westinghouse Electric Corporation Highly machinable cotton-phenolic base for decorative assemblies
WO1993011927A1 (fr) 1991-12-13 1993-06-24 Konrad Hornschuch Ag Panneau en matieres thermoplastiques pour l'habillage interieur de vehicules a moteur et son procede de fabrication
GB2322099A (en) 1997-02-15 1998-08-19 Tenmat Ltd Wear-resistant laminated articles
EP0922567A2 (fr) 1997-12-12 1999-06-16 The Standard Oil Company Structures multicouches
EP0947313A1 (fr) 1998-04-03 1999-10-06 Borealis AG Produits laminés à caractère textile
EP2083312A1 (fr) * 2008-01-24 2009-07-29 Klaus Stadlmann Cadre pour des lunettes optiques et son procédé de fabrication
US20100330333A1 (en) 2008-02-27 2010-12-30 Basf Se Multi-layer composite materials comprising a textile sheet material, production and corresponding method of use thereof
WO2010049743A1 (fr) 2008-04-07 2010-05-06 Guiseppe Giovanni Bogani Matériau multicouche
WO2010034911A1 (fr) * 2008-09-26 2010-04-01 Logo Branche de lunettes de type flexible et sans charniere
EP2177351A1 (fr) 2008-10-14 2010-04-21 Andrea Moretti Matériau textile multicouche
EP2199728A1 (fr) 2008-12-19 2010-06-23 TAG Composites & Carpets GmbH Matériau multicouche balistique
WO2011022031A1 (fr) 2009-08-19 2011-02-24 Milliken & Company Matériau composite multicouche
WO2011091878A1 (fr) 2010-02-01 2011-08-04 Benecke-Kaliko Ag Structure plane multicouche et son procédé de fabrication
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013021686B3 (de) * 2013-12-19 2015-03-12 Langmatz Gmbh Verfahren zur Herstellung eines Brillengestells
AT515224A1 (de) * 2013-12-19 2015-07-15 Langmatz Gmbh Verfahren zur Herstellung eines Brillengestells
EP2896987A1 (fr) 2014-01-17 2015-07-22 Marcolin S.P.A. Monture pour lunettes et procédé d'obtention associé
EP3045313A1 (fr) * 2015-01-19 2016-07-20 LA.ES. Laminati Estrusi Termoplastici Societa' per Azioni Procédé de production d'un matériau multicouche, en particulier pour lunettes, matériau multicouche pouvant être obtenu par un tel procédé
US20180298181A1 (en) * 2015-04-29 2018-10-18 ElkaR&D S.r.l. Comprising methyl methacrylate for making optical device frames, in particular glass frames and glasses having frames made of such a material
WO2017003352A1 (fr) * 2015-06-30 2017-01-05 Olsson-Sjöberg Lill Procédé de fabrication d'une pièce textile multicouche et pièce textile multicouche
IT201600097887A1 (it) * 2016-09-29 2018-03-29 Optimae Srl Montatura per occhiali in materiale polimerico termoplastico e relativo processo di produzione
WO2020016583A1 (fr) * 2018-07-19 2020-01-23 University Of Leeds Matériaux composites
JP2022503468A (ja) * 2018-07-19 2022-01-12 ユニヴァーシティ・オヴ・リーズ 複合材料
JP7335641B2 (ja) 2018-07-19 2023-08-30 ユニヴァーシティ・オヴ・リーズ 複合材料
US11485849B2 (en) 2021-03-04 2022-11-01 Balena Ltd. Composite biodegradable polymeric based material, a product and a method of making same

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